1. Precise Synthesis of Supramoiecules
1.1. An Integrated Systems-oriented Approach to Molecular
Electronics ................................................ 2
1.1.1. Introduction ........................................ 2
1.1.2. Catenane-based Devices .............................. 3
1.1.3. Amphiphilic Single-station Rotaxane-based
Devices ............................................ 10
1.1.4. Amphiphilic Bistable Pseudorotaxane-based
Devices ............................................ 13
1.1.5. A Slow Amphiphilic Bistable Rotaxane-based
Device ............................................. 15
1.1.6. A Fast Amphiphilic Bistable Rotaxane-based
Device ............................................. 18
1.1.7. The Best Amphiphilic Bistable Rotaxane-based
Device to Date ..................................... 20
1.1.8. Concluding Remarks ................................. 21
1.2. Supramolecular Polymers Containing Cyclodextrin ........... 26
1.2.1. Introduction ....................................... 26
1.2.2. Cyclodextrins ...................................... 27
1.2.3. Rotaxanes .......................................... 28
1.2.4. Polyrotaxanes ...................................... 30
1.2.5. Molecular Shuttle .................................. 33
1.2.6. Electronic Trap .................................... 34
1.2.7. Supramolecular Polymers ............................ 34
A. Intramolecular Complexation ..................... 34
B. Intermolecular Complexation ..................... 35
C. Supramolecular Polymers ......................... 36
1.2.8. Daisy Chain Necklace ............................... 39
1.2.9. Conclusion ......................................... 39
1.3. Cucurbituril: A Versatile "Bead" for Polyrotaxane
Synthesis ................................................. 41
1.3.1. Introduction ....................................... 41
1.3.2. Cucurbituril ....................................... 42
1.3.3. Conclusions ........................................ 59
1.3.4. Summary ............................................ 59
References ..................................................... 60
2. Macromolecular Organic Assemblies
2.1. Nanometer-size Multispin Macromolecules and Their
Magnetic Force Microscopic Images ......................... 66
2.1.1. Introduction ....................................... 66
2.1.2. Macromolecules Bearing Radical Groups .............. 66
2.1.3. Magnetic Force Microscopy .......................... 73
2.1.4. Magnetic Force Microscopic Images of
Magnetically Responsive Macromolecules ............. 74
2.2. Synthesis and Characterization of New Highly Soluble
Organic Polyimides ........................................ 80
2.2.1. Introduction ....................................... 80
2.2.2. Characterization of the Novel Polyimides ........... 81
A. Monomer Synthesis ............................... 81
B. Preparation of Novel Polyimides ................. 83
С. Solubility ...................................... 87
D. Crystallinity ................................... 93
E. Thermal Property ................................ 95
F. Electrical and Optical Properties ............... 98
2.3. "Inorganic" Combinatorial Chemistry Utilizing
Sol-Gel Transcription of Gelatinous Organic
Superstructures .......................................... 101
2.3.1. Introduction ...................................... 101
2.3.2. Sol-Gel Transcription with Different Gel
Templates ......................................... 102
A. Cholesterol-based Gels as Templates ............ 102
B. Gelators with Amide and Urea Moieties
as Templates ................................... 106
2.3.3. Combinatorial Approach to Sol-Gel
Transcription ..................................... 107
A. Carbohydrate-based Derivatives as a
Source for Novel Gel Templates ................. 109
B. Sol-Gel Transcription with Carbohydrate
Gels as Templates .............................. 112
2.3.4. Summary and Outlook ............................... 116
2.4. Development of Organogelators Based on
Supramolecular Chemistry ................................. 118
2.4.1. Introduction ..................................... 118
2.4.2. Low Molecular Weight Organogelators ............... 119
2.4.3. Organogelators of Amino Acid Derivatives .......... 119
2.4.4. Cyclic Dipeptides as Organogelators ............... 126
2.4.5. 01igo(peptide)s as Organogelators ................. 128
2.4.6. Two-component Type of Organogelators .............. 129
2.4.7. trans- 1,2-Cyclohexanediamine Derivatives
as Organogelators ................................. 131
2.4.8. Trialkyl-1,3,5-benzenetricarboxamide and
Trialkyl-d.v-1,3,5-cyclohexanetricarboxamide ...... 135
2.4.9. Organogelators Based on
2-Amino-2-phenylethanol ........................... 136
2.5. Synthesis and Self-association of
Stimuli-responsive Block Copolymers
by Living Cationic Polymerization ........................ 138
2.5.1. Introduction ...................................... 138
2.5.2. Results and Discussion ............................ 139
A. Living Cationic Polymerization in the
Presence of Added Bases and Synthesis
of Various Functional Polymers ................. 139
B. Synthesis of Copolymers of Various Shapes ...... 142
C. Synthesis and Self-association of
Stimuli-responsive Block Copolymers ............ 145
2.5.3. Summary ........................................... 148
References .................................................... 150
3. Macromolecular Inorganic Assemblies
3.1. Spherical, Fibrous Rock- and Sheet -like
Noncovalent Polymers ..................................... 156
3.1.1. Introduction ...................................... 156
3.1.2. Spheres ........................................... 156
3.1.3. Fibers ............................................ 160
3.1.4. Nanometer Rocks on Smooth Surfaces ................ 162
3.1.5. Planar Sheets ..................................... 165
3.1.6. Conclusion ........................................ 166
3.1.7. Summary ........................................... 167
3.2. Macromolecular Conjugated Complexes ...................... 168
3.2.1. Introduction ...................................... 168
3.2.2. Complexes with Redox-active π-Conjugated
Polymers .......................................... 170
3.2.3. Complexes with Redox-active π-Conjugated
Molecules ......................................... 174
3.2.4. Redox-active π-Conjugated Systems ................. 179
3.2.5. Conclusions ....................................... 181
3.3. Polymer-capped Bimetallic Nanoclusters as Active
and Selective Catalysts .................................. 182
3.3.1. Introduction ...................................... 182
3.3.2. Preparation and Structure of Polymer-capped
Bimetallic Nanoclusters ........................... 183
A. Coreduction of Mixed Ions of Precious
Metals ......................................... 186
B. Coreduction of Mixed Ions of Light
Transition Metals and Precious Metals .......... 189
С. Successive Reduction of Metal Ions ............. 189
D. Sacrificial Hydrogen Reduction ................. 191
E. Mixing of Two Kinds of Monometallic
Nanoclusters ................................... 193
3.3.3. Catalysis of Polymer-capped Bimetallic
Nanoclusters ...................................... 193
A. Hydrogenation .................................. 194
B. Hydration of Acrylonitrile ..................... 195
C. Photo-induced Generation of Hydrogen
from Water ..................................... 196
3.3.4. Future Aspects .................................... 196
3.4. Organic-Inorganic Hybrid Materials Based on
Silsesquioxanes .......................................... 197
3.4.1. Introduction ...................................... 197
3.4.2. Organic-Inorganic Hybrid Nanocomposites
Using Functionalized POSS as an Initiator ......... 198
A. Synthesis of Hybrid Micelles Using
PolyoxazoHnes Initiated by Monofunctional
POSS ........................................... 198
B. Synthesis of Star-shaped PolyoxazoHnes
Using Octatunctional POSS Initiator ............ 198
3.4.3. Organic-Inorganic Hybrid Polymers ................. 200
A. Synthesis of Hybrid Gels Having
Functionalized POSS ............................ 200
B. Synthesis of Liquid-Crystalline Hybrid
Polymers Using POSS as a Component of
Copolymerization ............................... 202
С. Synthesis of Liquid-Crystalline POSS ........... 202
3.4.4. Transparent Organic-Inorganic Polymer
Hybrids with Functionalized POSS .................. 205
A. Synthesis of Polymer Hybrids Using
POSS with Hydroxyl Groups ...................... 205
B. Synthesis of Ternary Polymer Hybrids of
POSS and Organic Polymers Utilizing the
Sol-Gel Reaction ............................... 206
C. Synthesis of Polymer Hybrids Using Two
Physical Bonding Interactions in One
System ......................................... 207
3.4.5. Conclusions and Future Perspectives ............... 208
3.5. Protonation-induced Intramolecular Electron
Transfer in the Ferrocene-Quinone Conjugated System ...... 209
3.5.1. Introduction ...................................... 209
3.5.2. Ll-D/A Complexes .................................. 210
3.5.3. 2:1-D/A Complexes ................................. 214
3.5.4. A 1.2-D/A Complex ................................. 219
3.5.5. Polymeric Ll-D/A Complexes ........................ 221
3.5.6. Concluding Remarks ................................ 222
3.6. Oligomers of Non-natural Metal Complex Amino Acids ....... 224
3.6.1. Introduction ...................................... 224
3.6.2. Design of Non-natural Amino Acid .................. 225
3.6.3. Oligomers of Ferrocene Amino Acid ................. 226
3.6.4. Ferrocene-Peptide Complexes ....................... 230
3.6.5. Bipyridine Complex Amino Acid ..................... 231
3.6.6. Terpyridine Complex Amino Acid .................... 233
3.6.7. Concluding Remark ................................. 234
References .................................................... 235
4. Biological Macromolecular Complexes
4.1. Macromolecular Metal Complexes in Biological
Systems .................................................. 244
4.1.1. Introduction ...................................... 244
4.1.2. Small Ligands and Polymeric Ligands Present
in Biology ........................................ 246
A. Coordination Behavior of Ligands towards
Metal Ions ..................................... 246
B. Brief Overview of Ligand Groups that
Bind to Metals in Biological Systems ........... 247
4.1.3. Reactivity of Metals Coordinated to
Biological Ligands General Aspects ................ 249
A. Metal Ions May Have Only a Structural
or Structure-organizing Role ................... 250
B. Transport and Storage of Metal Ions by
Biomacromolecules .............................. 250
С. Catalysis by Metal Ions Present in
Biomacromolecules .............................. 251
D. Toxic and Medicinal Functions of Metal
Ions Related to Biomacromolecules .............. 252
E. Binding of Pt-antitumor Drugs to DNA ........... 253
4.1.4. Concluding Remarks ................................ 255
4.2. Direct Observation of Supramolecular Structures of
Biorelated Materials by Atomic Force Microscopy .......... 258
4.2.1. Introduction ...................................... 258
4.2.2. Antibody Supramolecules ........................... 259
A. Single Molecular Images of Antibodies .......... 259
B. Direct Observation of Supramolecules
between Antibodies and Porphyrin ............... 261
С. Antibody Dendrimers: Combination of IgG
and IgM ........................................ 262
4.2.3. DNA Supramolecules ................................ 264
A. Imaging of Individual Plasmid DNA
Molecules ...................................... 264
B. Preparation of Nicked DNA by the Addition
of DNase I to Plasmid DNA pBR322 ............... 267
С. Catenation Reaction Using Topoisomerase I ...... 268
D. Single Molecular Images of DNA Catenanes
Observed by AFM ................................ 268
E. DNA [n]Catenanes Prepared by Irreversible
Reaction with DNA Ligase ....................... 270
4.2.4. Conclusions and Summary ........................... 272
4.3. Analyses of the Nanostructure of Calcium
Carbonate Composite in Biominerals of Pinctada
fucata ................................................... 273
4.3.1. Introduction ...................................... 273
4.3.2. Solid State l3C-NMR Analysis of the Nacreous
Layer ............................................. 274
4.3.3. High Resolution ТЕМ Analysis of the Nacreous
Layer ............................................. 277
4.3.4. Conclusions ....................................... 280
4.4. A Novel Triple Helix Consisting of One
Polynucleotide and Two Polysaccharide Chains ............. 281
4.4.1. Introduction ...................................... 281
4.4.2. Spectroscopic Changes upon the Complexation ....... 283
4.4.3. Molecular Specificity in the Complexation ......... 284
4.4.4. Temperature and Composition Dependences of
Circular Dichroism for the Complex ................ 285
4.4.5. Critical Molecular Weight to Induce the
Complexation ...................................... 287
4.4.6. Stoichiometry and Molecular Modeling .............. 287
4.4.7. Cation-induced Complexation ....................... 292
4.4.8. Switching the Complexation On/Off ................. 293
4.4.9. Chemical Modification to Enhance Affinity ......... 294
4.4.10.Summary ........................................... 296
4.5. Physicochemical Properties of Spider Silk—An
Approach to Nanostructure ................................ 297
4.5.1. Introduction ...................................... 297
4.5.2. Materials and Methods ............................. 299
A. Spider Silks ................................... 299
B. Samples for Thermal, Optical and Aging
Measurements ................................... 301
C. Preparation of Samples for Mechanical
Measurements ................................... 301
D. Weight of Nephila clavata Spiders .............. 301
E. Thermal Measurements ........................... 303
F. Density of Draglines ........................... 303
G. Scanning Electron Microscopy ................... 303
H. Elastic Modulus ................................ 304
I. ESR Measurements .............................. 304
J. Ultraviolet Rays .............................. 304
K. Amino Acid Composition ......................... 304
4.5.3. Results and Discussion ............................ 304
A. Thermal Properties ............................. 304
B. Mechanical Lifeline of Draglines ............... 307
C. Mechanical Lifeline for Immature Spiders ....... 310
D. Elastic Modulus ................................ 312
E. Degradation of Draglines by UV Rays ............ 314
F. Strengthening of Draglines by UV Rays .......... 316
G. Infrared Dichroism ............................. 317
H. Fine Structure of Dragline ..................... 319
4.5.4. Conclusion ........................................ 319
References .................................................... 321
Index ......................................................... 325
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