Tài liệu Khái niệm hóa học về vật liệu nano

XXI
Member Societies XXV
Part One Self-Organization, Nanoscience and Nanotechnology
1 Subcomponent Self-Assembly as a Route to New Structures and
Materials 3
Jonathan R. Nitschke
1.1 Introduction 3
1.2 Aqueous Cu(I) 5
1.3 Chirality 7
1.4 Construction 8
1.4.1 Dicopper Helicates 8
1.4.2 Tricopper Helicates 10
1.4.3 Catenanes and Macrocycles 11
1.4.4 [2 × 2] Tetracopper(I) Grid 12
1.5 Sorting 13
1.5.1 Sorting Ligand Structures with Cu(I) 13
1.5.2 Simultaneous Syntheses of Helicates 13
1.5.3 Sorting within a Structure 14
1.5.4 Cooperative Selection by Iron and Copper 17
1.6 Substitution/Reconfi guration 20
1.6.1 New Cascade Reaction 20
1.6.2 Hammett Effects 22
1.6.3 Helicate Reconfi gurations 23
1.6.4 Substitution as a Route to Polymeric Helicates 24
1.7 Conclusion and Outlook 27
1.8 Acknowledgments 27
Contents
V
Tomorrow’s Chemistry Today. Concepts in Nanoscience, Organic Materials and Environmental Chemistry.
Edited by Bruno Pignataro
Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31918-3
VI Contents
2 Molecular Metal Oxides and Clusters as Building Blocks for Functional
Nanoscale Architectures and Potential Nanosystems 31
Leroy Cronin
2.1 Introduction 31
2.2 From POM Building Blocks to Nanoscale Superclusters 33
2.3 From Building Blocks to Functional POM Clusters 37
2.3.1 Host–Guest Chemistry of POM-based Superclusters 38
2.3.2 Magnetic and Conducting POMs 39
2.3.3 Thermochromic and Thermally Switchable POM Clusters 40
2.4 Bringing the Components Together – Towards Prototype
Polyoxometalate-based Functional Nanosystems 42
2.5 Acknowledgments 44
3 Nanostructured Porous Materials: Building Matter from the Bottom
Up 47
Javier García-Martínez
3.1 Introduction 47
3.2 Synthesis by Organic Molecule Templates 48
3.3 Synthesis by Molecular Self-Assembly: Liquid Crystals and Cooperative
Assembly 50
3.4 Spatially Constrained Synthesis: Foams, Microemulsions, and
Molds 57
3.4.1 Microemulsions 57
3.4.2 Capping Agents 57
3.4.3 Foams 58
3.4.4 Molds 59
3.5 Multiscale Self-Assembly 59
3.6 Biomimetic Synthesis: Toward a Multidisciplinary Approach 61
3.7 Acknowledgments 69
4 Strategies Toward Hierarchically Structured Optoelectronically Active
Polymers 73
Eike Jahnke and Holger Frauenrath
4.1 Hierarchically Structured Organic Optoelectronic Materials via
Self-Assembly 73
4.2 Toward Hierarchically Structured Conjugated Polymers via the
Foldamer Approach 74
4.3 “Self-Assemble, then Polymerize” – A Complementary Approach and Its
Requirements 78
4.3.1 Topochemical Polymerization Using Self-Assembled Scaffolds 79
4.3.2 Self-Assembly of β-Sheet Forming Oligopeptides and Their Polymer
Conjugates 80
4.4 Macromonomer Design and Preparation 82
4.5 Hierarchical Self-Organization in Organic Solvents 85
Contents VII
4.6 A General Model for the Hierarchical Self-Organization of
Oligopeptide–Polymer Conjugates 89
4.7 Conversion to Conjugated Polymers by UV Irradiation 92
4.8 Conclusions and Perspectives 95
4.9 Acknowledgments 95
5 Mimicking Nature: Bio-inspired Models of Copper Proteins 101
Iryna A. Koval, Patrick Gamez and Jan Reedijk
5.1 Environmental Pollution: How Can “Green” Chemistry Help? 101
5.2 Copper in Living Organisms 102
5.2.1 Type 1 Active Site 102
5.2.2 Type 2 Active Site 103
5.2.3 Type 3 Active Site 104
5.2.4 Type 4 Active Site 104
5.2.5 The CuA Active Site 104
5.2.6 The CuB Active Site 105
5.2.7 The CuZ Active Site 105
5.3 Catechol Oxidase: Structure and Function 105
5.3.1 Catalytic Reaction Mechanism 107
5.4 Model Systems of Catechol Oxidase: Historic Overview 108
5.5 Our Research on Catechol Oxidase Models and Mechanistic
Studies 114
5.5.1 Ligand Design 114
5.5.2 Copper(I) and Copper(II) Complexes with [22]py4pz: Structural
Properties and Mechanism of the Catalytic Reaction 114
5.5.3 Copper(I) and Copper(II) Complexes with [22]pr4pz: Unraveling
Catalytic Mechanisms 118
5.6 Concluding Remarks 124
5.7 Acknowledgments 125
6 From the Past to the Future of Rotaxanes 129
Andreea R. Schmitzer
6.1 Introduction 129
6.2 Synthesis of Rotaxanes 131
6.2.1 Van der Waals Interactions in the Synthesis of Rotaxanes 132
6.2.2 Hydrophobic Interactions in the Synthesis of Rotaxanes 133
6.2.3 Hydrogen Bonding in Rotaxane Synthesis 134
6.2.4 Donor–Acceptor Interactions in the Synthesis of Rotaxanes 135
6.2.5 Transition-Metal Coordination in the Synthesis of Rotaxanes 136
6.3 Applications of Rotaxanes 137
6.3.1 Rotaxanes as Molecular Shuttles 137
6.3.1.1 Acid–Base-controlled Molecular Shuttle 139
6.3.1.2 A Light-driven Molecular Shuttle 140
6.3.2 Molecular Lifts 142
VIII Contents
6.3.3 Artifi cial Molecular Muscles 143
6.3.4 Redox-activated Switches for Dynamic Memory Storage 144
6.3.5 Bioelectronics 147
6.3.6 Membrane Transport 149
6.3.7 Catalytically Active Rotaxanes as Processive Enzyme Mimics 151
6.4 Conclusion and Perspectives 152
7 Multiphoton Processes and Nonlinear Harmonic Generations in
Lanthanide Complexes 161
Ga-Lai Law
7.1 Introduction 161
7.2 Types of Nonlinear Processes 162
7.3 Selection Rules for Multiphoton Absorption 164
7.4 Multiphoton Absorption Induced Emission 165
7.5 Nonlinear Harmonic Generation 176
7.6 Conclusion and Future Perspectives 181
7.7 Acknowledgments 181
8 Light-emitting Organic Nanoaggregates from Functionalized
para-Quaterphenylenes 185
Manuela Schiek
8.1 Introduction to para-Phenylene Organic Nanofi bers 185
8.2 General Aspects of Nanofi ber Growth 187
8.3 Synthesis of Functionalized para-Quaterphenylenes 189
8.4 Variety of Organic Nanoaggregates from Functionalized
para-Quaterphenylenes 193
8.5 Symmetrically Functionalized p-Quaterphenylenes 194
8.6 Differently Di-functionalized p-Quaterphenylenes 197
8.7 Monofunctionalized p-Quaterphenylenes 199
8.8 Tailoring Morphology: Nanoshaping 200
8.9 Tailoring Optical Properties: Linear Optics 201
8.10 Creating New Properties: Nonlinear Optics 203
8.11 Summary 205
8.12 Acknowledgments 205
9 Plant Viral Capsids as Programmable Nanobuilding Blocks 215
Nicole F. Steinmetz
9.1 Nanobiotechnology – A Defi nition 215
9.2 Viral Particles as Tools for Nanobiotechnology 216
9.3 General Introduction to CPMV 216
9.4 Advantages of Plant Viral Particles as Nanoscaffolds 219
9.5 Addressable Viral Nanobuilding Block 220
9.6 From Labeling Studies to Applications 222
9.7 Immobilization of Viral Particles and the Construction of Arrays on
Solid Supports 229
Contents IX
9.8 Outlook 231
9.9 Acknowledgments 232
10 New Calorimetric Approaches to the Study of Soft Matter 3D
Organization 237
J.M. Nedelec and M. Baba
10.1 Introduction 237
10.2 Transitions in Confi ned Geometries 238
10.2.1 Theoretical Basis 239
10.2.1.1 Confi nement Effect on Triple-point Temperature 239
10.2.2 Porosity Measurements via Determination of the Gibbs–Thomson
Relation 240
10.2.2.1 Thermoporosimetry 241
10.2.2.2 NMR Cryoporometry 241
10.2.2.3 Surface Force Apparatus 241
10.2.3 Thermoporosimetry and Pore Size Distribution Measurement 242
10.3 Application of Thermoporosimetry to Soft Materials 243
10.3.1 Analogy and Limitations 243
10.3.2 Examples of Use of TPM with Solvent Confi ned by Polymers and
Networks 244
10.3.2.1 Elastomers 244
10.3.2.2 Hydrogels 246
10.3.2.3 Polymeric Membranes 246
10.3.2.4 Crosslinking of Polyolefi ns 246
10.4 Study of the Kinetics of Photo-initiated Reactions by PhotoDSC 247
10.4.1 The PhotoDSC Device 247
10.4.2 Photocuring and Photopolymerization Investigations 247
10.5 Accelerated Aging of Polymer Materials 251
10.5.1 Study of Crosslinking of Polycyclooctene 251
10.5.1.1 Correlation between Oxidation and Crystallinity 251
10.5.1.2 Crosslinking and Crystallizability 253
10.5.1.3 Photo-aging Study by Macroperoxide Concentration
Monitoring 254
10.5.2 Kinetics of Chain Scissions during Accelerated Aging of
Poly(ethylene oxide) 255
10.5.2.1 Chain Scission Kinetics from Melting 256
10.6 Conclusion 258
Part Two Organic Synthesis, Catalysis and Materials
11 Naphthalenediimides as Photoactive and Electroactive Components in
Supramolecular Chemistry 265
Sheshanath Vishwanath Bhosale
11.1 Introduction 265
11.2 General Syntheses and Reactivity 266
X Contents
11.2.1 Synthesis of Core-substituted NDIs 268
11.2.2 General Chemical and Physical Properties 268
11.3 Redox and Optical Properties of NDIs 271
11.3.1 NDIs in Host–Guest Chemistry 272
11.3.2 NDI-DAN Foldamers 272
11.3.3 Ion Channels 273
11.3.4 NDIs in Material Chemistry 275
11.4 Catenanes and Rotaxanes 276
11.4.1 NDIs Used as Sensors 277
11.4.2 Nanotubes 279
11.5 NDIs in Supramolecular Chemistry 281
11.5.1 Energy and Electron Transfer 281
11.5.2 Covalent Models 281
11.5.3 Noncovalent Models 284
11.6 Applications of Core-Substituted NDIs 287
11.7 Prospects and Conclusion 290
11.8 Acknowledgment 290
12 Coordination Chemistry of Phosphole Ligands Substituted with Pyridyl
Moieties: From Catalysis to Nonlinear Optics and Supramolecular
Assemblies 295
Christophe Lescop and Muriel Hissler
12.1 Introduction 295
12.2 π-Conjugated Derivatives Incorporating Phosphole Ring 296
12.2.1 Synthesis and Physical Properties 296
12.2.2 Fine Tuning of the Physical Properties via Chemical Modifi cations of
the Phosphole Ring 298
12.3 Coordination Chemistry of 2-(2-Pyridyl)phosphole Derivatives:
Applications in Catalysis and as Nonlinear Optical Molecular
Materials 300
12.3.1 Syntheses and Catalytic Tests 300
12.3.2 Isomerization of Coordinated Phosphole Ring into
2-Phospholene Ring 301
12.3.3 Square-Planar Complexes Exhibiting Nonlinear
Optical Activity 303
12.3.4 Ruthenium Complexes 304
12.4 Coordination Chemistry of 2,5-(2-Pyridyl)phosphole Derivatives:
Complexes Bearing Bridging Phosphane Ligands and Coordinationdriven
Supramolecular Organization of π-Conjugated
Chromophores 305
12.4.1 Bimetallic Coordination Complexes Bearing a Bridging Phosphane
Ligand 305
12.4.1.1 Pd(I) and Pt(I) Bimetallic Complexes 306
12.4.1.2 Cu(I) Bimetallic Complexes 307
Contents XI
12.4.2 Supramolecular Organization of π-Conjugated Chromophores via
Coordination Chemistry: Synthesis of Analogues of
[2.2]-Paracyclophanes 310
12.5 Conclusions 314
12.6 Acknowledgments 315
13 Selective Hydrogen Transfer Reactions over Supported Copper Catalysts
Leading to Simple, Safe, and Clean Protocols for Organic Synthesis 321
Federica Zaccheria and Nicoletta Ravasio
13.1 Chemoselective Reduction of Polyunsaturated Compounds via
Hydrogen Transfer 323
13.2 Alcohol Dehydrogenation 325
13.3 Racemization of Chiral Secondary Alcohols 331
13.4 Isomerization of Allylic Alcohols 331
13.5 Conclusions 333
14 Selective Oxido-Reductive Processes by Nucleophilic Radical Addition
under Mild Conditions 337
Cristian Gambarotti and Carlo Punta
14.1 Introduction 337
14.2 Nucleophilic Radical Addition to N-heteroaromatic Bases 338
14.2.1 Acylation of N-heteroaromatic Bases 338
14.2.2 Acylation of N-heteroaromatic Bases Catalyzed by
N-hydroxyphthalimide 340
14.2.3 Photoinduced Nucleophilic Radical Substitution in the Presence of
TiO2 341
14.2.4 Hydroxymethylation of N-heteroaromatic Bases 343
14.2.5 Perfl uoroalkylation of N-heteroaromatic Bases and Quinones 344
14.3 Nucleophilic Radical Addition to Aldimines 345
14.3.1 Nucleophilic Radical Addition Promoted by TiCl3/PhN2
+ Systems 345
14.3.2 Nucleophilic Radical Addition Promoted by TiCl3/Pyridine
Systems 347
14.3.3 Nucleophilic Radical Addition Promoted by TiCl3/Hydroperoxide
Systems 348
Part Three Health, Food, and Environment
15 Future Perspectives of Medicinal Chemistry in the View of an Inorganic
Chemist 355
Palanisamy Uma Maheswari
15.1 Introduction 355
15.1.1 Conventional versus Targeted Therapy 358
15.2 Ruthenium Anticancer Drugs 359
15.2.1 Ru–Polypyridyl Complexes 359
XII Contents
15.2.2 Ru–Polyaminocarboxylate Complexes 361
15.2.3 Ru-Dimethyl Sulfoxide Complexes 362
15.2.4 Ru–Arylazopyridine Complexes 363
15.2.5 Ru–Organometallic Arene Complexes 365
15.2.6 NAMI-A Type Complexes 366
15.2.7 The Transferrin Delivery Mechanism 367
15.2.8 Discerning Estrogen Receptor Modulators Based on Ru 368
15.2.9 Ru–Ketoconazole Complexes 369
15.2.10 Protein Kinase Inhibitors Based on Ru 369
15.2.11 Ru–RAPTA Complexes 370
15.3 Chemical Nucleases as Anticancer Drugs 373
15.4 Inorganic Chemotherapy for Cancer: Outlook 378
15.5 Acknowledgments 381
16 Speeding Up Discovery Chemistry: New Perspectives in Medicinal
Chemistry 389
Matteo Colombo and Ilaria Peretto
16.1 Solid-phase Extraction 390
16.2 Polymer-assisted Solution-phase Synthesis 392
16.3 Microwave-assisted Organic Synthesis [10, 11] 395
16.4 Flow Chemistry 400
16.5 Analytical Instrumentation 404
16.6 Conclusions 405
17 Overview of Protein-Tannin Interactions 409
Elisabete Barros de Carvalho, Victor Armando Pereira de Freitas and
Nuno Filipe da Cruz Batista Mateus
17.1 Phenolic Compounds 409
17.2 Tannin Structures 410
17.2.1 Dietary Burden and Properties of Phenolic Compounds 411
17.3 Interactions between Proteins and Tannins 412
17.4 Experimental Studies of the Interactions between Proteins and
Tannins 412
17.4.1 Nephelometric Studies of BSA and Condensed Tannin
Aggregation 413
17.5 Factors That Infl uence the Interactions between Proteins and
Tannins 415
17.5.1 Structural Features 415
17.5.2 pH and Ionic Strength 415
17.5.3 Infl uence of Polysaccharide on the Interactions between Protein and
Tannin 417
17.6 Flow Nephelometric Analysis of Protein–Tannin Interactions 419
17.7 Interactions of Tannins with Salivary Proteins – Astringency 421
17.8 Polysaccharides and Astringency 423
17.9 Acknowledgments 425
Contents XIII
18 Photochemical Transformation Processes of Environmental
Signifi cance 429
Davide Vione
18.1 Introduction and Overview of Environmental Photochemistry 429
18.1.1 Photochemical Processes in the Atmosphere 429
18.1.2 Photochemical Reactions in Ice and Snow 434
18.1.3 Photochemical Reactions in Surface Waters 435
18.2 Transformation Reactions Induced by ãOH, ãNO2 and Cl2
ãư in Surface
Waters 437
18.2.1. Reactions Induced by ãOH 437
18.2.2 Reactions Induced by ãNO2 445
18.2.3 Reactions Induced by Cl2
ãư 446
18.3 Conclusions 448
18.4 Acknowledgments 449
Index 455