超分子化学 合成受体的分子识别与组装PDF电子书下载

1．1 From molecular chemistry to supramolecular chemistry 1

1．1 从分子化学到超分子化学 1

第1章 超分子化学概述 1

Chapter 1 Brief introduction of supramolecular chemistry 1

1．2 Fundamental concept of molecular recognition 2

1．2分子识别的基本概念 2

1．3分子组装的基本概念 3

1．3 Fundamental concept of molecular assembly 3

References 5

参考文献 5

2．1 Synthesis of crown compounds 6

2．1．1 Introduction 6

第2章 冠状化合物为受体的分子识别与组装 6

2．1冠状化合物的合成 6

2．1．1概述 6

Chapter 2 Molecular recognition and assembly with crown compounds as receptors 6

2．1．2 Nomenclature of crown compounds 7

2．1．2冠状化合物的命名 7

2．1．3 Synthesis of crown compounds 8

2．1．3冠状化合物的合成 8

2．2．1概述 38

2．2冠醚化合物的分子识别 38

2．2 Molecular recognition of crown ethers 38

2．2．1 Introduction 38

2．2．2 Symmetric crown ethers 40

2．2．2一般对称性冠醚 40

2．2．3 Crown ethers of low symmetry 48

2．2．3低对称性冠醚 48

2．2．4 臂式冠醚 57

2．2．4 Lariat ethers 57

2．2．5双冠醚 90

2．2．5 Bis(crown ether)s 90

2．2．6 Cryptands 104

2．2．6 穴醚 104

2．2．7 其他类型冠醚 114

2．2．7 Hybrid crown ethers 114

2．3．1由单一分子形成的组装体 123

2．3以冠醚为受体的分子组装 123

2．3 Molecular assembly of crown ethers 123

2．3．1 Assembly by single component 123

2．3．2 Assembly by double components 128

2．3．2由两种分子形成的组装体 128

2．3．3 Assembly by multiple components 132

2．3．3 由多种分子形成的组装体 132

2．3．4索烃（Catenanes） 137

2．3．4 Catenanes 137

2．3．5 Pseudorotaxanes and rotaxanes 143

2．3．5 轮烷（Rotaxanes）和准轮烷（Pseudorotaxanes） 143

References 150

参考文献 150

Chapter 3 Molecular recognition and assembly with cyclodextrins as receptors 166

3．1 Structural feature of cyclodextrin 166

3．1．1 Historical background of cyclodextrins 166

3．1．1环糊精研究的历史背景 166

3．1 环糊精的基本结构特征 166

第3章 以环糊精为受体的分子识别与组装 166

3．1．2 Peparation of cyclodextrins 167

3．1．2环糊精的制备 167

3．1．3 Structure and physical properties of cyclodextrins 168

3．1．3环糊精的结构和物理性质 168

3．2 Synthetic strategy of cyclodextrin derivatives 171

3．2 环糊精衍生物的合成方法 171

3．2．1 Mono modification on the primary side 172

3．2．1 6位单取代环糊精的制备 172

3．2．2 2位和3位单取代环糊精的制备 180

3．2．2 Mono modification on the secondary side 180

3．2．3 Multiple substituted cyclodextrins 187

3．2．3 多取代环糊精的制备 187

3．3．1 Intermolecular forces analysis of the inclusion complexation by cyclodextrins 191

3．3 Molecular recognition of cyclodextrins and their derivatives 191

3．3 环糊精及其衍生物的分子识别研究 191

3．3．1环糊精包结配位过程中的分子间力相关分析 191

3．3．2天然环糊精的包结配位作用 193

3．3．2 Inclusion complexation of native cyclodextrins 193

3．3．3 Molecular recognition of positively charged cyclodextrins 207

3．3．3 拥有电荷中心的简单修饰糊精的分子识别 207

3．3．4 Molecular recognition of chromophoric cyclodextrins 215

3．3．4 拥有生色基的简单修饰环糊精的分子识别 215

3．3．5 Molecular recognition of bridged bis(cyclodextrin)s 239

3．3．5 桥联环糊精的分子识别 239

3．4 环糊精及其衍生物的模拟酶研究 249

3．4 Cyclodextrins and their derivatives as enzyme models 249

3．4．1水解酶的模拟 250

3．4．1 Mimics of hydrolyse 250

3．4．2 Mimics of transaminase 255

3．4．2 转氨酶的模拟 255

3．4．3 核糖核酸酶的模拟 258

3．4．3 Mimics of ribonuclease 258

3．4．4 氧化还原酶的模拟 262

3．4．4 Mimics of oxido reductase 262

3．4．5 其他类型的人工酶 267

3．4．5 Other enzyme mimics 267

3．5．1 Self-assembly of cyclodextrin derivatives with hydrophobic substituent in solution and solid state 270

3．5 Molecular assembly with cyclodextrins as receptors 270

3．5以环糊精为受体的分子组装 270

3．5．1拥有疏水性取代基环糊精衍生物在溶液和固态中的自组 270

3．5．2 Self-assembly with small molecules as bridge in solution and solid state 273

3．5．2 通过小分子桥在水溶液和固态中的自组装 273

3．5．3 分子索烃 275

3．5．3 Catenanes 275

3．5．4 Pseudorotaxanes and rotaxanes 277

3．5．4 轮烷与准轮烷 277

3．5．5 Mono layers and multiple layers 286

3．5．5 单分子膜和多层膜 286

3．5．6其他类型的环糊精组装体 288

3．5．6 Other assembly of cyclodextrins 288

References 291

参考文献 291

Chapter 4 Molecular recognition and assembly with calixarenes as receptors 306

第4章 杯芳烃为受体的分子识别与组装 306

4．1杯芳烃的合成与制备 308

4．1．1一步合成法 308

4．1 Synthesis and preparation of calixarenes 308

4．1．1 One-pot procedures 308

4．1．2多步合成法 311

4．1．2 Stepwise synthesis 311

4．1．3 Fragment condensation 313

4．1．3片段缩合法 313

4．1．4其他类型杯状化合物的合成 317

4．1．4 Synthesis of other related macrocycles 317

4．1．5 Derivation of calixarenes 320

4．1．5 杯芳烃的衍生化 320

4．2 Conformations of calixarenes 328

4．2杯芳烃的构象 328

4．3．1对中性分子的识别 333

4．3．1 Neutral molecule recognition by calixarenes 333

4．3 Molecular and ion recognition of calixarenes 333

4．3杯芳烃的分子识别和离子识别 333

4．3．2 对有机阳离子的识别 338

4．3．2 Organic cation recognition by calixarenes 338

4．3．3 对金属阳离子的识别 340

4．3．3 Metal ion recognition by calixarenes 340

4．3．4 Anion recognition by calixarenes 351

4．3．4 对阴离子的识别 351

4．4 Molecular catalysis and artificial enzyme with calixarenes as receptors 356

4．4杯芳烃为受体的分子催化和模拟酶研究 356

4．4．1相转移催化 356

4．4．1 Phase transfer catalysis 356

4．4．2 Mimic enzymes 358

4．4．2模拟酶 358

4．5以杯芳烃为受体的分子组装 361

4．5 Moleculr assembly with calixarenes as receptors 361

References 372

参考文献 372

Chapter 5 Molecular recognition and assembly with other macrocycles as receptors 385

第5章 其他类型大环化合物为受体的分子识别与组装 385

5．1 Cucurbituril 385

5．1 葫芦脲 385

5．1．1 Molecular recognition 387

5．1．1分子识别 387

5．1．2超分子催化 393

5．1．2 Supramolecular catalysis 393

5．1．3 Molecular assembly 394

5．1．3分子组装 394

5．2卟啉和酞菁 400

5．2 Porphyrins and phthalocyanines 400

5．2．1分子识别 401

5．2．1 Molecular recognition 401

5．2．2超分子催化 420

5．2．2 Supramolecular catalysis 420

5．2．3 Supramolecular self-assembly 429

5．2．3超分子自组装 429

5．3．1 Ion recognition 439

5．3环肽 439

5．3．1离子识别 439

5．3 Cyclopeptides 439

5．3．2环肽构筑的有机纳米管道 443

5．3．2 Organo nanotube constructed by cyclopeptides 443

References 448

参考文献 448

6．1大环化合物离子识别的热力学性质 454

第6章 超分子体系中分子识别的热力学起源 454

Chapter 6 Thermodynamic origin of molecular recognition in supramolecular system 454

6．1 Thermodymamics of ion recognition by macrocycles 454

6．1．1离子-配体络合作用的热力学参数 455

6．1．1 Thermodynamic parameters for cation-ligand complexation 455

6．1．2 焓熵补偿 500

6．1．2 Enthalpy-entropy compensation 500

6．2大环化合物分子识别的热力学性质 510

6．1．3 结论 510

6．1．3 Conclusions 510

6．2 Thermodynamics of molecular recognition by macrocycles 510

6．2．1 Thermodynamic origin of molecular recognition by cyclodextrin 511

6．2．1环糊精分子识别的热力学起源 511

6．2．2 卟啉分子识别的热力学起源 573

6．2．2 Thermodynamic origin of molecular recognition by porphyrin 573

6．2．3 Thermodynamic origin of molecular recognition by cyclophane and calixarene 579

6．2．3 环番和杯芳烃分子识别的热力学起源 579

6．3 结论 583

6．3 Conclusions 583

References 585

参考文献 585

Chapter 7 Determination of stability constants in supramolecular system 597

第7章 超分子体系的稳定常数测定 597

7．1．2 量热数据的处理和计算方法 598

7．1．1基本原理 598

7．1量热滴定法 598

7．1．2 Data analysis and calculation method for calorimetry 598

7．1．1 General principle 598

7．1 Calorimetry 598

7．2 Extraction Techniques 604

7．2．1 Solvent extraction of metal ions and organic cations with electrically neutral extractants 604

7．2．1电中性萃取剂对金属离子及有机离子的溶剂萃取 604

7．2溶剂萃取法 604

7．2．2 Solvent extraction of metal ions with proton-dissociable extractants 609

7．2．2可质子化萃取剂对金属离子的溶剂萃取 609

7．3．1 Determination of stoichiometric quality 613

7．3 Spectroscopic methods 613

7．3 光谱滴定法 613

7．3．1化学计量比的确定 613

7．3．2 Measurement of complex stability constant by spectroscopic titration 616

7．3．2 光谱滴定法测定配合物稳定常数 616

7．3．3 Measurement of complex stability constant by competitive inclusion 620

7．3．3竞争包结法测定超分子配合物的稳定常数 620

References 621

参考文献 621

Concluding remarks 624

结束语 624