Characterization of supramolecular polymers

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14高分子科学导论Supramolecular polymersPPT课件

Driving Force for the Formation of Supramolecular Structures
Hydrophobic interaction
< 40 kJ/mol
Electrostatic interaction
- 20 kJ/mol
Hydrogen bond interaction
7
Hydrophobic interaction
Hydrophobic molecules tend to be non-polar and thus prefer other neutral molecules and non-polar solvents.
Hydrophobic molecules in water often cluster together forming micelles. Water on hydrophobic surfaces will exhibit a high contact angle.
Non-covalent forces that hold supramolecular polymers together include coordination, π-π interactions, and hydrogen bonding.
O
胸腺嘧啶 CH3 O
O P OH O
H2C O
腺嘌呤 H N H
12~30 kJ/mol
Van der Waals interaction
0.4-4 kJ/mol
Cation-π interaction
5-80 kJ/mol
π-π interaction
0-50 kJ/mol
Coordination interaction (Host-guest interaction)

苏忠民教授简历

苏忠民教授简历学院：化学学院姓名：苏忠民性别：男出生年月：1960年4月一、主要学习工作经历1978年9月—1983年7月，东北师大化学系本科学生1986年9月—1989年6月，东北师大化学系硕士研究生1994年9月—1997年6月，东北师大化学系博士研究生1998年4月—2000年4月，吉林大学理论化学研究所博士后1985年5月—1988年10月，东北师大化学系助教1988年10月—1992年12月，东北师大化学系讲师1992年12月—1994年9月，东北师大化学系物理化学专业副教授1994年9月—现在，东北师大化学系物理化学专业教授1998年10月—现在，东北师大化学系博士生指导教师2000年6月—现在，东北师大化学学院教授委员会教授1998年4月—现在，东北师大化学学院，功能材料化学研究所所长1999年1月—1999年10月，东北师大校长助理1999年10月—2003年12月，东北师大校长助理兼科技处处长2003年11月—现在，东北师大研究生院院长（副校级）2004年2月—现在，东北师范大学学位评定委员会副主席2006年3月—现在，东北师范大学自然科学学术委员会委员2007年3月—现在，东北师范大学自然科学学术委员会副主任2007年1月—现在，东北师范大学化学学院教育部长江学者特聘教授(无机化学专业)2008年1月—2010年12月，东北师范大学化学学院2007度教育部“长江学者和创新团队发展计划”创新团队负责人1995年11月—1997年11月，香港大学化学系访问学者2006年6月—现在，吉林省第六届化学会副理事长2006年11月—现在，中国化学会第二十七届理事会理事2006年11月—现在，第三届吉林省学位委员会委员2005年7月—现在，吉林省高校科研与学位管理学会，吉林省研究生教育与学位管理专业委员会理事长2005年7月—现在，香港大学内地校友联谊社第五届理事会理事2005年12月—2006年10月，长春市南关区第十五届人民代表大会代表2006年10月—现在，长春市南关区第十六届人民代表大会代表2008年1月—2012年12月，《科学通报》编辑委员会委员2009年1月—2014年12月，国务院学位委员会第六届学科评议组化学组成员2009年1月—2011年12月，长春市科学技术协会常委二、主要研究方向或领域(一) 功能材料化学的理论和实验研究1．有机分子/聚合物的导电性质研究(1) 合成表征聚并苯半导体导电材料并进行改性研究，其可作为电极材料用于制作二次电池和双电层电容器，性能指标达到国际先进水平，并曾小批量投放市场。

超分子化学Supramolecular Chemistry

参考书目
5. 超分子化学：概念与展望 (法)Jean-Marie Lehn著，北京大学化学科学译丛，北京大学出版社，北京，2002
（化学资料室） 6. 超分子化学：合成受体的分子识别与组装
刘育, 尤长城, 张衡益编著，南开大学出版社，天津，2001（化学资料室） 7. 超分子液晶晏华编著，科学出版社，北京，2000
参考书目
8. 超分子化学导论孙小强，孟启，阎海波编，中国石化出版社，北京，1997
9. Interfacial supramolecular assemblies Johannes G. Vos, Robert J. Forster, Tia E. Keyes，John Wiley & Sons, c2003.
超分子与普通分子的区别
不在于物种的大小，而在于是否能够把这个物种分裂为至少在原则上能独立存在的分子。
building blocks 以类似于原子结合形成分子的方式结合成超分子。
超分子化学是分子水平以上的化学（the chemistry beyond the molecule）
超分子化学与主客体化学
参考书目
1. 纳米超分子化学：从合成受体到功能组装体刘育[等]编著, 化学工业出版社, 北京，2004 （化学资料室）
2. 超分子层状结构：组装与功能沈家骢等著，科学出版社，北京，2004
3. 超分子化学研究中的物理方法童林荟, 申宝剑著，科学出版社，北京，2004
4. 生物超分子体系李惟等编著，化学工业出版社现代生物技术与医药科技出版中心，北京，2003
建议参考刊物
J. Supramol. Chem.（2001-2002） Supramol. Chem.（2002-） Supramol. Sci.（1994-1998） Inorg. Chem. Dalton Trans. Polyhedron Inorg. Chim. Acta J. Coord. Chem.

真核生物基因表达调控

酸性激活域 (D/E-rich) 谷氨酰胺(Q)富含域脯氨酸(P)富含域
蛋白质-蛋白质结合域（dimerization, co-factors）
1） TF最常见的DNA binding domain
Zinc Finger
bZIP
Homeodomain
bHLH
(1) 锌指(zinc finger)
2. The pri5’ capping 3’ formation / polyA splicing
3. Mature transcripts are transported to the cytoplasm for translation
Chromatin
epigenetic control
Protein degradation RNA silencing
一般而言的基因表达调控范畴
二、基因表达的时间性及空间性
（一）时间特异性
按功能需要，某一特定基因的表达严格按特定的时间顺序发生，称之为基因表达的时间特异性(temporal specificity)。
Cys-X2-4-Cys-X3-Phe-X5-Leu-X2-His-X3-His C-terminal: α-helix binding DNA
常结合GC box
(2) 碱性亮氨酸拉链 bZIP
(3) 碱性螺旋-环-螺旋bHLH
bHLH蛋白(basic Helix-Loop-Helix)
2） TF常见的trans-activation domain
– usually expressed at high level – the level of their gene expression may vary

补阳还五汤11种成分的药物动力学与谱动学关系研究

补阳还五汤11种成分的药物动力学与谱动学关系研究作者：贺琪珺周燕子肖美凤王敏存邓凯文贺福元陈新宇来源：《湖南中医药大学学报》2024年第05期〔摘要〕目的阐明中药复方药物动力学与谱动学总量统计矩的数学模型与参数关系，示范性地用补阳还五汤中11种成分进行药物动力学与谱动学研究，探讨其量-时关系，包括代谢时间和色谱保留时间关系。

方法采用HPLC/MS法测定补阳还五汤中黄芪甲苷等11种成分的药物浓度，并根据已建立的中药药物动力学与谱动学的总量统计矩数学模型，计算药物动力学与谱动学参数。

结果补阳还五汤中11种成分的药物动力学总量统计矩参数分别为AUCT为432.9 ng·h·mL-1，MRTT为2.185 h，VRTT为5.259 h2；CLT为82.95 mL·h-1；VT为139.9mL；95%的代谢时间区间为[0， 6.680] h。

谱动学的VUCT为457.5 ng·h·min·mL-1；MCRTT 为5.625 min；VCRTT为7.949 min2，95%的时间区间为[0.098 98， 11.15] min。

各取样点的谱动学总量零、一、二阶矩的RSD分别为86.09%、2.299%、7.587%，相似度基本上都在0.875以上。

结论中药药物动力学与谱动学总量统计矩法能表征多成分代谢的量-时关系，其中谱动学还能表征所测定代谢成分的构成比的变化和色谱学特征，可为临床合理用药奠定理论与实验研究基础。

〔关键词〕补阳还五汤；药物动力学；谱动学；总量统计矩；量-时关系〔中图分类号〕R284.1；R285.5 〔文献标志码〕A 〔文章编号〕doi：10.3969/j.issn.1674－070X.２０24.05.011Relationship between polypharmacokinetics and chromatopharmacokinetics of 11 components in Buyang Huanwu DecoctionHE Qijun1，3， ZHOU Yanzi2，3，4， XIAO Meifeng2，3，4，5，6， WANG Mincun2，3，4， DENG Kaiwen1，HE Fuyuan1，2，3，4，5，6*， CHEN Xinyui1*1. The First Hospital of Hunan University of Chinese Medicine， Changsha， Hunan 410007，China;2. School of Pharmacy， Hunan University of Chinese Medicine， Changsha， Hunan 410208， China;3. Hunan Key Laboratory of Druggability and Preparation for Chinese Medicine，Changsha， Hunan 410208， China;4. Engineering Technology Laboratory of Processing and Preparation for Chinese Medicine， Hunan University of Chinese Medicine， Changsha， Hunan 410208;5. Laboratory of Supramolecular Mechanism and Mathematic-Physics Characterization of Chinese Medicine， Hunan University of Chinese Medicine， Changsha， Hunan 410208， China;6. Key Laboratory of Property and Efficacy of Chinese Medicinal， National Administration of Chinese Medicine， Changsha， Hunan 410208， China〔Ａｂｓｔｒａｃｔ〕 Objective To elucidate the mathematical model and parameter relationship of the total statistical moment between polypharmacokinetics and chromatopharmacokinetics of the Chinese medicine compound formulas， to demonstrate the polypharmacokinetics and chromatopharmacokinetics study of 11 components in Buyang Huanwu Decoction （BYHWD）， and to explore their dose-time relationship， including the metabolic time and chromatographic retention time. Methods HPLC/MS was used to determine the concentrations of 11 components such as astragaloside IV in BYHWD， and the polypharmacokinetic and chromatopharmacokinetic parameters were calculated based on the established total statistical moment mathematical model of Chinese medicine. Results The total moment parameters of polypharmacokinetics of AUCT， MRTT， VRTT， CLT， and VT of the 11 components inBYHWD were 432.9 ng·h·mL-1， 2.185 h， 5.259 h2， 82.59 mL·h-1， and 139.9 mL respectively， and the 95% metabolic time interval was from 0 to 6.680 h. The total moment parameters of chromatopharmacokinetics of VUCT， MCRTT， and VCRTT were 457.5 ng·h·min·mL-1， 5.625 min， and 7.949 min2 respectively， with a 95% time interval from 0.098 98 to 11.15 min. The RSD of the total zero， first， and second moments of chromatopharmacokinetics at each sampling time-point were 86.09%， 2.299%， and 7.587% respectively， with the similarity basically above 0.875. Conclusion The total statistical moment method of polypharmacokinetics and chromatopharmacokinetics of Chinese medicine can represent the dose-time relationship of multi-component metabolism. Among them， the chromatopharmacokinetics can also represent the compositional changes and chromatographic characteristics of the measured metabolic components， laying a theoretical and experimental research foundation for clinical rational medication.〔Ｋｅｙｗｏｒｄｓ〕 Buyang Huanwu Decoction; polypharmacokinetics; chromatopharmacokinetics; total statistical moment; dose-time relationship中药复方作用量-时-效关系的阐明是进行中药复杂作用机制研究的基础性关键科学问题。

全球材料类SCI收录期刊影响因子排名投稿必备

全球材料类SCI收录期刊影响因子排名期刊英文名中文名影响因子Nature自然Science科学Nature Material自然（材料）Nature Nanotechnology自然（纳米技术）Progress in Materials Science材料科学进展Nature Physics自然（物理）Progress in Polymer Science聚合物科学进展Surface Science Reports表面科学报告Materials Science & Engineering R-reports材料科学与工程报告Angewandte Chemie-International Edition应用化学国际版Nano Letters纳米快报Advanced Materials先进材料Journal of the American Chemical Society美国化学会志Annual Review of Materials Research材料研究年度评论Physical Review Letters物理评论快报Advanced Functional Materials先进功能材料Advances in Polymer Science聚合物科学发展Biomaterials生物材料Small微观？Progress in Surface Science表面科学进展Chemical Communications化学通信MRS Bulletin材料研究学会（美国）公告Chemistry of Materials材料化学Advances in Catalysis先进催化Journal of Materials Chemistry材料化学杂志Carbon碳Crystal Growth & Design晶体生长与设计Electrochemistry Communications电化学通讯The Journal of Physical Chemistry B物理化学杂志，B辑：材料、表面、界面与生物物理Inorganic Chemistry有机化学Langmuir朗缪尔Physical Chemistry Chemical Physics物理化学International Journal of Plasticity塑性国际杂志Acta 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Materials & Structures智能材料与结构Solid State Sciences固体科学Polymer Testing聚合物测试Nanoscale Research Letters纳米研究快报Surface Science表面科学Optical Materials光学材料International Journal of Thermal Sciences热科学Thermochimica Acta热化学学报Journal of Biomaterials Applications生物材料应用杂志Journal of Thermal Analysis andJournal of Solid State Electrochemistry固体电化学杂志Journal of the European Ceramic Society欧洲陶瓷学会杂志Materials Science and Engineering B-Solid State Materials for Advanced Tech材料科学与工程B—先进技术用固体材料Applied Surface Science应用表面科学European Physical Journal B欧洲物理杂志Solid State Communications固体物理通信International Journal of Fatigue疲劳国际杂志Computational Materials Science计算材料科学Cement and Concrete Research水泥与混凝土研究Philosophical Magazine Letters哲学杂志（包括材料）Current Applied Physics当代应用物理Journal of Alloys and Compounds合金和化合物杂志Wear磨损Journal of Materials Science-Materials in Medicine材料科学杂志—医用材料Advanced Engineering Materials先进工程材料Journal of Nuclear Materials核材料杂志International Journal of Applied Ceramic Technology应用陶瓷技术Chemical Vapor 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Theoretical Nanoscience计算与理论纳米科学IEEE TRANSACTIONS ON ADVANCED PACKAGINGIEEE高级封装会刊Materials Characterization材料表征International Journal of Refractory Metals & Hard Materials耐火金属和硬质材料国际杂志Physica Status solidi A-Applied Research固态物理A——应用研究PHASE TRANSITIONS相变Journal of Thermal Spray Technology热喷涂技术杂志International Journal of Nanotechnology纳米工程Journal of Materials Science材料科学杂志Journal of Vacuum Science & Technology A-VACUUM Surfaces and Films真空科学与技术A 真空表面和薄膜PHYSICA STATUS SOLIDI B-BASIC RESEARCH固态物理B—基础研究MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING半导体加工的材料科学International Journal of Fracture断裂学报Journal of Materials Processing Technology材料加工技术杂志Metals and Materials International国际金属及材料IEEE TRANSACTIONS ON MAGNETICSIEEE磁学会刊Vacuum真空Journal of Applied Electrochemistry应用电化学Materials & Design材料与设计JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS固体物理与化学杂志Journal of Experimental Nanoscience实验纳米科学POLYMER COMPOSITES聚合物复合材料Journal of Materials Science-Materials in Electronics材料科学杂志—电子材料Journal of Composite Materials复合材料杂志Journal of the Ceramic Society of Japan日本陶瓷学会杂志JOURNAL OF ELECTROCERAMICS电子陶瓷杂志ADVANCES IN POLYMER TECHNOLOGY聚合物技术发展IEEE TRANSACTIONS ON COMPONENTS AND PACKAGING TECHNOLOGIESIEEE元件及封装技术会刊Journal of Porous Materials多孔材料IEEE TRANSACTIONS ON SEMICONDUCTOR MANUFACTURINGIEEE半导体制造会刊CONSTRUCTION AND BUILDING MATERIALS结构与建筑材料Journal of Engineering Materials and Technology-Transactions of The ASME工程材料与技术杂志—美国机械工程师学会会刊FATIGUE & FRACTURE OF ENGINEERING MATERIALS & STRUCTURES工程材料与结构的疲劳与断裂IEEE TRANSACTIONS ON APPLIED SUPERCONDUCTIVITYIEEE应用超导性会刊ACI STRUCTURAL JOURNAL美国混凝土学会结构杂志Materials Science and Technology材料科学与技术Materials and Structures材料与结构Reviews on Advanced Materials Science先进材料科学评论International Journal of Thermophysics热物理学国际杂志JOURNAL OF ADHESION SCIENCE AND TECHNOLOGY粘着科学与技术杂志Journal of Materials Science & Technology材料科学与技术杂志High Performance Polymers高性能聚合物BULLETIN OF MATERIALS SCIENCE材料科学公告Mechanics of Advanced Materials and Structures先进材料结构和力学PHYSICA B物理EUROPEAN PHYSICAL 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B现代物理国际杂志MATERIALS RESEARCH INNOVATIONS材料研究创新GLASS TECHNOLOGY -PART A玻璃技术JOURNAL OF MATERIALS IN CIVIL ENGINEERING土木工程材料杂志NEW DIAMOND AND FRONTIER CARBON TECHNOLOGY新型金刚石和前沿碳技术SCIENCE IN CHINA SERIES E-TECHNOLOGICAL SCIENCES中国科学E技术科学ATOMIZATION AND SPRAYS雾化和喷涂SYNTHESE合成HIGH TEMPERATURE高温Journal of Phase Equilibria and Diffusion相平衡与扩散INORGANIC MATERIALS无机材料MECHANICS OF COMPOSITE MATERIALS复合材料力学BIO-MEDICAL MATERIALS AND ENGINEERING生物医用材料与工程PHYSICS AND CHEMISTRY OF GLASSES玻璃物理与化学JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATERIALS SCIENCE EDITION武汉理工大学学报-材料科学版ADVANCED COMPOSITE MATERIALS先进复合材料Journal of Materials Engineering and Performance材料工程与性能杂志Solid State Technology固体物理技术FERROELECTRICS LETTERS SECTION铁电材料快报JOURNAL OF POLYMER MATERIALS聚合物材料杂志JOURNAL OF INORGANIC MATERIALS无机材料杂志GLASS SCIENCE AND TECHNOLOGY-GLASTECHNISCHE BERICHTE玻璃科学与技术POLYMERS & POLYMER COMPOSITES聚合物与聚合物复合材料Surface Engineering表面工程RARE METALS稀有金属HIGH TEMPERATURE MATERIAL PROCESSES高温材料加工JOURNAL OF TESTING AND EVALUATION测试及评价杂志AMERICAN CERAMIC SOCIETY BULLETIN美国陶瓷学会公告MATERIALS AT HIGH TEMPERATURES高温材料MAGAZINE OF CONCRETE RESEARCH混凝土研究杂志SURFACE REVIEW AND LETTERS表面评论与快报Journal of Ceramic Processing Research陶瓷处理研究JSME INTERNATIONAL JOURNAL SERIES A-SOLID MECHANICS AND MATERIAL ENGINEERIN日本机械工程学会国际杂志系列A－固体力学与材料工程MATERIALS TECHNOLOGY材料技术ADVANCED COMPOSITES LETTERS先进复合材料快报HIGH TEMPERATURE MATERIALS AND PROCESSES高温材料和加工INTEGRATED FERROELECTRICS集成铁电材料MATERIALS SCIENCE材料科学MATERIALS EVALUATION材料评价POWDER METALLURGY AND METAL CERAMICS粉末冶金及金属陶瓷RARE METAL MATERIALS AND ENGINEERING稀有金属材料与工程INTERNATIONAL JOURNAL OF MATERIALS & PRODUCT TECHNOLOGY材料与生产技术国际杂志METAL SCIENCE AND HEAT TREATMENT金属科学及热处理JOURNAL OF ADVANCED MATERIALS先进材料杂志ADVANCED MATERIALS & PROCESSES先进材料及工艺MATERIALS WORLD材料世界SCIENCE AND ENGINEERING OF COMPOSITE MATERIALS复合材料科学与工程MATERIALS PERFORMANCE材料性能。

Isothermal Titration Calorimetry of Supramolecular

* To whom correspondence should be addressed. E-mail: bouteil@ ccr.jussieu.fr.
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介孔材料(Mesoporous material).doc

介孔材料（Mesoporous material）classificationAccording to the classification of chemical composition, mesoporous materials can generally be divided into two major categories: silicon and non silicon.1. silicon based mesoporous materials have narrow pore size distribution, regular pore structure and mature technology. Silicon materials are available for catalysis, separation and purification, drug encapsulation, slow release, gas sensing and other fields. Silicon based materials can be divided into two groups according to pure silicon and other elements. The classification can be carried out according to the kinds of doped elements and the number of different elements. Heteroatom doping can be regarded as heteroatom instead of silicon atoms, introducing different heteroatoms will bring many new properties to the material, such as stability, changes of hydrophilic hydrophobic properties and the change of catalytic activity change and so on.2. non silicon mesoporous materials mainly include transition metal oxides, phosphates and sulfides. Because of their existence of variable valence states, it is possible to open new application fields for mesoporous materials and demonstrate the potential applications of silicon-based mesoporous materials. For example: aluminum phosphate molecular sieve P materials have been replaced by Si after the formation of silicon aluminium phosphate(silicon-aluminophosphate, SAPOs), aluminum phosphate introduced two valent metal in the architecture(metal-substituted AIPOs MAPOs) has been widely used in adsorption, catalyst, acid catalysis, oxidation catalysts (such as methanol Olefination of hydrocarbons oxidation) etc.. Activated carbon with large surface area and high pore volume has become the main industrial adsorbent because of its high adsorption capacity and the adsorption of different types of compounds from the gas and liquid. In addition, the charge storage capacity of the double layer capacitor material made of mesoporous carbon is higher than that of the metal oxide particle, and the capacitance is much higher than that of the commercial metal oxide double layer capacitor. Titania based mesoporous materials have many advantages such as high photocatalytic activity and high catalytic capacity. Many studies have been done on their structure, properties and characterization.synthetic methodIn general, mesoporous molecular sieves are inorganic materials that constitute the framework of the molecular sieve. In the solvent phase, a series of ordered porous materials are formed by supramolecular self-assembly under the action of surfactant templates. The most commonly used synthetic methods are hydrothermal synthesis, and others have been reported, such as room temperature synthesis, microwave synthesis, wet gum calcination, phase inversion, and synthesis in nonaqueous systems. The main theoretical basis for the selection of inorganic species is sol-gel chemistry, that is, the rate of hydrolysis and condensation of raw materials is equal, and the degree of polycondensation is improved by hydrothermal process. According to the skeleton composition of the target mesoporousmaterial, the inorganic species can be directly added inorganic salts, or organic metal oxides which can produce inorganic oligomers after hydrolysis, such as Si (OEt) 4, Al (i-OPr) 3, etc..Used for surface active synthesis of mesoporous molecular sieve material agent has many kinds, but according to the different electrical properties of hydrophilic groups, can be broadly divided into the following four categories: anionic, polar gene negatively charged; the cationic, with positive polarity genes; the non ionic, polar groups not charged; the amphoteric, with two hydrophilic groups, a positive and a negative charge, such as three CAPB (ethylene methyl amine in vinegar end is four yuan, the positively charged amine and the other end is negatively charged carboxyl) etc.. The interfacial force between the polar head of the surfactant and the inorganic species is one of the common points in the formation of mesoporous molecular sieves in different synthetic systems. Various synthetic routes can by changing the type of phase interface forces (such as electrostatic interaction, hydrogen bonding or coordination effect) or variable size (such as charge density modulation can adjust a two-phase micellar surface electrostatic attraction size; adjusting reaction temperature can be adjusted to achieve the size of the hydrogen bond force). Different inorganic species and surfactants can form specific synthetic systems under different assembly conditions and assemble into mesoporous molecular sieves with different structures, morphologies and pore sizes.Several important research stagesThe synthesis of mesoporous materials began in 1990, and Yanagisawa and other layered silicate materials Kanemite and long chain Wan Jisan amines (ATMA) were mixed under alkaline conditions,Three dimensional mesoporous silica materials with narrow pore size distribution were obtained by ion exchange. It was the earliest discovered mesoporous silica material, but it did not attract the attention of scientists at that time because of its unsatisfactory structure. Until 1992, Mobil's Kresge and Beck reported the successful use of cationic surfactant, synthesis of the new M41S series of silicon oxide with adjustable pore size in the range of 1.5-l0nm as template (aluminum) based ordered mesoporous materials, for the study of ordered mesoporous materials sounded the horn ring.Contains a series of cage mesoporous materials synthesized by Stucky in 1994, compared with the synthesis of M41S mesoporous materials, he is using the surface active agent double chain structure under acidic conditions at room temperature or short time low temperature synthesis.In 1995, chemical modification of mesoporous materials occurred successively, Es1. The chemical modification of mesoporous materials includes the doping of the backbone and the modification and functionalization of the pore surface. The doping of the framework mainly refers to the introduction of Al3+, Ti4 +, B3 + and other atoms in the framework of pure silicon mesoporous materials to give them the acid, alkali center or catalytic activity point. Functionalization of mesoporous pore surfaces is the most widespread and effectivemethod for preparing mesoporous host guest composite materials. For example, for modification can improve the hydrothermal stability of the materials by using hydrophobic substances, improve the adsorption performance of gas; modified catalyst performance developed for specific chemical reactions using with catalytic materials; mesoporous materials modified by thiol and thioether groups of Hg 2 + Pb 20 the adsorption of heavy metal ions such as sichuan.The successful synthesis of ordered mesoporous thin films was first reported by Brinker et al in 1997. The use of acid alcohol solution as reaction medium and evaporation inducedself-assembly (EISA) synthesis of high quality silicon oxide mesoporous films can process, which opened up broad prospects for the application of mesoporous materials in the field of membrane separation and catalysis, microelectronics, sensors and photoelectric devices etc..It was first reported in 1998 by Zhao non-ionic SBA-15 mesoporous materials with large aperture synthesis of three block copolymers, due to its large pore wall thickness (5-30nm) and (3.1-6.4nm) the thermal and hydrothermal stability has been significantly improved, so as to broaden the scope of application of mesoporous materials. At present, the research reports based on SBA-15 mesoporous materials are the most widely used in the field of mesoporous materials.In 1999, Ryoo successfully replicated other mesoporous materials with mesoporous materials as hard templates. He has to MCM-48, SBA-1, SBA-15 as template to replicate the CMK-1, CMK-2, CMK-3 mesoporous carbon molecular sieve materials, andprovides a feasible route and then the successful synthesis of precious metals, metal oxides, sulfides and other non silica based mesoporous materials.In 2003, Zhao et al proposed a "acid base" concept, using a pair of inorganic precursors of acid-base pairing to synthesize a series of non porous mesoporous materials in non-aqueous systems by self regulating acidity. This method has solved the problem of finding the precursor of metal sol to a certain extent and is a general method for synthesizing porous materials with multiple oxides.In 2004, Che reported the use of anionic chiral surfactants as templates to synthesize chiral mesoporous materials with helical channels. This mesoporous material with unique pore structure is expected to play a role in chiral molecular recognition, separation and catalysis.applicationChemical and chemical fieldsOrdered mesoporous materials have large specific surface area, relatively large pore size and regular pore structure, and can handle larger molecules or groups. They are very good shape selective catalysts. The ordered mesoporous materials show better catalytic activity than zeolite molecular sieves, especially in the reactions catalyzed by bulky molecules. Therefore, the use of ordered mesoporous materials opens up a new world for catalytic cracking of heavy oil and residuum. When ordered mesoporous materials are directly used as acid-basecatalysts, the carbon content of the solid acid catalyst can be improved, and the diffusion rate of the product can be improved. The conversion rate can reach 90%, and the selectivity of the product is up to 100%. In addition to direct acid catalysis,Graft materials can also be prepared by mixing transition elements in the framework of ordered mesoporous materials with redox power, rare earth elements, or supported redox catalysts. The graft material has higher catalytic activity and shape selectivity, which is the most active field for the development of mesoporous molecular sieve catalysts at present.Ordered mesoporous materials can also be used in the field of polymer synthesis, especially polymerization reactors, because of their large pore size. Because the hole reduces the chance of polymerization termination to a certain extent, prolong the life of free radicals, and molecular ordered mesoporous materials synthesized by weight distribution of the polymer was better than the corresponding condition of the free radical polymerization of narrow, by changing the molecular monomer and initiator amount can control the quantity of polymer. In addition, the active center can be typed or introduced into the framework of the polymerization reactor to accelerate the reaction process and increase the yield.In the environmental control and protection, it is used to degrade organic waste, and is used for water purification and the conversion treatment of automobile exhaust. In the field of high technology and advanced materials for energy storage materials for the assembly of functional nano object inmesoporous materials, such as assembly of guest molecules, luminescence properties for the light emitting assembly, photochemical active substances, allowed to use the advantages of mesoporous materials with large surface area of the prepared mesoporous structure of optical materials than conventional optical more excellent materials, such as the Chinese Academy of Sciences Shanghai Institute of ceramics Shi pan Jianlin with mesoporous composite film ultrafast nonlinear optics corresponding group preparation. The optical applications of mesoporous materials, Stucky, G, D and so on, have been discussed in 2000. In the uniform pore through the polymer mediated polymerization, then chemically removed pore, can form conductive polymer materials with regular mesoporous structure, the use of structured mesoporous materials as pore micro reactor and its carrier function to synthesize heterogeneous nanoparticles or quantum wire composite assembly system has a special advantage. The small size effect and quantum effect due to limited pore size and regular action, has observed this kind of composites can exhibit optical properties and electric and magnetic special, such as modified mesoporous zirconia materials after the show special room temperature photoluminescence. These can be used for the research and development of mesoporous and composite materials in optical devices, micro sensors and other fields.Ordered mesoporous materials are the branches of porous materials, and their rapid development also comes from the practical application of industrial (such as petroleum, chemical, fine chemical). At the same time, we should also see that the ordered mesoporous materials, the pore size in the range of 2~50nm, which provides a "reaction vessel" for thepreparation of new nano materials and nano composite materials, or "tools". In 1992 M41S, the rapid development of nano science and technology coincided with the period during which they prepared many new materials nanometer size, nano structure, such as the typical study of carbon nanotubes. I think, on the other hand, in the late twentieth Century, the development of nanotechnology led to the development of ordered mesoporous materials.Biomedical fieldIn general, biological macromolecules such as proteins, enzymes, nucleic acids and so on, when their molecular mass of about 1~100, between the size of less than 10nm, the relative molecular mass of about 10 million of the virus, its size is about 30nm. The pore size of ordered mesoporous materials can be adjusted continuously in the range of 2 - 50nm and has no physiological toxicity, which makes it suitable for the immobilization and separation of enzymes and proteins. It is found that ordered mesoporous materials such as glucose and maltose can successfully solidify the enzyme and inhibit the leakage of enzymes, and the enzyme immobilization method can keep the enzyme activity very well.The appearance of biochip is a very important progress in the field of high and new technology in recent years. It is a new technology that combines physics, microelectronics and molecular biology. The advent of ordered mesoporous materials has led to a breakthrough in this technique, and the formation of successive, firmly bound membrane materials on different ordered mesoporous material substrates,These membranes can be directly separated from cell /DNA for use in building microchip labs.Direct encapsulation and controlled release of drugs are also good applications of ordered mesoporous materials. With ordered mesoporous materials, large specific surface area and pore volume, pore in the material can be set on porphyrin, pyridine, or immobilized protein and other biological drugs, through the modification of controlled-release drugs, improve the efficacy of persistence. Biological targeting can effectively and accurately hit targets, such as cancer cells and lesions, and give full play to the efficacy of drugs.Environment and energyThe application of ordered mesoporous materials as photocatalyst for the treatment of environmental pollutants is one of the focuses in recent years. For example, the mesoporous TiO2 ratio of nano TiO2 (P25) has a higher photocatalytic activity, because mesoporous structure with high surface area in contact with organic molecules increased, increasing the surface adsorbed water and hydroxyl reaction, hole water and hydroxyl with the catalyst surface excitation produces hydroxyl radical, and hydroxyl radical is the strong oxidant degradation of organic matter, can put a lot of refractory organic matter oxidation to CO2 and inorganic water etc.. In addition, selective doping in ordered mesoporous materials can improve the photocatalytic activity and increase the efficiency of photocatalytic degradation of organic wastes.Chlorine disinfection process is currently widely used in domestic water while killing all bacteria, but also produce chloroform and carbon tetrachloride and chloroacetic acid and a series of toxic organic compounds, the serious "three letter" effect (carcinogenic, teratogenic, mutagenic) has caused widespread concern in the international science and medicine. The school received gamma 3-chloropropyltriethoxysilane in the inner wall of mesoporous materials, obtained mesoporous molecular sieve CPS function of HMS, the functional mesoporous molecular sieve to remove the effect of trace chloroform water significantly, the removal rate is up to 97%. The concentration of chloroform in the treated water is lower than that of the national standard, even lower than the standard of drinking water.Ordered mesoporous materials also have unique applications in the field of separation and adsorption. In the range of 20% - 80%, ordered mesoporous materials have the characteristics of rapid desorption, and the range of controlling humidity can be controlled by the size of pore size. Compared with traditional microporous adsorbents, ordered mesoporous materials have higher adsorption capacity for argon, nitrogen, volatile hydrocarbons and low concentration heavy metal ions. Ordered mesoporous materials do not require special adsorbent activation devices to recover heavy metals such as lead and mercury in various volatile organic pollutants and waste liquids. Moreover, ordered mesoporous materials can be rapidly desorbed and reused so that they have good environmental and economic benefits.Ordered mesoporous materials with large pore, the pore can bein situ produced carbon or Pd storage material, increase the energy storage material tractability and surface area, so that energy is released slowly to transfer storage effect.At present, many research institutes and institutions, including Beijing University of Chemical Technology, Fudan University, Jilin University, Chinese Academy of Sciences and so on, have been engaged in the research and development of ordered mesoporous materials. It can be believed that with the further development of the research work, ordered mesoporous materials, such as zeolite molecular sieves, are widely used as an ordinary porous material in industry。

supramolecular chemistry 分区

Supramolecular ChemistrySupramolecular chemistry is a branch of chemistry that focuses on the study of non-covalent interactions and the formation of complex molecular structures. It involves the design, synthesis, and characterization of molecules that can self-assemble into larger functional units through non-covalent interactions.IntroductionSupramolecular chemistry arose in the mid-20th century as a result of pioneering work by researchers such as Jean-Marie Lehn, Donald Cram, and Charles J. Pedersen, who were awarded the Nobel Prize in Chemistry in 1987. These scientists explored the concept of self-assembly, where smaller molecules can spontaneously organize into larger structures through weak intermolecular forces such as hydrogen bonding,electrostatic interactions, hydrophobic interactions, and van der Waals forces.Non-Covalent InteractionsAt the heart of supramolecular chemistry are the various non-covalent interactions that govern the assembly of molecular structures. These interactions are reversible and relatively weak compared to covalent bonds, allowing for dynamic and adaptable systems to be formed. Some key non-covalent interactions include:1.Hydrogen bonding: It occurs when a hydrogen atom is attracted toan electronegative atom such as oxygen, nitrogen, or fluorine.Hydrogen bonding is important for the stabilization ofsupramolecular structures.2.Electrostatic interactions: These interactions occur betweenoppositely charged species, such as cations and anions. They playa crucial role in the formation of ionic complexes andcoordination compounds.3.Van der Waals forces: These forces include London dispersionforces, which arise from temporary fluctuations in electrondensity and induce polarity in neighboring molecules. Van derWaals forces also include dipole-dipole interactions and dipole-induced dipole interactions.4.π-π interactions: These interactions occur between the π-electron clouds of aromatic rings, leading to stackingarrangements and the formation of π-conjugated systems.Self-Assembly and Supramolecular StructuresSupramolecular chemistry utilizes the principles of self-assembly to create larger structures from smaller molecular building blocks. Theself-assembly process can be controlled by carefully designing the molecular components and their interactions. This allows for the construction of a wide range of supramolecular structures, including:1.Host-guest complexes: These structures involve the encapsulationof a smaller molecule (guest) within a larger molecule or cavity(host). Examples include cyclodextrin inclusion complexes andcrown ether complexes.2.Supramolecular polymers: These polymers are formed through theself-assembly of smaller monomer units held together by non-covalent interactions.3.Coordination complexes: These complexes are formed through thecoordination of metal ions with ligands. The metal-ligandinteractions can result in the formation of intricatesupramolecular architectures.4.Supramolecular aggregates: These are larger structures formedthrough the assembly of multiple smaller molecules. Examplesinclude micelles, vesicles, and liquid crystals.Applications of Supramolecular ChemistrySupramolecular chemistry finds applications in various fields, including materials science, drug delivery, sensing, catalysis, and molecular recognition. Some notable applications include:1.Drug delivery systems: Supramolecular complexes can be used toencapsulate and transport drugs to specific target sites withinthe body, improving their efficacy and reducing side effects.2.Sensors: Supramolecular systems can be designed to detect specificanalytes, such as ions, small molecules, or biomolecules. Thesesensors can provide a sensitive and selective means of detectingand quantifying substances.3.Catalysis: Supramolecular catalysts can be used to enhance theefficiency and selectivity of chemical reactions. The controlledenvironment provided by supramolecular assemblies can lead toimproved catalytic properties.4.Molecular machines: Supramolecular chemistry has enabled thedevelopment of molecular machines, which are synthetic molecularsystems capable of performing mechanical tasks at the nanoscale.These machines hold promise for applications in nanotechnology and molecular electronics.ConclusionSupramolecular chemistry offers a versatile and exciting approach to the design and synthesis of complex molecular systems. By harnessing the power of non-covalent interactions, researchers can create functional structures with unique properties and applications. As our understanding of supramolecular chemistry continues to grow, so too will its impact on various scientific disciplines.。

小角X射线散射原理与应用

小角X射线散射原理与应用小角X射线散射原理与应用庄文昌指导老师陈晓课程主要内容小角X射线散射基础理论小角X射线散射研究的几种常见体系小角X射线散射系统简介小角X射线散射基础理论 20世纪初伦琴发现了比可见光波长小的辐射由于对该射线性质一无所知伦琴将其命名为X 射线 X-ray 到20世纪30年代人们以固态纤维和胶态粉末为研究物质发现了小角度X射线散射现象当X射线照射到试样上时如果试样内部存在纳米尺度的电子密度不均匀区则会在入射光束周围的小角度范围内一般2 6o出现散射X 射线这种现象称为X射线小角散射或小角X射线散射Small Angle X-ray Scattering简写为SAXS 其物理实质在于散射体和周围介质的电子云密度的差异 SAXS已成为研究亚微米级固态或液态结构的有力工具 SAX与WAX的区别为什么是电子云密度分布两个电子对X射线的散射散射强度 SAXS用于数埃至数百埃尺度的电子密度不均匀区的定性和定量分析系统的电子密度起伏△决定其小角散射的强弱相关函数 r 决定着散射强度的分布小角X射线散射研究的几种常见体系胶体分散体系溶胶凝胶表面活性剂缔合结构生物大分子蛋白质核酸聚合物溶液结晶取向聚合物工业纤维薄膜嵌段聚合物溶致液晶液晶态生物膜囊泡脂质体小角X射线散射研究的几种常见粒子体系 Sketch maps of the typical colloid particle systems in SAXS research respectively for monodisperse and polydisperse particle systems and their complementary systems 粒子及其互补体系的SAXS分析定性分析 1 体系电子密度的均匀性不均匀才有散射 2 散射体的分散性单分散或多分散由Guinier图判定 3 两相界面是否明锐对Porod或Debye定理的负偏离 4 每一相内电子密度的均匀性对Porod或Debye定理的正偏离 5 散射体的自相似性是否有分形特征定量分析散射体尺寸分布平均尺度回转半径相关距离平均壁厚散射体体积分数比表面平均界面层厚度分形维数等Guinier Law Solution SAX-Scattering of Ag nanoparticlesX-ray power 2kW CuKα exposure-time 1000 s Distance Distribution Function P r 尼龙 11 Porod principle Porod定理如曲线①即在散射矢量h较大值区域曲线走向趋于平行横坐标轴曲线②表示正偏离这是由于体系中除散射体外还存在电子密度不均匀区或者热密度起伏曲线③表示负偏离这是由于两相间界面模糊存在弥散的过渡层过渡层的厚度E为为界面厚度参数比表面 Porod定理主要提示了散射强度随散射角度变化的渐近行为它可用于判断散射体系的理想与否以及计算不变量Q和比表面SP等结构参数 Fractal Systems SURFACE FRACTALS Different DS PHYSICAL METHODS FOR LIPOPROTEIN Characterisation of the LDL - DOT drug complexes with SAXS The peak imum at large distances for native LDL was r 202±04 nm which corresponds to the electron density autocorrelation of the phospholipid headgroups and protein moiety Broadening of imum peak for LDL control without significant difference in r value indicate formation of LDL aggregates during incubation Increase in r value Dr 13±06 nm and broadening of peak imum for LDL-DOT indicate slightly increase in the imum particle diameter and formation of LDL aggregates Characterisation of the LDL-MOT drug complexes with SAXS No significant differences have been observed in r value of peak imum for native reconstituted LDL as also for LDL-MOT complex with 50 molecules of drug per LDL particle Incorporation of MOT have no significant effect on particle diameter and core lipid arrangement 聚合物SAXS曲线不均一体系SAXS散射强度实验曲线是凹面曲线如右图 a 在稠密体系中考虑粒子间相互干涉对散射的影响实验曲线产生极大部分如右图 b 和 c 有长周期结构存在的纤维其小角散射强度曲线常属于此类型一维电子密度相关函数 SDCF 可求得过渡层厚度 dtr 平均片层厚度 d 长周期 L 以及比内表面积等常见溶致液晶种类 lyotropic liquid crystal respectively for lamellar Hexagonal and Cubic phase lyotropic lamellar liquid crystal lyotropic Hexagonal liquid crystal lyotropic Cubic liquid crystal 小角X射线散射系统 SAXS 准直系统针孔准直系统四狭缝准直系统 Kratky U 准直系统锥形准直系统 Bruker SAXS 仪 Rigaku SAXS仪 Philips SAXS仪同步辐射SAXS仪 HMBG小角X射线散射系统简介 HMBG－SAX 小角X－射线散射系统 Philips公司SAXS系统主要由准直系统试样架样品台真空泵循环水泵X射线发生器氩甲烷保护气位敏检测器及其控制系统等部分组成X射线发生器中采用Cu靶作为发射源 X射线波长1542最高功率可达4Kw真空泵可迅速抽真空至1 mbar样品台分为三种块状固体样品台粉末或粘稠液体样品台毛细管样品台SAXS是一种非破坏性的分析方法在实验过程中具有许多优点适用样品范围宽干湿态样品都适用与透射电子显微镜 TEM 比较几乎不需特殊样品制备能表征TEM无法测量的样品对弱序液晶性结构取向和位置相关性有较灵敏的检测可以直接测量体相材料有较好的粒子统计平均性Scheme of the HECUS-MBraun SWAXS- System Data Collection and transaction 3D-VIEW PS Calculation of the Radius of gyration of Lysozyme ASA p00 3D view PS 大型仪器介绍课程不同仪器可能探测的物质结构尺寸范围 Bragg equation Small Large Large d Small d Small – Angle Supramolecular Envelope Wide - Angle – AtomicMolecular Lattice SAX WAX X-rays 带电粒子电场强度E 带电粒子所受作用力F Eq ma a Eqm 带电粒子的散射强度正比于带电粒子的加速度对一个原子而言 o p 如左图所示入射方向与散射方向夹角为2θ散射矢量散射强度散射矢量电子云密度起伏 X射线辐照体积相关函数散射体间距 q 1R Guinier 范围 Scattering curve Radius of GyrationR Measure of particle size Rg 355 Background-subtracted raw-dataGuinier-Plot q -1 Intensity counts log I q q2 ①②③ h2 I h h3 Schematic description for Porod principle and its deviationsCharacterization of Fractal System For surface fractalwhere 3 4It holds that Ds＝6 - ln h ln[I h h-1] Slope - For mass fractal wh。

糖基配合物的结构与配位模式

糖基配合物的结构与配位模式谢步云;杨娉娉;戈根武;杨瑞卿;谢永荣【摘要】本文探讨了五类糖基配合物的结构与配位模式,对糖基配合物的设计与合成有重要的指导意义.【期刊名称】《赣南师范学院学报》【年(卷),期】2010(031)003【总页数】4页(P79-82)【关键词】糖;配合物;结构;配位模式【作者】谢步云;杨娉娉;戈根武;杨瑞卿;谢永荣【作者单位】赣南师范学院,化学与生命科学学院,江西,赣州,341000;赣南师范学院,化学与生命科学学院,江西,赣州,341000;赣南师范学院,化学与生命科学学院,江西,赣州,341000;赣南师范学院,化学与生命科学学院,江西,赣州,341000;赣南师范学院,化学与生命科学学院,江西,赣州,341000【正文语种】中文【中图分类】O641.4糖是生物圈中最丰富且可再生的资源，是植物将太阳能转化为化学能的典型物质.在配位化学中糖是很宝贵的廉价手性配体，由于糖分子复杂的构型、构象变化和分子内部及分子之间较强的氢键作用，致使糖类配合物的合成比较困难，相关研究报道较少.然而糖类配合物金属中心之间通过电子传递的相互作用以及它们与桥基、端基配体的相互协调和影响，呈现出多种奇特的化学活性和生物活性.因此对其配位化学的研究有利于药学、材料学和生命科学的发展.例如：在许多参与代谢过程的糖酶和糖蛋白中, 含有糖桥联的Mg2+、Mn2+、Co2+、Zn2+和Ca2+等各种金属离子配位结构，它们在生物体中起着信息传递、能量转移及物质传输等作用，它们在环保、毒理学及应用医学等方面具有潜在的应用价值[1-2]；同时糖及苷配合物或包合物可作为有机反应催化剂、药物缓释剂、外消旋体拆分剂等[3-6]具有重要的研究价值.通过对近几年来糖基配合物研究的文献调研，总结出五类糖基配合物的结构与配位模式，对新糖基配合物的设计与合成有重要的指导意义.1 中性糖配合物自然界的单糖双糖等中性糖可以单独与金属，例如：碱土金属和过渡金属等，形成配合物，也可以和其它配体一起与金属形成混配物.2000年P. Rao [7]等合成了稀土Pr (III)、Nd(III)等金属与一些单糖及二糖的配合物，并用热力学、FT-IR、CD、CV、NMR等分析手段对其进行了结构表征.其中图1显示了D-葡萄糖、D-核糖和D-麦芽糖与稀土金属形成配合物的配位模式.在这三种配合物中，其中(a)和(b)中的金属离子与3个单糖相连，单糖的三个相邻羟基与金属离子配位，(c)中金属与2个二糖相连，也是相邻的羟基与金属离子配位，它们的配位数都为9. (a)M-D-葡萄糖 (b)Pr-D-核糖 (c)M-D-麦芽糖图1 单、双糖金属配合物的配位模式吴光瑾等[8-10]合成了一系列金属与不同糖的配合物.其中α-D-吡喃核糖与氯化钕反应，形成的糖配合物的配位模式见图2，可知钕离子与核糖上相邻的三个醇羟基配位，其中2个是a键上的羟基和1个是e键上的羟基.而链状糖与锶的配位是通过同侧相邻的两个羟基氧与锶离子配位(见图3) [11-12].图2 NdCl3·C5H10O5·5H2O的配位模式图3 Sr(NO3)2·C6H14O6配位模式Peter Klüfers[13]等则以乙二胺为混配体，在Pd : D-glucose摩尔比为3:1的水溶液中得到了分子式为[(en)2Pd2-(α-D-Glcp1,2,3,4H-4)]·7H2O的晶体，分子结构见图4所示，可见每个糖分子提供四个羟基氧原子与两个钯金属原子发生配位，其中是相邻两个羟基氧原子与一个金属钯原子配位.C.A.Bunton等[14]报导了以蔗糖(sucrose)和1,10-邻菲啰啉(phenanthroline)为混配体与CoCl3反应，得到了D-[Co(III)(phen)2(sucrose)]3+的配合物，其结构见图5所示，蔗糖分子中的两个环分别提供一个羟基与同一个钴离子配位，Co(III)离子的配位数为6，形成了扭曲的八面体配位环境.图4 [(en)2Pd2-(α-D-Glcp)]·7H2O的配位模式图5 D-[Co(III)(phen)2(sucrose)]3+的配位模式2 糖酸配合物中性糖分子中的醛基氧化成羧基后形成相应的糖酸，糖酸较中性糖有更强的配位能力，可以和大多数金属离子配位.2002年M. Saladini等[15]合成了半乳糖酸(GalaH2)与Co(Ⅱ)、Ni(Ⅱ)、Cd(Ⅱ)、Hg(Ⅱ)等离子的配合物，其中图6展示了半乳糖酸与金属Cd(Ⅱ)的配位模式，可见Cd(Ⅱ)离子与半乳糖酸相邻的2个羟基和羧基上的羟基以及3个水分子一起形成了6配位的、扭曲的八面体配位环境. M. Kato等[16]合成了一系列糖酸与铜离子的配合物.其中α-D-葡萄糖-1-磷酸酯与铜离子配位，形成了四核铜配合物阳离子(见图7).由图7可见：每个配阳离子含有两个葡萄糖酸分子单元，每个葡萄糖酸分子通过羧酸上去质子化羟基和相邻的醇羟基与金属配位，磷酸酯基团起到桥联两个分子单元的作用.金属之间不发生直接的作用，四个铜原子的空间构型随着葡萄糖构象的改变而改变.图6[Cd(Gala)·3H2O]的分子结构图7含葡萄糖酸的铜配阳离子结构3 氨基糖配合物中性糖的羟基被氨基取代后形成氨基糖，氨基具有较强的配位能力.2001年K. Hegetschweiler等[17-19]合成了一些1,3,5-脱氧-三-(二甲基氨基)-cis-肌糖(tdci)及其衍生物与金属的配合物，在tdci的结构中三个羟基和三个二甲基氨基交错排列在六元环上，具备了很强的与金属形成配位的能力，并且配位形式多样化.图8显示了配合物[Gd3(H-3tdci)2(H2O)6]3+的配位模式，两个Taci分子将三个Gd(III)金属离子夹在中间形成了1个新奇的三核夹心型笼状结构.图8 [Gd3(H-3tdci)2(H2O)6]3+的三核夹心型笼状结构图9[Ni(HL)]C12·2H2O的配位模式江涛等[20]合成了镍金属配合物[Ni(HL)]C12·2H2O (HL=1-[(2-氨乙基)氨基]2-氨基-1,-二脱氧-葡萄糖)(见图9).图10展示了Ni(Ⅱ)与2个配体HL分子中的6个氮原子配位，形成了1个6配位的畸形八面体，且催化试验表明：该配合物对硝基苯吡啶甲酸酯(PNPP)的水解具有一定的催化活性.图10 D-葡萄糖胺Schiff碱金属配合物图11 [Ni(HsalNO2Glc)(tptz)]+配阳离子的结构单元4 氨基糖Schiff碱配合物氨基糖与不同醛缩合形成各种schiff碱，schiff碱再与各种金属反应形成氨基糖Schiff碱配合物.Matsuhiro等[21]合成了D-葡萄糖胺与水杨醛或β-萘酚醛反应得到的Schiff碱的Ni(Ⅱ)配合物(见图10).图10展示了Ni(Ⅱ)中心离子分别与来自2个Schiff碱分子的亚胺N和酚羟基O原子配位，形成了四面体配位模式.W. Plass[22,23]等合成了2-脱氧-2-(5-硝基-亚水杨氨基)-α-D-葡萄糖苷(H2salNO2Glc)和2,4,6-三-(2-吡啶)-1,3,5-三嗪(tptz) 在乙腈水混合溶剂中得到的分子式为[Ni(HsalNO2Glc)(tptz)]ClO4·0.375CH3CN·0.75H2O的配合物(见图11)，图11显示了中心配离子[Ni(HsalNO2Glc)(tptz)]+结构单元，中心镍离子展示了扭曲的八面体配位环境.5 壳聚糖配合物图12 壳聚糖-钯配合物的配位模式壳聚糖(CS)在糖元的2位为-NHCOCH3或游离的-NH2，3位为仲-OH，6位为伯-OH.壳聚糖对过渡金属以及稀土金属甚至碱土金属离子均有良好的配位能力.可应用于生物学、医药工业、催化、纳米微晶生长诱导、金属的回收与检测以及农业等方面[24]，因此，对其开发利用研究受到广泛重视.T. Skrydstrup[25]等研究了铂系金属与壳聚糖的作用，并且提出了一种铂系金属与氨基壳聚糖的配位模式(见图12)，可见，中心钯离子与两条壳聚糖链上的氨基配位，形成交联结构.刘蒲等[26]以壳聚糖为载体，合成了壳聚糖钯(0)配合物，并研究了其催化碘代苯与丙烯酸Heck芳基化反应，结果表明：该催化剂具有较高的催化活性和立体选择性，可高转化率、高产率地合成反式苯丙烯酸.6 小结6.1 糖及其衍生物能与二价或三价主族金属、过渡金属和稀土金属形成不同稳定性的配合物.6.2 糖分子的配位能力较弱,通常可采用:a)碱使糖的一个或多个羟基发生去质子化形成氧负离子；b)将糖分子中的羟基转化为配位能力较强的其它官能团(如氨基、羧羧基或巯基等)；c)将带有易配位官能团的化合物与糖分子偶联；d)一些易配位的中性分子与糖分子一起混配等来提高糖分子的配位能力.6.3 X-射线衍射单晶结构分析可知：a)吡喃和呋喃糖与金属配位时，采取环上一个、二个或三个相邻羟基同时与一个金属配位的模式；b)双糖中两个环可以分别提供一个羟基与同一金属配位；c)链状糖易采取两个相邻羟基同时与一个金属配位的模式；b)糖酸采用羧基上的羟基和相邻醇羟基与同一个金属配位.【相关文献】[1] Predki F., Whitfield M., Sarkar B., Characterization and cellular distribution of acidic peptide and oligosaccharide metal-binding compounds from kidneys. [J].Biochem. J. 1992，281：835-841.[2] Singh P.R., Jones S.G., et al. New Modes of Action of Desferrioxamine Scavenging of Semiquinone Radical and Stimulation of Hydrolysis of Tetrachlorohydroquinone [J].Chem. Biol. 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The crystal structure and FT-IR study of PrCl-α-D-ribopyranose·5H2O.[J].Carbohydr. Res.2001,334:91-95.[9] Su Y, Yang L, Wu J ,et al. Complex of trivalent lanthanum ion with galactitol in the solid state: the crystal structure and an FT-IR study of LaC13·galactitol·6H20. [J]. J. Mole. Structr. 2002, 616: 221-230.[10] Yang L, Xu Y, Wu J, et al. Complexation oftrivalent lanthanide cations by erythritol in the solid state. The crystal structure and FT-IR study of2EuCl3·2C4H10O4·7H20.[J].Carbohydr.Res. 2004, 339:1679-1687.[11] Yang L, Su Y, Wu J, et al. Interactions between Metal Ions and Carbohydrates. Coordination Behavior of Neutral Erythritol to Ca(II) and Lanthanide Ions[J].InorgChem.2003,42:5844-5856.[12] Su Y, Yang L, Wu J, et al. Interaction between Metal Nitrates and Carbohydrates: The Topology Coordination Behavior of Galactitol with Trivalent Lanthanide and Divalent Alkaline Earth Ions[J].Inorg Chem.2007,46:5508-5517.[13] Peter Klüfers,Thomas Kunte. A Transition Metal Complex of D-Glucose.[J]. Angew. Chem. Int. Ed. 2001, 40(22):4210-4212 .[14] Parada J., Bunton C. A.,et al. Sucrose bis(1,10-phenanthroline) cobalt(III) comparisonof semi-empirical and ab initio geometrical optimizations.[J].Pol, 2005,24 :1002-1006.[15] Saladini M., Ferrari E., Menabue L.. Coordination of transition metal ions by galactaric acid: a potentiometric and spectroscopic study[J]. J. Inorg Bio. 2002,92:121-127.[16] Kato M., Kumar Sah A., Tanase T.. Tetranuclear Copper(II) Complexes Bridged by α-D-Glucose-1-Phosphate and Incorporation of Sugar Acids through the Cu4 Core Structural Changes[J]. Inorg. Chem. 2006, 45: 6646-6660.[17] Gajda T., Du1pre Y., Hegetschweiler K. et al. Highly Efficient Phosphodiester Hydrolysis Promoted by a Dinuclear Copper(II) Complex[J]. Inorg. Chem. 2001, 40:4918-4927.[18] Morgenstern B., Sander J., Hegetschweiler K. ,et al. Complexation of a Heptanuclear Polyox- otantalate Anion with K+: Formation of a Supramolecular [K6-(μ-OH2)6-(OH2)8]6+ Ring Structure [J]. Inorg. Chem. 2001, 40:5307-5310.[19] Sanna D. , Hegetschweiler K., Nagy L. ,et al. Complex Formation of Vanadium(IV) with 1,3,5 -Triamino-1,3,5-trideoxy-cis-inositol and Related Ligands[J]. Inorg. Chem. 2004, 43:3116-3126.[20] 张炜,江涛,等.Ni(Ⅱ)-糖胺金属配合物的合成、晶体结构及催化PNPP水解的活性研究[J].化学学报,2005,63:555-558.[21] Costamagna J, L illo L E, Matsuhiro B. Ni (Ⅱ) complexes with Schiff bases derived from amino sugars[J]. Carbohydr Res, 2003, 338: 1535-1542.[22] Burkhardt A., Plass W.. Modeling the coordination chemistry of chitosan: Synthesis and characterization of a nickel(II) complex with a 2-aminoglucose Schiff-base ligand[J]. Inor.Chem Comm,2008,11:303-306.[23] Burkhardt A, Gorls H, Plass W. Nickel(II) complexes with Schiff-base ligands derived from epimeric pyranose backbones as 2,3-chelators: modeling the coordination chemistry of chitosan[J]. Carbohydr. 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The physical characterization of supermacroporous

Materials Science and Engineering A464 (2007) 93–100The physical characterization of supermacroporous poly(N-isopropylacrylamide)cryogel:Mechanical strengthand swelling/de-swelling kineticsAkshay Srivastava,Era Jain,Ashok Kumar∗Department of Biological Sciences and Bioengineering,Indian Institute of Technology,Kanpur208016,IndiaReceived29September2006;received in revised form19January2007;accepted15March2007AbstractPoly(N-isopropylacrylamide)[poly(NiPAAm)]and poly(acrylamide)[poly(AAm)]cryogels were synthesized by radical polymerization at −12◦C for12h using monomers of N-isopropylacrylamide(NiPAAm)and acrylamide(AAm)with N,N-methylene bisacrylamide(MBAAm)as cross-linking agent,respectively.The cryogels synthesized in freezing conditions provided spongy,elastic and supermacroporous character as compared to the hydrogels synthesized at ambient temperatures.Our earlier observations revealed that the elastic deformation of cryogels either by external forces(mechanical deformation)or internal forces(shrinkage-swelling of poly(NiPAAm)cryogels)led to detachment of afﬁnity bound bioparticles to these gels,which promises great potential in understanding cell interactions on elastic matrices[M.B.Dainiak,A.Kumar,I.Y. Galaev,B.Mattiasson,Proc.Natl.Acad.Sci.U.S.A.103(2006)849–854].The deformation characteristic of cryogels as measured by Young’s modulus indicates that the modulus of elasticity of poly(NiPAAm)cryogel(33–65kPa)is comparatively lower than the Young’s modulus for poly(AAm)cryogel(42–86kPa).The Young’s modulus of both the cryogels was found to be dependent on monomer concentration in cryogels and increases with the increase in concentration.Thus,poly(AAm)cryogel are mechanically more rigid than poly(NiPAAm)cryogel.Further,the swelling/de-swelling kinetics study on poly(NiPAAm)cryogel and hydrogel showed,higher swelling ratios for cryogels in the range of13–16as compared to poly(NiPAAm)hydrogels which were in the range of7–10.However,the extent of de-swelling is more in the case of poly(NiPAAm) hydrogels.© 2007 Elsevier B.V. All rights reserved.Keywords:Thermo-responsive cryogels;Swelling/de-swelling;Young’s modulus;Cryogel elasticity;Mechanical strength of gels1.IntroductionPolymeric gel is physically or chemically cross-linked net-work of polymer chains,within which low molecular weight liquid is immobilized and the amount of solvent present within the network is much higher than the amount of polymer con-stituting the network.Speciﬁcally,the xerogels which swell in aqueous medium are called as‘hydrogels’.Based on the response to the surrounding medium conditions,hydrogels can be categorized into two classes:(a)conventional hydrogels(b) stimuli-responsive hydrogels.The stimuli-responsive hydrogels demonstrates sensitivity towards various external stimuli such as pH,temperature,light,ions,electricﬁeld,etc.In such class of polymeric gels,the pH and temperature responsive gels have ∗Corresponding author.Tel.:+915122594051;fax:+915122594010.E-mail address:ashokkum@iitk.ac.in(A.Kumar).shown great potential in various biotechnological applications [1].The poly(N-isopropylacrylamide)[poly(NiPAAm)]is a well known reversibly thermo-responsive polymer which exhibits a lower critical solution temperature(LCST)in an aqueous solution generally at32◦C[2].The swelling and de-swelling behavior of poly(NiPAAm)hydrogels is due to the change in temperature that causes changes in theﬁne balance between the elastic force of chains and the interaction between water and hydrophilic chains[3].This volume transition from swollen to shrunken state of poly(NiPAAm)hydrogels occurs around 34◦C[4].However,such critical temperatures depend on vari-ous factors,including molecular weight and chain tacticity for linear polymers,and on the degree of cross-linking and type of cross-linking agent for poly(NiPAAm)hydrogels.Another category of gels,so called‘cryogels’,are the gels that are formed in moderately frozen media[5–7].Cryogels are polymeric gel matrices that are formed as a result of cryogenic polymerization of low or high molecular weight precursors.The0921-5093/$–see front matter© 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2007.03.05794 A.Srivastava et al./Materials Science and Engineering A 464 (2007) 93–100cryogels have a continuous system of interconnected macrop-ores.The pore size in cryogels is quite large and pore sizes up to 200␮m have been obtained in spongy cryogels[8].Due to pres-ence of such supermacroporus structure these gels exhibit very lowﬂow resistance and allow unhindered diffusion of solutes of practically any size.The‘supermacroporous cryogels’synthe-sized from poly(acrylamide)or any other gel forming polymers or polymeric precursors have recently been used for various applications in biotechnology[8].Poly(acrylamide)cryogels have been used successfully in the area of bioseparation[9] speciﬁcally for direct recovery of products from fermentation media[10],separation of lymphocytes[11],and also human tumor cells[12],capture of enzyme from crude homogenate [13]and chromatography of microbial cells by afﬁnity and ion-exchange columns[14].Also cryogels have demonstrated their potential in cell[15]and enzyme[16]immobilization,and tissue engineering applications[17].In one of our recent co-works[18]it was shown that elastic deformation of cryogel can be utilized in physical desorption of afﬁnity bound bioparticles—the phenomenon of particle detach-ment upon elastic deformation was shown to be of a generic nature,because it was applicable for a variety of bioparticles of different sizes and nature.This detachment was believed to be caused when either external force like mechanical force or internal forces within the gel caused deformation of the gel and thus the detachment of the particles by multivalent interactions [18].Using poly(NiPAAm)cryogel the shrinkage and swelling of thermosensitive,macroporous hydrogel upon an increase and decrease of the temperature resulted in the deformation of the gel utilizing internal forces[18].The aim of the present study was to optimize the synthesis of cryogel matrix based on poly(NiPAAm)and to characterize the physical properties of the poly(NiPAAm)cryogel.The physical properties,such as porosity,mechanical strength and swelling kinetics of poly(NiPAAm)cryogel were studied and compared with the corresponding hydrogel.Here,we have studied the basic property of poly(NiPAAm),i.e.,temperature responsive-ness in the form of a cryogel.Also the mechanical strength of poly(NiPAAm)and poly(AAm)cryogel were studied and compared.These studies were done to characterize cryogel deformation through internal force like shrinkage of cryogel upon increase in temperature and by external force like mechan-ical pressure.2.Experimental2.1.MaterialsN-isopropylacrylamide(NiPAAm)was purchased from Acr`o s Organics(New Jersey,USA.).Acrylamide(AAm) was purchased from Merck(India).N,N -Methylene-bis (acryalamide)(MBAAm),ammonium persulphate(APS), N,N,N ,N -tetramethylethylenediamine(TEMED)were bought from Sisco Research Laboratories(Mumbai,India).Ethylene diamine tetraacetic acid(EDTA)was purchased from S.D.Fine Chemicals Ltd.(Boisar,India.)All other chemicals used were of analytical grade.2.2.Methods2.2.1.Preparation of NiPAAm hydrogelsThe cross-linked poly(NiPAAm)hydrogels of6,7and8% total monomer concentration were prepared by mixing5,5.84 and6.67g of NiPAAm and1,1.17and1.33g MBAAm,respec-tively,in degassed deionized water to a total volume of100ml. The mixture was again degassed and TEMED(95␮l)and APS (110mg)were then added into the reaction mixture.The reac-tion mixture was then poured into2.5ml syringe and kept at room temperature.2.2.2.Preparation of poly(NiPAAm)cryogel(cryogenic polymerization of NiPAAm)The poly(NiPAAm)cryogels were synthesized by mixing5g (6%),5.84g(7%)and6.67g(8%)of NiPAAm monomer and 1g(6%),1.17g(7%)and1.33g(8%)of MBAAm in degassed deionized water and the mixture was again degassed and kept in ice for30min.TEMED(95␮l)and APS(110mg)were then added and mixed thoroughly.The mixture was then poured into 5and2.5ml syringes and was immediately frozen at−12◦C and incubated at this temperature for12h.After thawing,the gels were immediately washed with distilled water and were vacuum dried and stored at room temperature.Cryogels were synthe-sized by varying monomer concentration of6,7and8%.At each concentration the cross-linking agent ratio was also varied. These were further used for mechanical strength determination and swelling/de-swelling studies.2.2.3.Swelling and de-swelling measurementThe kinetics of swelling was carried out following con-ventional gravimetric procedure[19,20].Brieﬂy,it involved measurement of water uptake by samples placed in deion-ized water,kept in a thermostated water bath at20◦C.The poly(NiPAAm)hydrogels and cryogels of6,7and8%were dried at60◦C for3days and then kept in vacuum desiccate till further use.The dried cryogels were swollen at20◦C in deion-ized water and removed from swelling medium at regular time intervals.The excess water on surface was whipped off byﬁl-ter paper and the weight of all the gels was taken after regular time intervals until the equilibrium was reached.The samples (hydrogels and cryogels)were of2cm in length and1cm in diameter.At least four samples with similar dimension of each concentration of the gel were used for the study.The water uptake capacity(W u)(%)is given by:W u=100×(M t−M g)M ewhere W u is the water uptake capacity,M t the weight at regular time interval,M g the weight of the xerogel,and M e is the weight of water in swollen hydrogels or cryogels at swelling equilibrium at a particular temperature.The weight-swelling ratio(q w)can also be calculated as:q w=weight of swollen gel(M s)weight of xerogel(M g)A.Srivastava et al./Materials Science and Engineering A 464 (2007) 93–10095Similarly the de-swelling kinetics of hydrogels and cryogelswere also performed by the gravimetric method at a constanttemperature of40◦C maintained in a thermostated water bath.The swollen hydrogels equilibrated at20◦C were transferred towater bath maintained at40◦C and weight of all the swollengels were taken before it was transferred to40◦C.After regulartime intervals the gels were removed and water was whipped offfrom the surface byﬁlter paper.The weight changes of the gelswere recorded during the course of de-swelling at regular timeintervals.The percentage of water retention(W r)is given by:W r=100×M t−M g M ewhere M t is the weight at regular time interval,M g the weight of the xerogel,and M e is the weight of water in hydrogels or cryogel at de-swelling equilibrium at a particular temperature.Poly(NiPAAM)cryogels with varying cross-linking agent concentration ratios were further selected to study swelling/de-swelling kinetics by above-mentioned procedure to determine the effect of cross-linking agent on swelling/de-swelling kinetics of the cryogels.The physical change in dimension of cryogels was also deter-mined by increasing and decreasing the temperatures above and below LCST of poly(NiPAAm).Initial diameter of the cryogel was determined at room temperature that is at25◦C and then the cryogels were placed in water bath at40◦C for a deﬁnite time. The decrease in diameter of the cryogel(T)was determined as follows:T=D25◦−D40◦where D25◦is diameter of gel at25◦C and D40◦is diameter at 40◦C.The(T)value,i.e.,decrease in diameter of gels caused due to shrinkage of gels as a result of increase in temperature also deter-mines the thermoresponse of the gels.The greater the change in diameter(T)by increasing the temperature,better the thermore-sponse of the gel.2.2.4.Mechanical strengthThe compression test on poly(NiPAAm)cryogel and poly(AAm)cryogel was performed using uniaxial compression test.The samples were tested by mechanical tester(NI DAQ card USB6009with labview software and load cell from Eltek), where the samples were placed between two arms of load frame and then compressed up to80%of the total length,from where the compressed cryogel can regain its original shape on addition of liquid.The applied force was recorded and change in column length due to compression was measured.The compression modulus of cryogel monolith was estimated using the equation:E=F/Al/l kPawhere E is the elastic modulus,F the applied force,A the cross-sectional area of the test sample,l the initial length of the test sample and l is the change in length under the compressive force.2.2.5.Measurement ofﬂow resistance of cryogel columnTheﬂow resistance of the cryogel columns(5ml)evaluated atﬂow rates of1–5ml/min was determined using peristaltic pump,registering theﬂow rate at given pump settings.In a separateexperiment,the pump settings were calibrated againstﬂow ratewith no column connected according to Adrados et al.[21]. 2.2.6.Scanning electron microscopic(SEM)analysisPoly(NiPAAm)cryogel and hydrogels of different concen-trations were subjected to SEM analysis.All the samples wereethanol dried[12].The samples were put consecutively inincreasing concentration of ethanol that is20%(v/v),40%(v/v),60%(v/v),80%(v/v)andﬁnally in100%(v/v)ethanol.The sam-ples were then vacuum dried overnight before gold coating.TheSEM pictures were taken using FEI Quanta200and the porediameters of cryogel column were measured arbitrarily.3.Results and discussion3.1.Synthesis and optimization of poly(NiPAAm)cryogelThe process of poly(NiPAAm)cryogel formation is same asthat for polyacrylamide cryogels.The poly(NiPAAm)cryogelmatrices were synthesized by co-polymerization of monomersof NiPAAm and MBAAm as cross-linking agent.The monomerswere mixed under chilled conditions and the polymerization wasallowed to proceed at sub-zero temperature until completion.The poly(NiPAAm)cryogel columns were made at−12◦C.The gels were formed completely only after12h.The condi-tions employed to make the poly(NiPAAm)cryogel ensuredminimum competition between the factors facilitating gelationand factor decelerating it(low temperature,high viscosity inunfrozen liquid microphase).A temperature regime lower than −12◦C will cause the formation of smaller and numerous sol-vent crystals and hence smaller pore sizes.This has been wellestablished from earlier works published on poly(AAm)cryogel,which deﬁnes the optimum range of temperature to lie between −10and−15◦C for formation of supermacroporous structure [5].The synthesis of poly(NiPAAm)cryogel involves cryotropicgelation and polymerization of(NiPAAm)via free radical poly-merization.The principle and mechanism of cryogelation isdiscussed elsewhere[9].The different concentration range ofpoly(NiPAAm)cryogel with varying weight ratio(w/w)ofNiPAAm to MBAAm from5:1to20:1were synthesized inorder to optimize and determine the effect of cross-linking onswelling-shrinkage behavior of poly(NiPAAm)cryogels.Thecryogel were selected such that they have large contractionresponse to temperature and a goodﬂow rate.Hence,the ther-mal shrinkage andﬂow rate of all the synthesized gels weredetermined and compared.The comparative study of thermalshrinkage,morphology andﬂow rates of poly(NiPAAm)cryo-gel made at different ratio of NiPAAm to MBAAm are shownin Table1and visually can be seen in Fig.1.From the physicalobservation of the gels it was shown that as the concentra-tion of the monomer increases from6to8%,the cryogelbecomes more rigid and less spongy.This may be due to forma-96 A.Srivastava et al./Materials Science and Engineering A 464 (2007) 93–100Table 1Physical properties of poly(NiPAAm)cryogels Total monomer concentration (%)Ratio a Flow rate (ml/min)Shrinkage at 40◦C (mm)Physical characteristic 65:121Less spongy 10:1 1.42Spongy 15:1 1.34Spongy 20:1 1.15Very spongy 75:1 4.71Less spongy 10:142Spongy 15:1 3.22Spongy 20:1 2.55Very spongy 85:1 1.81Less spongy 10:1 1.31Spongy 15:1 1.22Spongy 20:113Very spongyaConcentration of NiPAAm/concentration of MBAAm.tion of thicker walls.The thermal shrinkage of cryogel varies within each concentration and increases as the concentration of cross-linking agent decreases.This is shown by the fact that 6and 7%poly(NiPAAm)cryogel shows thermal shrink-age in the range of 1–5mm in diameter for the ratio of 5:1–20:1(NiPAAm:MBAAm)but 8%cryogel at 20:1ratio showed less shrinkage up to 3mm in diameter due to thicker walls of cryogel.The 7%cryogel shows better morphology and ﬂow rate in the range of 2.5–4.7ml/min than 6and 8%cryogel.Fig.1demon-strates the shrinkage of poly(NiPAAm)cryogel in response to increase in temperature above its LCST.On the other hand,the control gel (hydrogel)was allowed to polymerize at room temperature and it has been found that control gel polymerized within 1–2h as compared to poly(NiPAAM)cryogels which need approximately 12h or above to polymerize at −12◦C.The hydrogel adopted transpar-ent,glassy and rigid morphology and all the solvent was bound within polymer network.Contrarily,poly(NiPAAm)cryogels having exactly the same chemical composition had heterophasic non-transparent morphology with spongy and elastic character.In poly(NiPAAm)cryogels solvent is retained within the gel both due to binding by polymer network and entrapment within cap-illary.The binding of solvent molecules on thepoly(NiPAAm)Fig.1.Digital photographs of 7%supermacroporous poly(NiPAAm)cryogel:(A)dried poly(NiPAAm)cryogel,(B)water swollen poly(NiPAAm)cryogel,(C)de-swollen poly(NiPAAm)cryogel after keeping in water at 40◦C.backbone is through hydrogen bonding and single NiPAAm monomer has at least four sites for hydrogen bonding with water (two lone pairs from carbonyl oxygen and one each from nitrogen and hydrogen amide atoms).3.2.Poly(NiPAAm)cryogel morphologyThe mechanism for formation of poly(NiPAAm)cryogel is similar to that of polyacrylamide cryogel.When the polymer-ization of monomer solution is allowed to proceed at sub-zero temperature,cryoconcentration of monomers takes place in non-frozen solvent phase where they polymerize and results in a chemically cross-linked poly(NiPAAm)cryogel [9].The morphology of poly(NiPAAm)cryogel formed at −12◦C is clearly reﬂected in the SEM picture taken at low vacuum (Fig.2).The poly(NiPAAm)cryogel prepared at 7%total monomer concentration have interconnected and large pore size in the range of 30–99␮m.The interconnectivity of pores determine the convective ﬂow of solvent while large pore size demonstrates the potential of cryogel for particle process-ing,like cells,cell organelles and inclusion bodies [9–12,22].Highly porous structure and sufﬁciently large pore size of poly(NiPAAm)cryogel provides non-hindered diffusion of all solutes including macromolecules.The porosity,interconnectiv-ity and convective liquid ﬂow of all these poly(NiPAAm)cryogel formed at different monomer concentration deciphers the ﬂow rate of the corresponding poly(NiPAAm)cryogel (Table 1)pression analysis of cryogel monolithThe elastic and compression properties of the cryogel was determined by exerting physical stress on the gel which was in turn used to calculate Young’s modulus,which is a mathematical description of an object or substance’s tendency to be deformed when a force is applied to it.Fig.3shows the Young’s modulus of each cryogel sample of same size as calculated by analyzing the stress and strain values of each cryogel.The Young’s moduli of poly(NiPAAm)cryogel were calculated to be in the range of 33–65kPa which was less than poly(AAm)cryogel which show values in the range of 42–86kPa.The poly(NiPAAm)cryogelA.Srivastava et al./Materials Science and Engineering A 464 (2007) 93–10097Fig.2.Scanning electron microscopy pictures of:(A)supermacroporus poly(NiPAAm)cryogels and (B)poly(NiPAAm)hydrogel.The total monomer concentration was 7%and NiPAAM:MBAAm ratio was 5:1.undergoes more strain up to 90%as compared to 80%com-pression in poly(AAm).It is well demonstrated that the stress required by the poly(NiPAAm)cryogel to undergo compres-sion is less than the poly(AAm)cryogel which infers that the poly(NiPAAm)cryogel is more elastic and soft.It was also seen that with the change in total monomer concentration from 6to 8%,the rigidity of cryogels is also altered.As the concentra-tion increases the sponginess and elasticity decreases which in turn decreases the compressibility and squeezability of cryogel.This is due to the fact that at high concentration of monomer,the cross-linking increases the rigidity of cryogel and in turn the elastic behavior decreases.It can be assumed that as the cross-linking agent concentration increases in total monomer concentration,it causes the formation of more compactandFig. parative study of mechanical strength of poly(NiPAAm)and poly(AAm)cryogel.The Young’s modulus of 6,7and 8%poly(NiPAAm)( )and poly(AAm)( )cryogel.The parameters were determined at 80%compres-sion from where the cryogel regains its original shape after swelling in water.For details see Section 2.rigid cryogels.If the compression force applied on cryogel is increased further,the gel gets deformed and the original length cannot be regained.In contrast when hydrogels were tested for compression,it was not possible to apply the compressing force as the gel could not withstand the applied force and broke down.It is observed that poly(NiPAAm)cryogel is more spongy than poly(AAm)cryogel and undergoes greater change in length.One of the potential applications of these cryogels,that has recently been established,is in detachment of bioparticles which are attached/adsorbed to the surface of cryogel [18].This detach-ment of bioparticles is facilitated by elastic deformation of cryogels.Thus,it can be said that elasticity of cryogel is an important factor for such applications.It would be beneﬁcial to know elasticity of cryogels in mathematical terms and the max-imum force up to which they can regain their shape,which is one of the aims of the present study.3.4.Swelling/de-swelling kineticsThe swelling kinetics of poly(NiPAAm)(5:1)cryogels and hydrogels of different monomer concentration studied by gravi-metric method is shown in Fig.4.Both the gel systems were compared on the basis of the time required to reach a particu-lar value of W u (or W r ).It is clearly evident from the obtained data that poly(NiPAAm)cryogel irrespective of the monomer concentration attains swelling equilibrium within 20min,while hydrogels of similar monomer concentration took more than 2days to reach equilibrium.This difference in swelling kinetics of poly(NiPAAm)cryogels and hydrogels is due to the basic difference in their pore morphology and wall thickness.Though the conventional hydrogels consist of an interconnected network of pores (the pore size is rather small and the distance between pores is long)made up of thick walls.In comparison to this,cryogels have pores that are quite large (up to 200␮m)and are interconnected via thin walls.This allows fast transport of sol-vent molecules within thin walls over short distances across the macroporous structure.This phenomenon is quite useful specif-98 A.Srivastava et al./Materials Science and Engineering A464 (2007) 93–100Fig.4.Swelling kinetics of poly(NiPAAm)gels.Water uptake capacity was determined at increasing time interval for(A)poly(NiPAAm)cryogel and(B) poly(NiPAAm)hydrogel at three different monomer concentrations:( )6%, ( )7%and( )8%.For details see Section2.ically in case of responsive gels like that of poly(NiPAAm).One important performance criteria for stimuli-responsive systems is the rate at which they respond to any change in their environ-ment.It is obvious that response time depends upon the size of the system,larger the thermo-sensitive gel slower is its swelling and shrinkage as the response time required depends upon rate of heat and mass transfer process as well as the distance of the periphery of the gel to the center of gel.This response time is greatly reduced in macroporous gel structure as the heat and mass transfer process takes place only at short distance in the thin walls of the macropores contrary to the long distances of the conventional gels[9].One of the characteristic feature of poly(NiPAAm)cryogels is their rapid response to any change in temperature.In response to change in temperature of its envi-ronment poly(NiPAAm)changes its property from hydrophilic to hydrophobic or vice versa above or below its LCST(32◦C), respectively[23].The rapidity of response in such supermacro-porous structure depends upon total monomer concentration, cross-linking density,pore wall thickness,temperature,etc.at which the gels are prepared.The response time is also affected by the thickness of gel,i.e.,the distance between the outer bound-aries to central parts of cryogel,larger the distance slower the rate of swelling and shrinkage due to slow rate of mass andheat Fig.5.Swelling ratio of6,7and8%poly(NiPAAm)hydrogel and cryogel. Swelling ratio of poly(NiPAAm)hydrogel(ﬁlled bar)and cryogel(wide upward diagonal bar).Swelling ratio was determined as the ratio of wet weight to dry weight of hydrogel and cryogel.For details see Section2.exchange due to increased distance[24–26].Interconnectivity of pores plays a crucial role in fast swelling and de-swelling of cryogels as solvent molecule could move by convection across this network,while in conventional hydrogels this process is diffusion dependent and thus slower.This difference in pore morphology leads to a faster swelling/de-swelling kinetics in poly(NiPAAm)cryogels.The swelling ratio(q w)of poly(NiPAAm)cryogels ranges from13.5to16,while that of hydrogels is in the range of7–10. The swelling ratio in cryogels decreases slightly as the monomer concentration increases from6to8%with6%gels having the highest swelling ratio of16(Fig.5).This decrease in swelling ratio with concentration can be explained on the basis that as the monomer concentration increases,wall thickness increases and more rigid and less porous cryogel is formed,thus exhibiting reduced swelling.As the porosity of gel increases the swelling ratio increases because large amount of water molecule diffuses inside the gel with high porosity than the low porous gel system. Connectivity of pores plays a crucial role and leads to faster swelling rate of the gels.Water can enter or leave the cryo-gel through interconnected pores by convection.Similar studies on swelling/de-swelling kinetics of ionic poly(AAm)cryogel based on the volume changes of the gel have demonstrated that ionic poly(AAm)cryogel swells and de-swells much faster than poly(AAm)hydrogel[27].The swelling/de-swelling weight ratio of poly(NiPAAm) cryogel with varying concentration of cross-linking agent (MBAAm)was also studied and it was seen that,there is not much difference in swelling/de-swelling ratio on varying cross-linking agent concentration(Fig.6).The swelling ratio of all the cryogel at different cross-linking agent concentration are in the range of17–21,the cryogel with1%cross-linking agent concentration have little higher swelling ratio than other cryo-gels with a higher cross-linking agent concentration.It may beA.Srivastava et al./Materials Science and Engineering A 464 (2007) 93–10099Fig.6.The swelling/de-swelling ratio of poly(NiPAAm)cryogel at different concentration of cross-linking agent.Swelling ratio(A)and de-swelling ratio(B) of poly(NiPAAm)cryogel at cross-linking agent concentration of:( )1wt%, ( )1.25wt%and( )1.5wt%at different time interval during swelling.For details see Section2.probably because the concentration of cross-linking agent effect the cross-linking of polymer at localized concentration which makes the pore wall of the cryogel loose or rigid but it would not affect much on the interconnectivity of pores and pore distri-bution.The solvent molecules still travels through the walls by convection and moves in and out of the gel structure resulting in swelling and de-swelling of cryogel which can be independent of cross-linking agent concentration.These poly(NiPAAm)cryo-gels with different cross-linking agent concentration undergoes about25%de-swelling,which was found to be independent of cross-linking agent concentration.De-swelling kinetics of poly(NiPAAm)cryogel and hydro-gel was determined at40◦C for three different initial monomer concentration.A graph of W r versus time was plotted(Fig.7). It can be clearly seen from these results that de-swelling rate of poly(NiPAAm)cryogels is10–15times faster than the con-ventional hydrogels.Also it can be seen that the cryogels attain their de-swelling equilibrium almost instantaneously while the hydrogels show a two phase response curve,in which maximum de-swelling occurs in theﬁrst30–50min while the equilibriais Fig.7.De-swelling kinetics of poly(NiPAAm)gels.Water retention capacity was determined at increasing time intervals for:(A)poly(NiPAAm)cryogel and (B)poly(NiPAAm)hydrogel for three different concentrations( )6%,( )7% and( )8%.For details see Section2.achieved slowly over a period of350min.This difference in the de-swelling kinetics of cryogel and hydrogel can be attributed to the mechanism by which the solvent transport occurs in these polymer networks.In conventional hydrogel systems the solvent moves in and out of the polymer network by diffusion while in supermacroporus like structures as found in cryogels the solvent moves by convection through the thin walls around the pore.The biphasic response seen in hydrogels can be explained as follows. Initially as the gel samples are placed above LCST only the outer surface chains attain the surrounding temperature and begun to shrink while due to slow heat transfer by diffusion in hydrogels the inner surface comes in equilibrium with the surroundings only after a lag period.This difference in response time leads to formation of two layers within the hydrogel consisting of an outer layer largely in de-swollen state while the inner layer is constantly decreasing as more and more de-swelling takes place, which is a slow process and thus leads to an extended de-swelling phase after initial rapid response.Further the de-swelling kinetics of poly(NiPAAm)cryogel as shown in Fig.7demonstrates about25%de-swelling or75% water retention capacity.Thermo-induced de-swelling ratio or water retention capacity of the cryogel is found to be smaller。

advanced materials technologies文献名称缩写

Advanced Materials Technologies (AMT)IntroductionThe field of advanced materials technologies (AMT) is a rapidly evolving and highly interdisciplinary area of research and development. It encompasses a wide range of materials, including composites, nanomaterials, biomaterials, and electronic materials, and their applications across various industries. AMT holds great promise for advancing technological innovation and addressing pressing challenges in sectors such as energy, healthcare, electronics, and transportation.This article aims to provide a comprehensive and in-depth exploration of AMT, covering its foundational principles, significant advancements, and future prospects.I. Fundamentals of Advanced Materials TechnologiesA. Definition and ScopeB. Classification of Advanced Materials 1. Structural Materials i. Composites ii. Ceramics iii. Metals and Alloys 2. Functional Materials i. Nanomaterials ii. Biomaterials iii. Electronic MaterialsC. Characterization Techniques for Advanced Materials 1. Microscopy 2. Spectroscopy 3. X-ray Diffraction 4. Thermal AnalysisII.Key Advancements in Advanced Materials TechnologiesA. Advanced Materials for Energy Applications 1. Batteries and Energy Storage 2. Solar Cells and Photovoltaics 3. Fuel Cells and Hydrogen StorageB. Advanced Materials for Healthcare 1. Drug Delivery Systems 2. Tissue Engineering and Regenerative Medicine 3. Bioactive Coatings and ImplantsC. Advanced Materials for Electronics 1. Integrated Circuits andFlexible Electronics 2. Nanoelectronics and Quantum Computing 3. Graphene and 2D MaterialsD. Advanced Materials for Transportation 1. Lightweight Materials for Vehicles 2. Advanced Coatings for Corrosion Resistance 3. Self-Healing Materials for Durability EnhancementIII.Fabrication and Processing TechniquesA. Additive Manufacturing and 3D Printing 1. Selective Laser Sintering 2. Stereolithography 3. Fused Deposition ModelingB. Nanofabrication and Nanolithography 1. Electron Beam Lithography 2. Scanning Probe Lithography 3. Nanoimprint LithographyC. Chemical Vapor Deposition 1. Atmospheric Pressure CVD 2. Plasma-Enhanced CVD 3. Molecular Beam EpitaxyD. Sol-Gel Chemistry 1. Synthesis of Thin Films 2. Fabrication of Nanoparticles 3. Templated Material SynthesisIV.Challenges and Future DirectionsA. Scalability and Cost-Effectiveness of AMTB. Environmental and Safety ConsiderationsC. Integration of AMT in Industrial ProcessesD. Emerging Trends in AMT Research and Development 1. Artificial Intelligence and Machine Learning 2. Bio-inspired Materials 3. Self-Assembly and Supramolecular ChemistryConclusionThe field of advanced materials technologies is continuously pushing the boundaries of what is possible in materials science and engineering. Through a multidisciplinary approach, AMT has enabled significant advancements in various industries, revolutionizing energy storage, healthcare diagnostics and treatments, electronics manufacturing, and transportation systems. However, several challenges remain, including scalability, cost-effectiveness, and ensuring the safety and environmental sustainability of AMT processes. Looking ahead, emerging trends such as artificial intelligence, bio-inspired materials, andself-assembly hold immense potential for shaping the future of advanced materials technologies. With ongoing research and collaborative efforts, AMT has the potential to address global challenges and lead to breakthrough innovations.。

14-高分子科学导论-Supramolecular polymers

Intermolecular Interactions
“Supramolecular Chemistry is the chemistry of the intermolecular bond, concerning the structure and functions of the entities formed by the association of two or more
and concentrated solutions, as well as in the bulk.
molecular chemistry atom + atom → molecular（covalent） supramolecular chemistry molecular + molecular → supramolecular （noncovalent）
O P OH O H2 C O
N
O O P OH O O H2 C
鸟嘌呤 O N N H
N N N H H
CH2 O HO P O O
Supramolecular polymer
Colloid Early 20th century Supramolecular polymer from 1997
Linear polymer from 1930

Non-covalent forces that hold supramolecular polymers together include coordination, π-π interactions, and hydrogen bonding.
O 胸腺嘧啶 CH3 O 腺嘌呤 N H N H N N H N O 胞嘧啶 H H N N O N O N O CH2 O HO P O O

材料科学与工程专业英语 Unit 4 Chemistry and Advanced Materials

Unit 4 Chemistry and Advanced MaterialsBeing closely related to materials science, chemistry focuses on the atomic or molecular level, and materials science deals with macroscopic properties, howeverboth together provide a proper understanding of how chemical composition, structure and bonding of materials are related to the particular properties.be related to……..focus on….译文：和材料科学紧密相关的化学，关注原子或者分子水平，材料科学处理宏观性质，然而，两者一起可以理解材料的化学组成、结构和键如何同具体的性质联系起来。

But many arising problems like pollution of the environment or the toxicity of different materials nowadays clearly reveal the need of a better understanding of the basic chemistry. It is becoming widely recognized that no new method for extracting or processing a material can be considered without good understanding of the real costs as well as its fate after its lifetime.like ….it is becoming widely recognized that…as well as ….译文：但是许多出现的问题，象现在的环境污染、不同材料的毒性，清晰地显示需要很好地理解基础化学。

化学专业英语前沿词汇-推荐下载

化学专业英语前沿讲座Seminar专业英语Professional English现代分析化学Modern analytical chemistry生物分析技术Bioanalytical techniques高分子进展Advances in polymers功能高分子进展Advances in functional polymers有机硅高分子研究进展Progresses in organosilicon polymers高分子科学实验方法Scientific experimental methods of polymers高分子设计与合成The design and synthesis of polymers反应性高分子专论Instructions to reactive polymers网络化学与化工信息检索Internet Searching for Chemistry & Chemical Engineering information　有序分子组合体概论Introduction to Organized Molecular Assembilies两亲分子聚集体化学Chemistry of amphiphilic aggregates 表面活性剂体系研究新方法New Method for studying Surfactant System微纳米材料化学Chemistry of Micro-NanoMaterials分散体系研究新方法New Method for studying dispersion分散体系相行为The Phase Behavior of Aqueous Dispersions溶液-凝胶材料Sol-Gel Materials高等量子化学Advanced Quantum Chemistry分子反应动力学Molecular Reaction Dynamic计算量子化学Computational Quantum Chemistry群论Group Theory分子模拟理论及软件应用Theory and Software of Molecular Modelling & Application 价键理论方法Valence Bond Theory量子化学软件及其应用Software of Quantum Chemistry & its Application分子光谱学Molecular Spectrum算法语言Computational Languange高分子化学Polymer Chemistry高分子物理Polymer Physics药物化学Medicinal Chemistry统计热力学Statistic Thermodynamics液-液体系专论Discussion on Liquid-Liquid System配位化学进展Progress in Coordination Chemistry无机材料及物理性质Inorganic Materials and Their Physical Properties物理无机化学Physical Inorganic Chemistry相平衡Phase Equilibrium现代无机化学Today's Inorganic Chemistry无机化学前沿领域导论Introduction to Forward Field in Inorganic Chemistry量子化学Quantum Chemistry分子材料Molecular Material固体酸碱理论Solid Acid-Base Theory萃取过程物理化学Physical Chemistry in Extraction表面电化学Surface Electrochemistry电化学进展Advances on Electrochemistry现代电化学实验技术Modern Experimental Techniques of Electrochemistry金属-碳多重键化合物及其应用Compounds with Metal-Carbon multiple bonds and The ir Applications叶立德化学:理论和应用Ylides Chemistry: Theory and Application立体化学与手性合成Stereochemistry and Chiral Synthesis杂环化学Heterocyclic Chemistry有机硅化学Organosilicon Chemistry药物设计及合成Pharmaceutical Design and Synthesis超分子化学Supramolecular Chemistry分子设计与组合化学Molecular Design and Combinatorial Chemistry纳米材料化学前沿领域导论Introduction to Nano-materials Chemistry纳米材料控制合成与自组装Controlled-synthesis and Self-assembly of Nano-materials 前沿讲座Leading Front Forum专业英语Professional English超分子化学基础Basics of Supramolecular Chemistry　液晶材料基础Basics of Liquid Crystal Materials　现代实验技术Modern analytical testing techniques色谱及联用技术Chromatography and Technology of tandem发光分析及其研究法Luminescence analysis and Research methods胶束酶学Micellar Enzymology分析化学中的配位化合物Complex in Analytical Chemistry电分析化学Electroanalytical chemistry生物分析化学Bioanalytical chemistry分析化学Analytical chemistry仪器分析Instrument analysis高分子合成化学Polymers synthetic chemistry高聚物结构与性能Structures and properties of polymers有机硅化学Organosilicon chemistry功能高分子Functional polymers有机硅高分子Organosilicon polymers高分子现代实验技术Advanced experimental technology of polymers高分子合成新方法New synthetic methods of polymers液晶与液晶高分子Liquid crystals and liquid crystal polymers大分子反应Macromolecules reaction水溶性高分子Water-soluble polymers聚合物加工基础The basic process of polymers聚合物复合材料Composite materials高等化工与热力学Advanced Chemical Engineering and Thermodynamics高等反应工程学Advanced Reaction Engineering高等有机化学Advanced Organic Chemistry高等有机合成Advanced Organic synthesis有机化学中光谱分析Spectrum Analysis in Organic Chemistry催化作用原理Principle of Catalysis染料化学Dye Chemistry中间体化学与工艺学Intermediate Chemistry and Technology化学动力学Chemical Kinetics表面活性剂合成与工艺Synthesis and Technology of Surfactants环境化学Environmental Chemistry化工企业清洁生产Chemical Enterprise Clean Production化工污染及防治Chemical Pollution and Control动量热量质量传递Momentum, Heat and Mass Transmission化工分离工程专题Separation Engineering耐蚀材料Corrosion Resisting Material网络化学与化工信息检索Internet Searching for Chemistry & Chemical Engineering information　新型功能材料的模板组装Templated Assembly of Novel Advanced Materials　胶体与界面Colloid and Interface纳米材料的胶体化学制备方法Colloid Chemical Methods for Preparing Nano-materials脂质体化学Chemistry of liposome　表面活性剂物理化学Physico-chemistry of surfactants高分子溶液与微乳液Polymer Solutions and Microemulsions两亲分子的溶液化学Chemistry of Amphiphilic Molecules in solution介孔材料化学Mesoporous Chemistry超细颗粒化学Chemistry of ultrafine powder分散体系流变学The Rheolgy of Aqueous Dispersions量子化学Quantum Chemistry统计热力学Statistic Thermodynamics群论Group Theory分子模拟Molecular Modelling高等量子化学Advanced Quantum Chemistry价键理论方法Valence Bond Theory量子化学软件及其应用Software of Quantum Chemistry & its Application计算量子化学Computational Quantum Chemistry分子模拟软件及其应用Software of Molecular Modelling & its Application分子反应动力学Molecular Reaction Dynamic分子光谱学Molecular Spectrum算法语言Computational Languange高分子化学Polymer Chemistry高分子物理Polymer Physics腐蚀电化学Corrosion Electrochemistry物理化学Physical Chemistry结构化学structural Chemistry现代分析与测试技术(试验为主）Modern Analysis and Testing Technology（experime tally)高等无机化学Advanced Inorganic Chemistry近代无机物研究方法Modern Research Methods for Inorganic Compounds萃取化学研究方法Research Methods for Extraction Chemistry单晶培养Crystal Culture固态化学Chemistry of Solid Substance液-液体系专论Discussion on Liquid-Liquid System配位化学进展Progress in Coordination Chemistry卟啉酞箐化学Chemistry of Porphyrine and Phthalocyanine无机材料及物理性质Inorganic Materials and Their Physical Properties物理无机化学Physical Inorganic Chemistry相平衡Phase Equilibrium生物化学的应用Application of Biologic Chemistry生物无机化学Bio-Inorganic Chemistry绿色化学Green Chemistry金属有机化合物在均相催化中的应用Applied Homogeneous Catalysis with Organometa llic Compounds功能性食品化学Functionalized Food Chemistry无机药物化学Inorganic Pharmaceutical Chemistry电极过程动力学Kinetics on Electrode Process电化学研究方法Electrochemical Research Methods生物物理化学Biological Physical Chemistry波谱与现代检测技术Spectroscopy and Modern Testing Technology理论有机化学theoretical Organic Chemistry合成化学Synthesis Chemistry有机合成新方法New Methods for Organic Synthesis生物有机化学Bio-organic Chemistry药物化学Pharmaceutical Chemistry金属有机化学Organometallic Chemistry金属-碳多重键化合物及其应用Compounds with Metal-Carbon multiple bonds and The ir Applications分子构效与模拟Molecular Structure-Activity and Simulation过程装置数值计算Data Calculation of Process Devices石油化工典型设备Common Equipment of Petrochemical Industry化工流态化工程Fluidization in Chemical Industry化工装置模拟与优化Analogue and Optimization of Chemical Devices化工分离工程Separation Engineering化工系统与优化Chemical System and Optimization高等化工热力学Advanced Chemical Engineering and Thermodynamics超临界流体技术及应用Super Cratical Liguid Technegues and Applications膜分离技术Membrane Separation Technegues溶剂萃取原理和应用Theory and Application of Solvent Extraction树脂吸附理论Theory of Resin Adsorption中药材化学Chemistry of Chinese Medicine生物资源有效成分分析与鉴定Analysis and Detection of Bio-materials相平衡理论与应用Theory and Application of Phase Equilibrium计算机在化学工程中的应用Application of Computer in Chemical Engineering微乳液和高分子溶液Micro-emulsion and High Molecular Solution传递过程Transmision Process反应工程分析Reaction Engineering Analysis腐蚀电化学原理与应用Principle and Application of Corrosion Electrochemistry腐蚀电化学测试方法与应用Measurement Method and Application of Corrosion Elect rochemistry耐蚀表面工程Surface Techniques of Anti-corrosion缓蚀剂技术Inhabitor Techniques腐蚀失效分析Analysis of Corrosion Destroy材料表面研究方法Method of Studying Material Surfacc分离与纯化技术Separation and Purification Technology现代精细有机合成Modern Fine Organic Synthesis化学工艺与设备Chemical Technology and Apparatuas功能材料概论Functional Materials Conspectus油田化学Oilfield Chemistry精细化学品研究Study of Fine Chemicals催化剂合成与应用Synthesis and Application of Catalyzer低维材料制备Preparation of Low-Dimension Materials手性药物化学Symmetrical Pharmaceutical Chemistry光敏高分子材料化学Photosensitive Polymer Materials Chemistry纳米材料制备与表征Preparation and Characterization of Nanostructured materials 溶胶凝胶化学Sol-gel Chemistry纳米材料化学进展Proceeding of Nano-materials Chemistry。

超分子聚合物Supramolecular polymers的研究进展

超分子聚合物Supramolecular polymers的研究进展XXX（华中师范大学xx学院，20xx级，x班，学号：20xx21xxxx）摘要：介绍了超分子聚合物领域的研究进展及其应用,阐述了其主要类别(如氢键超分子聚合物、配合物型超分子聚合物、π-π堆积超分子聚合物及离子效应超分子聚合物), 超分子聚合物工程(加工与应用)方面发展和应用前景。

关键词：超分子化学超分子聚合物氢键金属配位1937年Wolf[1]首次提出超分子( Supermolecule )这一术语，引起了社会极大的反响，而法国科学家Lehn J.M .[2]第一次系统性地研究并定义超分子，为超分子化学和超分子聚合物化学的发展做出了重要贡献,使他获得了1987年的诺贝尔化学奖。

超分子的发现，打破了分子只能以共价键的形式结合，标志着分子化学史上的一大飞跃。

在超分子化学中，非共价键相互作用、分子识别和自组装是三个最重要的概念。

非共价键包括静电作用力、氢键、范德华力、给体一受体相互作用和金属离子配价键等[3]。

非共价键的键能远小于共价键，但通过非共价键的自组装能生成稳定的超分子和超分子聚合物。

超分子聚合物定义为重复单元经可逆的和方向性的非共价键相互作用连接成的阵列[3，4]，它的诞生和发展起源于超分子化学，此后，以非共价键为主的超分子聚合物成为了科学家研究的一大热点。

1超分子超分子化学可定义为研究分子组装和分子间键的化学[5]。

超分子化学的研究对象是基于分子间弱的相互作用（如非共价键）形成的分子聚集体。

非共价键主要包括氢键、静电作用、范德华力和疏水效应。

作为超分子相互作用的主要结合力,虽然强度远不如共价键,但对温度、溶剂等外部条件的变化具有高度的响应性能,使材料的各种可逆性能变为可能。

正是这种可逆性能使超分子材料在分子器件、传感器、药物缓释、细胞识别、膜传递等方面有着重要作用。

人们认为,超分子聚合物是一种新材料,它不仅具有各种可逆特征[6]（见图1）,更重要的是组装的灵活性。

材料期刊排名及影响因子

材料期刊排名及影响因子【自然科学】材料期刊排名及影响因子NatureScienceNature MaterialNature NanotechnologyProgress in Materials ScienceNature PhysicsProgress in Polymer ScienceSurface Science ReportsMaterials Science Engineering R-reports Angewandte Chemie-International EditionNano LettersAdvanced MaterialsJournal of the American Chemical SocietyAnnual Review of Materials ResearchPhysical Review LettersAdvanced Functional MaterialsAdvances in Polymer ScienceBiomaterialsSmallProgress in Surface ScienceChemical CommunicationsMRS BulletinChemistry of MaterialsAdvances in CatalysisJournal of Materials ChemistryCarbonCrystal Growth DesignElectrochemistry CommunicationsThe Journal of Physical Chemistry BInorganic ChemistryLangmuirPhysical Chemistry Chemical PhysicsInternational Journal of PlasticityActa MaterialiaApplied Physics LettersJournal of power sourcesJournal of the Mechanics and Physics of Solids 自然31.434 科学28.103 自然（材料）23.132 自然（纳米技术）20.571 材料科学进展18.132 自然（物理）16.821 聚合物科学进展16.819 表面科学报告12.808 材料科学与工程报告12.619 应用化学国际版10.879 纳米快报10.371 先进材料8.191 美国化学会志8.091 材料研究年度评论7.947物理评论快报7.180 先进功能材料 6.808 聚合物科学发展 6.802 生物材料 6.646 微观？6.525 表面科学进展 5.429 化学通信 5.34 材料研究学会（美国）公告 5.290 材料化学 5.046 先进催化 4.812 材料化学杂志4.646 碳4.373 晶体生长与设计4.215 电化学通讯4.194 物理化学杂志，B辑：材料、表面、界面与生物物4.189 理有机化学 4.147 朗缪尔4.097 物理化学4.064 塑性国际杂志3.875 材料学报3.729 应用物理快报 3.726 电源技术 3.477 固体力学与固体物理学杂志3.467International Materials ReviewsNanotechnologyJournal of Applied CrystallographyMicroscopy and MicroanalysisCurrent Opinion in Solid State Materials ScienceScripta MaterialiaThe Journal of Physical Chemistry ABiometalsUltramicroscopyMicroporous and Mesoporous MaterialsComposites Science and TechnologyCurrent NanoscienceJournal of the Electrochemical SocietySolid State IonicsIEEE Journal of Quantum ElectronicsMechanics of MaterialsJournal of nanoparticle research*****ON *****Journal of Applied Physics 3.462 3.446 3.212 2.992 固态和材料科学的动态 2.976 2.887 材料快报 2.871 物理化学杂志，A辑 2.801 生物金属2.629 超显微术2.555 多孔和类孔材料2.533 复合材料科学与技术2.437 当代纳米科学2.437 电化学界2.425 固体离子2.413 IEEE量子电子学杂志 2.374 材料力学 2.299 纳米颗粒研究 2.293 腐蚀科学 2.201 应用物理杂志生物材料科学―聚合物Journal of Biomaterials Science-Polymer Edition 2.158 版IEEE Transactions on Nanotechnology 2.154 IEEE 纳米学报Progress in Crystal Growth and Characterization of 晶体生长和材料表征进2.129 Materials 展Journal of Physics D-Applied Physics 物理杂志D――应用物理2.104 Journal of the American Ceramic Society 2.101 美国陶瓷学会杂志Diamond and Related Materials 2.092 金刚石及相关材料Journal of Chemical Engineering Data 2.063 化学和工程资料杂志Intermetallics 2.034 金属间化合物Electrochemical and Solid State Letters 2.001 固体电化学快报Synthetic Metals 1.962 合成金属复合材料A应用科学与Composites Part A-Applied Science and Manufacturing 1.951 制备Journal of Nanoscience and Nanotechnology 1.929 纳米科学和纳米技术Journal of Solid State Chemistry 1.91 固体化学Journal of Physics: Condensed Matter 物理学学报：凝聚态物质1 .9 生物活性与兼容性聚合Urnal of Bioactive and Compatible Polymer 1.896 物杂志International Journal of Heat and Mass Transfer 1.894 传热与传质应用物理A－材料科学和Applied Physics A-Materials Science Processing 1.884 进展Thin Solid Films 1.884 固体薄膜Surface Coatings Technology 1.860 表面与涂层技术Materials Science Engineering C-Biomimetic and 材料科学与工程C―仿生1.812 国际材料评论纳米技术应用结晶学Supramolecular Systems 与超分子系统Materials Research Bulletin 1.812 材料研究公告International Journal of Solids and Structures 1.809 固体与结构Materials Science and Engineering A-Structural 材料科学和工程A―结构1.806 Materials Properties Microst 材料的性能、组织与加工Materials Chemistry and Physics 1.799 材料化学与物理Powder Technology 1.766 粉末技术Materials Letters 1.748 材料快报Journal of Materials Research 1.743 材料研究杂志Smart Materials Structures 1.743 智能材料与结构Solid State Sciences 1.742 固体科学Polymer Testing 1.736 聚合物测试Nanoscale Research Letters 1.731 纳米研究快报Surface Science 1.731 表面科学Optical Materials 1.714 光学材料International Journal of Thermal Sciences 1.683 热科学Thermochimica Acta 1.659 热化学学报Journal of Biomaterials Applications 1.635 生物材料应用杂志Journal of Thermal Analysis and Calorimetry 1.63 Journal of Solid State Electrochemistry 1.597 固体电化学杂志Journal of the European Ceramic Society 1.58 欧洲陶瓷学会杂志Materials Science and Engineering B-Solid State 材料科学与工程B―先进1.577 Materials for Advanced Tech 技术用固体材料Applied Surface Science 1.576 应用表面科学European Physical Journal B 1.568 欧洲物理杂志BSolid State Communications 1.557 固体物理通信International Journal of Fatigue 1.556 疲劳国际杂志Computational Materials Science 1.549 计算材料科学Cement and Concrete Research 1.549 水泥与混凝土研究Philosophical Magazine Letters 哲学杂志（包括材料）1.548 Current Applied Physics 1.526 当代应用物理Journal of Alloys and Compounds 1.51 合金和化合物杂志Wear 1.509 磨损材料科学杂志―医用材Journal of Materials Science-Materials in Medicine 1.508 料Advanced Engineering Materials 1.506 先进工程材料Journal of Nuclear Materials 1.501 核材料杂志International Journal of Applied Ceramic Technology 应用陶瓷技术1.488 Chemical Vapor Deposition 1.483 化学气相沉积*****TES PART B-*****RING 1.481 复合材料B工程Composite Structures 1.454 复合材料结构Journal of Non-crystalline Solids 1.449 非晶固体杂志Journal of Vacuum Science Technology B 真空科学与技术杂志B 1.445 Semiconductor Science and Technology 1.434 半导体科学与技术溶胶凝胶科学与技术杂1.433 志Science and Technology of Welding and Joining 1.426 焊接科学与技术Metallurgical and Materials Transactions A-Physical 冶金与材料会刊A――物1.389 Metallurgy and Material 理冶金和材料Modelling and Simulation in Materials Science and 材料科学与工程中的建1.388 Engineering 模与模拟哲学杂志A凝聚态物质Philosophical Magazine A-Physics of Condensed Matter 结构缺陷和机械性能物1.384 Structure Defects and Mechanical Properties 理Philosophical Magazine 1.384 哲学杂志Ceramics International 1.369 国际陶瓷Oxidation of Metals 1.359 材料氧化Modern Physics Letters A 1.334 现代物理快报ACement Concrete Composites 水泥与混凝土复合材料1.312 Journal of Intelligent Material Systems and Structures 智能材料系统与结构 1.293 Journal of Magnetism and Magnetic Materials 1.283 磁学与磁性材料杂志Journal of Electronic Materials 1.283 电子材料杂志Surface and Interface Analysis 1.272 表面与界面分析Science and Technology of Advanced Materials 1.267 Journal of Computational and Theoretical Nanoscience 计算与理论纳米科学1.256 IEEE *****TIONS ON *****D *****NG 1.253 IEEE高级封装会刊Materials Characterization 1.225 材料表征International Journal of Refractory Metals Hard 耐火金属和硬质材料国1.221 Materials 际杂志Physica Status solidi A-Applied Research 固态物理A――应用研究1.205 PHASE *****IONS 1.201 相变Journal of Thermal Spray Technology 1.2 热喷涂技术杂志International Journal of Nanotechnology 1.184 纳米工程Journal of Materials Science 1.181 材料科学杂志Journal of Vacuum Science Technology A-VACUUM 真空科学与技术A真空1.173 Surfaces and Films 表面和薄膜***** STATUS SOLIDI B-BASIC *****H 固态物理B―基础研究1.166 *****LS ***** IN *****DUCTOR *****ING 半导体加工的材料科学1.158 International Journal of Fracture 1.147 断裂学报Journal of Materials Processing Technology 1.143 材料加工技术杂志Metals and Materials International 1.139 国际金属及材料IEEE *****TIONS ON *****CS 1.129 IEEE磁学会刊Vacuum 1.114 真空Journal of Applied Electrochemistry 1.111 应用电化学Materials Design 1.107 材料与设计***** OF ***** AND *****RY OF SOLIDS 1.103 固体物理与化学杂志Journal of Experimental Nanoscience 1.103 实验纳米科学***** *****TES 1.054 聚合物复合材料Journal of SOL-GEL Science and TEchnology材料科学杂志―电子材1.054 料Journal of Composite Materials 1.034 复合材料杂志Journal of the Ceramic Society of Japan 1.023 日本陶瓷学会杂志***** OF 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志美国混凝土学会材料杂ACI *****LS ***** 0.568 志********** 0.565 半导体********** 0.562 铁电材料*****TIONAL ***** OF MODERN ***** B 0.558 现代物理国际杂志B *****LS *****H *****IONS 0.54 材料研究创新GLASS *****OGY -PART A 0.529 玻璃技术***** OF *****LS IN CIVIL *****RING 0.526 土木工程材料杂志新型金刚石和前沿碳技0.500 术***** IN CHINA SERIES E-*****OGICAL *****S 中国科学E技术科学0.495 *****TION AND SPRAYS 0.494 雾化和喷涂*****E 0.477 合成HIGH *****TURE 0.469 高温Journal of Phase Equilibria and Diffusion 0.457 相平衡与扩散*****IC *****LS 0.455 无机材料*****CS OF *****TE *****LS 0.453 复合材料力学BIO-***** *****LS AND *****RING 0.446 生物医用材料与工程***** AND *****RY OF ***** 0.429 玻璃物理与化学***** OF WUHAN *****ITY OF 武汉理工大学学报-材料0.424*****OGY-*****LS ***** ***** 科学版*****D *****TE *****LS 0.404 先进复合材料Journal of Materials Engineering and Performance 0.403 材料工程与性能杂志Solid State Technology 0.400 固体物理技术********** ***** ***** 0.375 铁电材料快报***** OF ***** *****LS 0.373 聚合物材料杂志***** OF *****IC *****LS 0.37 无机材料杂志GLASS ***** AND *****OGY-********** 0.365 玻璃科学与技术*****E 聚合物与聚合物复合材*****S ***** *****TES 0.355 料Surface Engineering 0.354 表面工程NEW ***** AND *****R CARBON *****OGYRARE METALSHIGH *****TURE *****L *****ES***** OF ***** AND *****ION*****N ***** ***** *****N*****LS AT HIGH *****TURES*****E OF *****E *****H***** REVIEW AND *****Journal of Ceramic Processing Research 0.347 稀有金属0.34 高温材料加工0.324 测试及评价杂志0.324 美国陶瓷学会公告0.323 高温材料0.315 混凝土研究杂志0.309 表面评论与快报0.294 陶瓷处理研究日本机械工程学会国际JSME *****TIONAL ***** SERIES A-SOLID 杂志系列A－固体力学与0.291 *****CS AND *****L *****RIN 材料工程*****LS *****OGY 0.288 材料技术*****D *****TES ***** 0.27 先进复合材料快报HIGH *****TURE *****LS AND *****ES 0.268 高温材料和加工*****TED ********** 0.242 集成铁电材料*****LS ***** 0.226 材料科学*****LS *****ION 0.21 材料评价POWDER *****RGY AND METAL *****S 0.201 粉末冶金及金属陶瓷RARE METAL *****LS AND *****RING 0.162 稀有金属材料与工程*****TIONAL ***** OF *****LS ***** 材料与生产技术国际杂0.157*****OGY 志METAL ***** AND HEAT *****NT 0.157 金属科学及热处理***** OF *****D *****LS 0.14 先进材料杂志*****D *****LS *****ES 0.129 先进材料及工艺*****LS WORLD 0.122 材料世界***** AND *****RING OF *****TE 0.098 复合材料科学与工程*****LS *****LS *****ANCE 0.074 材料性能。

2010年化学与制药工程学院教师发表学术论文情况

乔占平
党元林，张书申
J. Chem. Eng. Data
2010.7
SCI
8
Investigation on the Equilibrium Phase Diagram of the Ternary System TmCl3-CdCl2-H2O at 298.15 K and Standard Molar Enthalpy of Formation of Cd3TmCl9•15H2O
邱东方
郭应臣，、冯玉全，陈书阳，赛明泽
无机化学学报
2010.9
SCI
13
Study on heterogeneous degradation of chitosan with H2O2catalysed by a new supermolecular assembly crystal: [C6H8N2]6H3[PW12O40]•2H2O
邱东方
冯玉全，王宏伟，包晓玉，郭应臣
Inorg. Chem. Commun.
2010.13
SCI
2
Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Novel Supramolecular Compound {[2-(2-Pyridyl)benzimidazoleH_2]_2·[BiCl_6]·Cl}
谢海泉
杨启超，乔占平，陈欣，张平允
J. Chem. Eng. Data
2010.9
SCI
7
Phase Equilibrium System of Cadmium Chloride + DL-Alanine + Water at 298.15K and Standard Molar Enthalpy of Formation of Cd3(Ala)2Cl6·4H2O

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Cite this:Chem.Soc.Rev .,2012,41,5922–5932Characterization of supramolecular polymers wYiliu Liu,Zhiqiang Wang and Xi Zhang*Received 20th March 2012DOI:10.1039/c2cs35084jSupramolecular polymers are made of monomers that are held together by noncovalentinteractions.This is the reason for the wide range of novel properties,such as reversibility and responses to stimuli,exhibited by supramolecular polymers.A range of supramolecular polymerization methods have been developed leading to a number of novel supramolecular materials.However,standard techniques for the characterization of supramolecular polymers have yet to be established.The dynamic nature of supramolecular polymers makes them diﬃcult to be fully characterized using conventional polymer techniques.This tutorial review summarizes various methods for characterizing supramolecular polymers,including theoretical estimation,size exclusion chromatography,viscometry,light scattering,vapor pressure osmometry,mass spectrometry,NMR spectroscopy,scanning probe microscopy,electron microscopy,and atomic force microscopy-based single molecule force spectroscopy.Each of these methods has its own particular advantages and disadvantages.Most of the methods are used to characterize the supramolecular polymer chain itself.However,some of the methods can be used to study the self-assembled state formed by supramolecular polymers.The characterization of asupramolecular polymer cannot be realized with a single method;a convincing conclusion relies on the combination of several diﬀerent techniques.IntroductionSupramolecular polymer chemistry originated from a close integration of polymer science and supramolecular chemistry,and now stands as a popular and independent research area.1–3In contrast to conventional polymers,the connection between monomers of supramolecular polymers is noncovalent.4–8The dynamic nature of noncovalent interactions gives supramo-lecular polymers many novel properties,which can be comple-mentary to conventional polymers.9For example,supramolecular polymers possess very sensitive thermal responsiveness.A small change in temperature can lead to a large variation in viscosity,which makes supramolecular polymers much easier to process than conventional polymers.In addition,the reversibility derived from the noncovalent interactions gives supramolecular polymers the potential to be recyclable and self-healing.10–11The evolution of supramolecular polymers has resulted from two streams of eﬀort.One is to develop new mechanisms for supramolecular polymerization,such as hydrogen bonding,Key Lab of Organic Optoelectronics and Molecular Engineering,Department of Chemistry,Tsinghua University,Beijing,100084,China.E-mail:xi@w Part of a themed issue on supramolecular polymers.Yiliu LiuYiliu Liu got his BA in the Department of Environmental Engineering,Xi’an Jiaotong University.In 2008,he joined Prof.Xi Zhang’s group as a PhD student in the Depart-ment of Chemistry at Tsinghua University.Currently,he is working on supramolecular polymerization based on host-enhanced noncovalent in-teractions.Zhiqiang WangZhiqiang Wang is a full pro-fessor of the Department of Chemistry,Tsinghua Univer-sity.His research interests are focused on supramolecular self-assembly and organic thin ﬁlms.Chem Soc RevDynamic Article Links/csrTUTORIAL REVIEWP u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.View Article Online / Journal Homepage / Table of Contents for this issuemetal coordination,and host–guest interactions.4–8The other is to approach practical applications for supramolecular polymers.12However,each stream requires the characterization of supra-molecular polymers.Concerning the available information on supramolecular polymers,the average molar mass is especially useful,because the polymer-like properties only can be discerned when the supramolecular polymers possess a high degree of polymerization (DP).13However,the dynamic nature of supramolecular polymer bonding,which guarantees their unique properties,also makes their characterization diﬃcult.The change of solvent concen-tration,temperature,composition,or the stimuli from the surrounding environment always signiﬁcantly inﬂuences the original molecular organization of a supramolecular polymer.Though some eﬀorts have been made to settle these problems,such as capturing supramolecular polymers by post chemical stabilization,14–16in most cases,the characterization remains a challenge.Many well-established characterization methods do not work as well as when applied to conventional polymers.Mostly,only partial information can be obtained from indi-vidual methods.Therefore,a combination of several charac-terization methods in diﬀerent conditions is always required.Characterization approachesTheoretical estimation of molecular weight from binding constantSupramolecular polymerization is essentially a self-assembly process,in other words,it is a thermodynamic equilibrium.From the equilibrium constant,it is possible to use established theoretical models to estimate the average molar mass of supramolecular polymers.Several indeﬁnite self-association models have been discussed by R.B.Martin,which can also be applied to supramolecular polymerization systems.17The simplest model is called the isodesmic model,which assumes that the association of the end-groups of the monomers does not change during the supramolecular polymerization process.With this simplifying assumption,the DP can be very simply estimated as DP E (K a C )1/2,where K a is the equilibrium constant between the monomers and C is the total monomer concentration.3According to this method of estimation,to obtain long chain supramolecular polymers,either a large binding constant or high monomer concentration is required.As shown in Fig.1,to obtain supramolecular polymer chains of around 100repeating units,a monomer concentration of 0.05M and binding constant of 105M À1are needed.Measuring the binding constant is an important issue.Many experimental methods,such as NMR titrations,isothermal titration calori-metry,and UV-vis spectroscopy are readily available.18For more complicated supramolecular polymerization systems,other factors must be considered in theoretical deri-vations.For example,the binding constant K a may vary with the growth in chain size of a supramolecular polymer.It is diﬃcult to express them by general ﬁtting equations.It is recommended to combine the obtained experimental data with a proper theoretical estimation to get qualitative information.Some examples will be given later on.Size exclusion chromatographySize exclusion chromatography (SEC),especially gel permeation chromatography (GPC),is widely used in conventional polymer characterization and provides good information about the molar mass distribution of a polymer.Generally,the polymers in solution are separated based on their molecular size,which can be determined by the retention time.Referring to known standard samples, e.g.polystyrene,it is easy to deduce a molecular mass distribution.However,it must be pointed out that the whole experimental process is accompanied by the dilution of the sample.Considering the supramolecular polymers are reversible and dynamic systems,the DP is always strongly concentration dependent,which results in signiﬁcant tailing in the distribution obtained from SEC.Consequently on its own,SEC is not a very suitable approach.However,in some cases,such those involving metal-coordination and multiple hydrogen bonding arrays,in which the noncovalent bonds possess suﬃciently slow association and disassociation kinetics,SEC has been used to get useful information.19–23Schubert et al.reported a supramolecular polymer where the ‘‘monomers’’bearing two terpyridine moieties both at the head and tail and were held together by coordination with ruthenium(II )(Fig.2).19The formation of high molecularFig.1Theoretical relationship between K a and DP in the isodesmic model (Reproduced with permission of the American Chemical Society from ref.3).Xi ZhangXi Zhang is a full professor and the chair of the depart-ment of chemistry,Tsinghua University.His research inter-ests are focused on supra-amphiphiles,supramolecular polymers,selenium-containing polymers,layer-by-layer assem-bly,and single-molecule force spectroscopy of polymers.He serves as a Senior Editor of Langmuir and is a member of the Advisory Board of several journals,including Accounts of Chemical Research,Chemical Communications,Polymer,and Polymer Chemistry.He was elected a Member of the Chinese Academy of Sciences in 2007,and a fellow of the Royal Society of Chemistry,UK in 2008.Currently,he is the vice president of the Chinese Chemical Society.P u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.weight supramolecular polymers was revealed by GPC analysis.From GPC traces of P1and P2,it is obvious that P2has a higher molecular weight than P1.Moreover,using a refractive-index detector and a linear poly(methyl methacrylate)calibra-tion sample revealed a number averaged molecular weight of 1.38Â105and a polydispersity index (PDI)of 1.55.This calculated molecular weight of P2corresponds to 15mono-mers (P1).Zimmerman et al.also reported a series of supra-molecular dendrimers that were formed by strong hydrogen bonding.21The experimental molecular weights of the mono-mers were determined from the SEC retention times with polystyrene as the standard.The formed dendrimers showed molecular weights within 20%of the calculated values.Another type of supramolecular polymer is that formed by mechanical bonding.24Besides being connected through non-covalent interactions,the monomers are also topologically interlocked,and thus the DP does not decrease under SEC processing conditions.Stoddart et al.synthesized a mecha-nically interlocked poly[c2]daisy chain,as shown in Fig.3.25The number average molecular weight (M n )was determined by SEC/multi-angle light scattering analysis,giving a value of 32.9Æ2.5kDa with a PDI of 1.85.Huang et al.also reported a daisy chain prepared by esteriﬁcation of a well-designed crown ether–viologen complex at low temperature.26By GPC analysis with polystyrene as the standard,the M n and PDI of this daisy chain were estimated to be 64kDa and 1.5.The DP was calculated to be up to 45.ViscometryViscometry is a classic method used to determine a polymer molecular weight distribution.The relationship between the intrinsic viscosity and the molecular weight can be expressedby the empirical Mark–Houwink equation,[Z ]=KM a ,in which K and a are both empirical constants.For a given polymer,values of K and a may be obtained from suitable calibration experiments with a series of sharp ing this equation the molecular weight of a polymer can be determined from the intrinsic viscosity.In principle,whenFig.2The formation of metallo-supramolecular polymer P2and the GPC traces for P1and P2.19Fig.3Synthesis of the poly[c2]daisy chain and its SEC chromato-gram result (Reproduced with permission of the American Chemical Society from ref.25).P u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.applying this approach to supramolecular polymers,as long as the Mark–Houwink parameters can be obtained,the molecular weight of the supramolecular polymers can be deduced.However,the diﬃculty here is to ﬁnd a suitable covalent model for this dynamic system to obtain these parameters.Bouteiller et al.describe a nice example.They prepared a series of supramolecular polymers based on hydrogen bonds between benzoic acid monomers 1–3(Fig.4).Meanwhile,a model polymer which possesses a similar struc-ture was synthesized as a covalent model.By analyzing the experimental data obtained from this model,the visco-metric parameters can be estimated.The calculated curves ﬁt well with the experimental data of the supramolecular polymer formed by monomer 1,but not that well with the other two,probably owing to the relatively crude nature of the model polymer.27Meijer et al.showed a diﬀerent train of thought.They designed a monofunctional compound,which can act as a chain stopper.Adding this compound into the solution of supra-molecular polymers,a dramatic drop in viscosity was observed.If the mole fraction of this compound is x ,the DP can be simply assumed to be 2/x .Fitting of the experimental viscosity data revealed the DP to be 700at 40mM,which corresponds to an average molar mass of 500kDa.28However,in most cases,viscometry methods are only used to study supramolecular polymerization in a quantitative manner.29–32One of the common uses is to deduce the critical polymerization concentration (CPC)of the supramolecular polymerization.A CPC always exists in the cases of supra-molecular polymerization with a ring–chain mechanism.4There exists an equilibrium between linear supramolecular polymers and cyclic species.Below the CPC,cyclic species dominate,and above the CPC,linear supramolecular polymers are favored.As linear and cyclic species’viscosities have diﬀerent correlations with concentration,the critical concen-tration can be easily found in a viscosity–concentration plot.For instance,Gibson and Huang et al.achieved ring–chain supramolecular polymerization by using a homoditopic crown ether derivative and a homoditopic bis-paraquat derivative (Fig.5).As shown in the concentration-dependent viscosity log–log plot,a slope of 1.02in the low concentration regime and a slope of 2.08at high concentration were found,which gave a CPC of 80mM.29Light scatteringLight scattering is a well-established method in determining the molecular size and morphology of the samples.Two methods are commonly used:static light scattering (SLS)and dynamic light scattering (DLS).SLS is extensively used in polymer science to measure the molar mass.The classical Zimm plot representation works by double-extrapolation of the concentration and measurement angle to zero;the characteristicFig.4Structures of monomers,supramolecular polymers and the model polymer.27Fig.5Schematic illustration of the ring–chain supramolecular polymerization and the speciﬁc viscosity–concentration plot (Reproduced with permission of the American Chemical Society from ref.29).P u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.information gained includes weight-average molar mass (M w ),radius of gyration (R g ),and second virial coeﬃcient (A 2).It should be noted that for covalent polymers that form no aggregates,the plots are linear.However,in the case of supramolecular polymers,nonlinear plots appear since the molar mass evolution with concentration leads to the variation of A 2,which brings problems in extrapolating the concentration to zero.An eﬀective strategy is to utilize a stopper to assist mass control (Fig.6a).33,34As in the supramolecular polymers system formed by 2,4-bis(2-ethylhexylureido)toluene (EHUT)(Fig.6b),diﬀerent ratios of chain stopper 2,4-bis(dibutylureido)toluene (DBUT)were added.By analyzing the SLS data,the values of M w and R g were found to decrease signiﬁcantly,and the value of A 2seemed to be unaﬀparing the measured values of M w and expected molar mass,the ratio lies between 9and 13.33Provided that the supramolecular polymers can form under very dilute concentration,the eﬀect of A 2can be neglected.For example,Ma and Li et al.reported a multivalency-based supramolecular copolymer formed by coordination of pyridines and zinc-porphyrins.SLS experiments showed the average molecular weight of the supramolecular copolymers in toluene is more than 4.2Â106g mol À1,which corresponds to a copolymerization degree higher than 459.35DLS is a popular technique in determining the size distribution of small particles or aggregates.Most commonly,DLS is used to get size distribution information from aggregates formed by supramolecular polymers and to aﬀord auxiliary evidence.36,37For example,Weck and co-workers constructed a kind of supramolecular alternating block copolymer based on coordination between Pd and pyridines.The DLS data clearly showed thatadding AgBF 4,which facilitates the supramolecular polymer-ization,can lead to a signiﬁcant increase in size.36Vapor pressure osmometryThe determination of M n by vapor pressure osmometry (VPO)is based on the principle that the vapor pressure of a solution is lower than that of the pure solvent at the same temperature and pressure.Through Raoult’s law,the M n and the vapor pressure can be related.This method also has been used to deduce the molar mass of supramolecular polymers.Harada et ed VPO as a common approach for the study of the molar mass of supramolecular polymers.38–40For example,supramolecular polymers formed from a cyclodextrin dimer (CD dimer)and homoditopic adamantane derivative (Ad dimer)were prepared (Fig.7a).A 1:1mixture of CD dimer and Ad dimer was measured.The M n was found to rise as the concentration increased,higher than 6Â104at 5mM and reaching 1Â105at 20mM.As a control,the molecular weights of the CD dimer are almost independent of the concentration (Fig.7b).39Mass spectrometryMass spectrometry (MS)has been used for at least two decades for polymer analysis,to determine chemical composi-tions and for end-group identiﬁcation.However,the applica-tion of MS to analyze the molar mass of biomolecules and polymers has been limited owing to the low volatility and thermal instability of these materials.The emergence of so-called soft ionization methods such as matrix-assisted laser desorption ionization time-of-ﬂight MS (MALDI-TOF-MS)has overcomeFig.6(a)Schematic representation of chain stopper inﬂuenced supramolecular polymerization.(b)Structures of EHUT and DBUT (Reproduced with permission of the American Chemical Society from ref.33).Fig.7(a)Structure of the CD dimer and Ad dimer.(b)VPO results for 1:1mixtures of the CD dimer and Ad dimer (rhombus)and CD dimer itself (triangle)(Reproduced with permission of the American Chemical Society from ref.39).P u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.these problems to a great extent.However,to precisely study the molecular weight of supramolecular polymers remains a problematic task.In most cases,only short species or oligo-mers can be detected.41,42Harada et al.showed an example that obtained good mass spectra from supramolecular polymers formed by the host–guest interaction between a -cyclodextrin and the p-tert -butoxyaminocinnamoylamino group.These materials were characterized by turbo ion spray TOF MS,showing that up to 14mer can be detected (Fig.8).38NMR spectroscopyNMR can be used to determine the M n of a polymer by end-group analysis.Once the ratio of protons on the end-groups to protons on the polymer chain is determined,the M n value can be obtained by a simple calculation.In the case of supra-molecular polymers,with properly simpliﬁed assumptions,it also can be used to estimate the DP.Take host–guest inter-action based supramolecular polymers as an example.Assuming that complete complexation will cause a chemical shift D d ,and D d C at a certain monomer concentration.Deﬁning p =D d C /D d ,the DP can be easily calculated to be 1/(1Àp ).43In addition,many supramolecular polymerization processes are similar to a step-wise polymerization mechanism and always have broad distributions.To study the supramolecular poly-merization process,concentration-dependent NMR can be performed.With the increase of monomer concentration,the NMR peaks become more and more broad,indicating the formation of supramolecular polymers.44,45Diﬀusion ordered 1H NMR spectroscopy (DOSY)can directly measure the diﬀusion coeﬃcient and is becoming increasingly popular for supramolecular polymer characterization.46–51The sizes of supramolecular polymers can be qualitatively compared using their corresponding diﬀusion coeﬃcients.Haino and co-workers reported the construction of a supramolecular polymer by molecular recognition between bisporphyrin and trinitroﬂuorenone.49The electron deﬁcient guest moiety at the head,4,5,7-trinitroﬂuorenone-2-carboxylate (TNF),can bind within the bisporphyrin cleft at the tail through a charge-transfer interaction,and the head-to-tail style complexation leads to supramolecular polymerization (Fig.9a).The monomer and its analogue,which is without the TNF moiety,were tested by DOSY.As shown in Fig.9b,the diﬀusion coeﬃcient of the analogue D avg =3.02Â10À10m 2s À1was not noticeably inﬂuenced by concentration.In other words,the independence of the diﬀusion coeﬃcient from concentration indicates that there is no supramolecular polymerization.In contrast,the diﬀusion coeﬃcient of the monomer was stronglyFig.8Positive turbo ion spray TOF mass spectra of 3-p -BocCiNH-a -CD in the range of 3200–18000(Reproduced with permission of the American Chemical Society from ref.38).Fig.9(a)Molecular structures of the heteroditopic monomer and its analogue,and a schematic illustration of the formation of supramolecular polymers.(b)Diﬀusion coeﬃcients of the monomer (cycle)and its analogue (rhombus)under diﬀerent concentrations (Reproduced with permission of Wiley-VCH from ref.49).P u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.dependent on concentration,showing a diﬀusion constant of 2.96Â10À10m 2s À1at 2.34mM,and 3.4Â10À11m 2s À1at 66mM,respectively (Fig.9b).The signiﬁcant decrease of the diﬀusion coeﬃcient with increasing concentration implies that large polymeric aggregates were formed at the higher concen-tration.Simplistically assuming that all the aggregations are hydrodynamically spherical,the Stokes–Einstein equation was used to calculate the average size of the supramolecular polymer at approximately 660times the monomeric form,in other words,the degree of supramolecular polymerization can be estimated to be 660.The above mentioned relationship between diﬀusion and supramolecular polymerization holds true for many systems.Wang et al.prepared a quadruple hydrogen bonded linear supramolecular polymer and then cross-linked it into networks via bisparaquat molecules.50The DOSY results showed that as the monomer concentration increased,the diﬀusion coeﬃcient decreased gradually,which suggests that longer supramolecular polymers were formed.After cross-linking,the diﬀusion coeﬃcient became much smaller than those of linear supra-molecular polymers.Scherman et ed DOSY to probe cucurbit[8]uril-mediated supramolecular block copolymers.51Polymers bearing a naphthalene moiety and a bisparaquat derivative can assemble together by the encapsulation of cucurbit[8]uril (CB[8])and form a kind of polymer-based supramolecular block polymer.The naphthalene attached polymer and bisparaquat derivative showed log D =À10.12and À9.53,respectively.Upon adding CB[8],the whole system only shows a single diﬀusion coeﬃcient (log D =À10.2).This means that all the components are diﬀusing as one entity,thus conﬁrming the formation of the target supramolecular block copolymer.Scanning probe microscopy and electron microscopyScanning probe microscopy (SPM)and electron microscopy are commonly used in studying supramolecular polymer morphology over various scales.Scanning tunneling micro-scopy (STM)can image the sample at the atomic scale and is capable of characterizing a supramolecular polymer when it is rigid and big enough.52–54To avoid supramolecular polymers interlacing together,a dilute sample concentration is always required.For example,Liu and co-workers used cyclodextrin–Tb polyads and C 60constructed supramolecular polymers (Fig.10).The end-to-end inclusion complexation of cyclodextrin cavities with C 60s drive the polyads and C 60to assemble into a polymer chain structure.The STM images clearly displayed the ﬁne structure of the supramolecular polymer chain.The width and height of the structure ﬁt the model quite well.54Atomic force microscopy (AFM)is another high-resolution type of SPM,with resolution in the order of a single nano-metre.The technique has been widely used in imaging the morphology of sample surfaces and can provide a three-dimensional surface proﬁle.55,56For surface grafted supra-molecular polymers,AFM has proved to be a suitable technique to measure growth height.Kim et al.constructed poly(pseudo-rotaxane)on a gold surface (Fig.11).Using AFM analysis,the height of the substrate was seen to have increased by 3.9nm onaverage after the growth of the poly(pseudorotaxane),which suggests that the poly(pseudorotaxane)was grown on the gold substrate with four repeating units.57Hayashi et al.prepared a surface grafted supramolecular polymer by speciﬁc heme–heme pocket interactions between zinc porphyrins and hemo-proteins.The average height of the assemblies on the surface was 15.5nm measured by AFM,which corresponds to around seven repeating units.58Normally,transmission electron microscopy (TEM)can be used to visualize aggregates formed by supramolecular polymers.Schmuck et ed metal coordination and self-complementary zwitterions two orthogonal binding interactions to construct switchable supramolecular polymers.Cryo-TEM,which provides direct structural data from vitriﬁed aqueous solution,revealed linear supramolecular polymer strands.The presence of metal ions in the aggregates gave a good contrast to the images.59Scanning electron microscopy can be used to image supramolecular polymer assemblies with micro-or even larger sizes.For example,rod-like ﬁbers with a regular diameter drawn from high concentration supramolecular polymer solution were clearly observed.60AFM-based single molecule force spectroscopyThe application of atomic force microscopy (AFM)has extended our ability to see the small world.Actually,AFM is not only a powerful tool for the imaging of surfaces with high resolution,but also a highly sensitive force sensor.Single molecule force spectroscopy (SMFS),a developing technique based on AFM,has become a platform for studying the minute forces in polymers as well as in supramolecular systems.61–63In a general SMFS experiment,the polymer chain can form a bridge between the AFM tip and the substrate;such a polymer chain will be stretched when the tip and the substrate separate.At the same time,the deﬂection of the cantilever and the displacement of the piezotube are recorded.Then the deﬂection is converted into a force signal,and the relationship between the force and the extension length is obtained.Many elegant experiments about SMFS have been done,such as the entropic and enthalpic elasticity of a single polymer chain,force-induced conformational transition,the melting and unzipping force of double-stranded DNA,interaction between macromolecules and small molecules,interfacial conformation and desorption force of macromolecules.Owing to similar ‘‘polymer chain’’structures,supramolecular polymers can also be characterized by SMFS.64–70An example of characterization of hydrogen bonding supramolecular poly-mers by SMFS was reported by Vancso and co-workers.64As shown in Fig.12,the SMFS experiments were performed with AFM tips and substrates that were both functionalized with 2-ureido-4[1H ]-pyrimidinone (UPy)moieties in the presence of a homoditopic monomer UPy-UPy solution.Supramolecular polymers formed bridges between the tip and substrate.Stretching lengths of more than 150nm were detected,which suggests that supramolecular polymers with a DP up to 15were formed.As a control,after adding DMSO,which can disrupt hydrogen bonds,no long supramolecular polymers were detected.Similarly,by using chemical anchoring approaches,other types of supramolecular polymers haveP u b l i s h e d o n 06 J u n e 2012. D o w n l o a d e d b y B e i j i n g U n i v e r s i t y o f C h e m i c a l T e c h n o l o g y o n 04/04/2015 01:57:32.。