Molecular Recognition and Polymers: Control of Polymer Structure and Self-Assembly

MOLECULAR RECOGNITION AND POLYMERS......Page 4
CONTENTS......Page 10
Preface......Page 20
Acknowledgments......Page 22
List of Contributors......Page 24
List of Figures......Page 28
List of Tables......Page 50
Editor Biographies......Page 52
PART I FUNDAMENTALS OF SUPRAMOLECULAR POLYMERS......Page 54
1.1. Introduction and Background......Page 56
1.2. Main-Chain Versus Side-Chain Supramolecular Polymers......Page 57
References......Page 59
2.1. Introduction......Page 62
2.2. Amphiphilic Block Copolymers......Page 64
2.2.1. Nonspecific Interactions......Page 66
2.2.2. Specific Interactions......Page 70
2.3. Amphiphilic Homopolymers......Page 75
2.3.1. Container Properties......Page 77
2.3.2. Recognition of Protein Surfaces......Page 78
2.3.3. Protein Sensing......Page 79
2.3.4. Recognition and Detection of Peptides......Page 81
2.5. Conclusions......Page 82
References......Page 83
3.1. Introduction and Background......Page 90
3.2. Mechanical Properties of Linear SPs......Page 93
3.3. Mechanical Properties of SP Networks......Page 99
3.4. Mechanical Properties in SPs at Interfaces......Page 103
3.5. Mechanical Forces and Supramolecular Interactions......Page 108
3.6. Conclusions......Page 110
References......Page 111
PART II POLYMER FORMATION AND SELF-ASSEMBLY......Page 116
4.1. Scientific Rationale and Perspective......Page 118
4.2.1. Fundamentals of Hydrogen Bonding......Page 119
4.2.2. Performance Advantages of Hydrogen Bond Containing Polymers......Page 122
4.3. Hydrogen Bond Containing Block Copolymers......Page 126
4.3.1. Block Copolymers Involving Single Hydrogen Bonding Groups......Page 127
4.3.2. Nucleobase Containing Hydrogen Bonding Block Copolymers......Page 129
4.3.3. Block Copolymers Containing DNA Oligonucleotides......Page 133
4.3.4. Block Copolymers Containing Other Hydrogen Bonding Arrays......Page 136
4.3.5. Order–Disorder Transitions (ODTs) in Hydrogen Bonding Block Copolymers......Page 137
4.4. Telechelic Hydrogen Bond Functional Polymers......Page 138
4.5. Combining Hydrogen Bonding with Other Noncovalent Interactions......Page 143
4.6. Reversible Attachment of Guest Molecules via Hydrogen Bonding......Page 144
4.7. Conclusions and Summary......Page 146
References......Page 147
5.1. Introduction......Page 156
5.1.1. Supramolecular Polymers......Page 157
5.2.1. Side Chain Functionalization Using Hydrogen Bonding......Page 158
5.2.2. Side Chain Functionalization Using Metal Coordination......Page 161
5.2.3. Side Chain Functionalization Using Coulombic Interactions......Page 162
5.3. Noncovalent Multifunctionalization of the Side Chains of Polymeric Scaffolds......Page 164
5.3.1. Combination of Hydrogen Bonding and Metal Coordination Interactions......Page 165
5.3.2. Combination of Hydrogen Bonding and Coulombic Charges......Page 167
5.3.3. Multiple Hydrogen Bonding Interactions: Self-Sorting on Polymers......Page 168
5.3.4. Terpolymer Functionalization Strategies: Combing Hydrogen Bonding, Metal Coordination, and Pseudorotaxane Formation......Page 169
5.4.1. Self-Assembled Functional Materials......Page 171
5.4.2. Network Formation Using Side Chain Supramolecular Polymers......Page 173
5.5. Conclusions and Outlook......Page 184
References......Page 185
6.1. Introduction......Page 190
6.2. Design of Nanoparticles and Polymers......Page 191
6.3.1. Control of Interparticle Spacing......Page 192
6.3.2. Self-Assembly of Nanoparticles Mediated by Polymers on the Planar Substrates......Page 195
6.3.3. Control of 3-D Hierarchical Organization in the Solution......Page 201
References......Page 204
7.1. Introduction......Page 210
7.2. Metal–Ligand Binding Motifs......Page 212
7.3. Linear and Macrocyclic Main Chain MSPs......Page 214
7.4. Metallosupramolecular Networks and Gels......Page 222
References......Page 228
8.1. Introduction......Page 232
8.2. Methods of Encapsulation......Page 233
8.2.2. Interfacial Polymerization......Page 235
8.2.3. Colloidosomes......Page 236
8.2.4. Colloidal Templating......Page 237
8.2.5. Vesicles......Page 238
8.3.1. General......Page 239
8.3.2. Encapsulated Catalysts......Page 241
8.4.1. Homogeneous Particles......Page 244
8.4.3. Colloidal Templates......Page 245
8.4.4. Vesicles......Page 246
References......Page 250
9.1. Introduction......Page 260
9.2. General Design: Information-Storing Molecular Duplexes Based on the Recombination of H Bond Donors and Acceptors......Page 261
9.3. Quadruply H Bonded Duplexes with Sequence-Independent Stability......Page 262
9.4. Tuning Binding Strength by Varying the Number of Interstrand H Bonds......Page 265
9.5. Probing Sequence Specificity......Page 266
9.6. Unexpected Discovery: Duplexes Containing Folded Strands......Page 269
9.7.1. Directed Assembly: Templated Formation of Two-Stranded β-Sheets......Page 272
9.7.2. Supramolecular Block Copolymers......Page 273
9.8.1. Templated Olefin Cross-Metathesis......Page 276
9.8.2. Directed, Sequence-Specific Disulfide Cross-Linking in Water......Page 277
9.9. Conclusions and Future Perspectives......Page 283
References......Page 284
10.1.1. Design of Synthetic Polymers with High Order Structures......Page 288
10.1.2. Biomimetic Design of Oligomers with High Order Structures......Page 289
10.2.1. Titin as Model for Modular Polymer Designs......Page 290
10.2.2. Biomimetic Modular Domain Strategy for Polymer Designs......Page 292
10.3.1. Synthesis and Studies of 2-Ureido-4-pyrimidone (UPy) Modular Polymers......Page 293
10.3.2. Synthesis and Single Molecule Nanomechanical Studies of Peptidomimetic β-Sheet Modular Polymers......Page 297
10.3.3. 3-D Network Polymers Containing Biomimetic Reversibly Unfolding Crosslinkers for Advanced Mechanical Properties......Page 301
10.4. Conclusion and Perspective......Page 304
References......Page 306
11.1. Introduction......Page 312
11.2.1. Unimolecular Micelle Analogy......Page 313
11.2.2. Location of Terminal Groups......Page 316
11.2.3. Polyelectrolyte Dendrimers......Page 318
11.3.1. Dendrimers and Dendrons......Page 322
11.3.2. Linear–Dendritic Multiblock Copolymers......Page 326
11.3.4. Steric Impact of Dendritic Block......Page 328
11.3.5. Rigid Linear Block Copolymers......Page 332
11.3.6. Supramolecular Gels......Page 335
11.4. Folded Amphiphilic Dendrimers......Page 336
11.4.1. Conformational Switching in Water......Page 338
11.4.2. Amphiphilic Self-Assembly of Peptide–Dendrons......Page 339
11.5. Langmuir–Blodgett Monolayers......Page 342
11.5.1. Effect of Hydrophobic/Hydrophilic Balance......Page 343
11.5.2. Packing Effect......Page 346
11.5.3. Photoresponsive Monolayers......Page 347
11.5.4. Fullerene Monolayers......Page 348
References......Page 350
PART III BIOMOLECULAR RECOGNITION USING POLYMERS......Page 360
12.1. Introduction......Page 362
12.2. PDA......Page 363
12.2.1. Glycolipids......Page 364
12.2.3. Small Molecules......Page 367
12.2.4. Cation and pH Sensors......Page 368
12.2.5. Membrane-Binding Peptides......Page 369
12.2.7. Pattern Recognition......Page 370
12.2.8. Whole Cells......Page 371
12.2.9. Supported PDAs......Page 372
12.3. Polythiophenes......Page 376
12.5. Conclusion......Page 381
References......Page 382
13.1. Introduction......Page 388
13.2. Dendrimers to Glycodendrimers......Page 391
13.3. Multivalency......Page 395
13.4. Heteromultivalent Carbohydrate Systems......Page 398
13.5. Comments Regarding the Synthesis of Heteromultivalent Carbohydrate Systems......Page 400
13.6. Electron Paramagnetic Resonance (EPR) Characterization of Heterogeneously Functionalized Dendrimers......Page 401
13.7. Conclusions and Outlook......Page 406
References......Page 407
14.1. Introduction......Page 412
14.2. Self-Assembly of Nanofibers Based on α-Helices......Page 414
14.3.1. Helix-Sheet Conversion and Nanofiber Formation......Page 422
14.3.2. Antiparallel β-Sheet Based Nanofibers......Page 425
14.3.3. Nanofibers Derived from Short Peptide Sequences......Page 428
14.3.4. Parallel β-Sheet Nanofibers......Page 429
14.4. Collagen Mimetics......Page 436
References......Page 440
15.1. Introduction to Sensing Platforms......Page 448
15.2.1. General Types of Imprinted Polymers (Covalent and Noncovalent)......Page 450
15.2.2. Types and Preparation of MIPs......Page 451
15.2.3. Polymerization Conditions......Page 455
15.3.1. Binding Site Heterogeneity......Page 458
15.3.2. Limitations of the Recognition Properties of MIPs......Page 460
15.4.1. Ground MIP Particles......Page 462
15.4.2. Thin Films and Membranes......Page 464
15.4.3. Self-Assembled Monolayers......Page 465
15.5.1. General Considerations......Page 466
15.5.2. Competitive Binding Assays......Page 467
15.5.3. Mass-Sensitive Sensors......Page 468
15.5.4. Optical MIP Sensors......Page 469
15.5.5. Electrometrical MIP Sensors......Page 471
References......Page 473
Index......Page 484