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List of Abbreviations XIII
List of Contributors XIX
1 History of Post-polymerization Modification 1
Kemal Arda G¨unay, Patrick Th´eato, and Harm-Anton Klok
1.1 Introduction 1
1.2 Post-polymerization Modification via Thiol-ene Addition 3
1.3 Post-polymerization Modification of Epoxides, Anhydrides, Oxazolines, and Isocyanates 4
1.4 Post-polymerization Modification of Active Esters 13
1.5 Post-polymerization Modification via Thiol-Disulfide Exchange 19
1.6 Post-polymerization Modification via Diels-Alder Reactions 20
1.7 Post-polymerization Modification via Michael-Type Addition 22
1.8 Post-polymerization Modification via Azide Alkyne Cycloaddition Reactions 27
1.9 Post-polymerization Modification of Ketones and Aldehydes 32
1.10 Post-polymerization Modifications via Other Highly Efficient Reactions 35
1.11 Concluding Remarks 39
References 39
2 Post-polymerization Modifications via Active Esters 45
Ryohei Kakuchi and Patrick Theato
2.1 Introduction 45
2.2 Active Esters in the Side Group 46
2.2.1 Homopolymers 47
2.2.1.1 General 47
2.2.1.2 Stimuli-Responsive Polymers 48
2.2.1.3 Biologically Active Polymers 49
2.2.1.4 Thin Films 51
2.2.1.5 Polymeric Ligands for Nanoparticles 52
2.2.1.6 Miscellaneous Uses of Active Ester Polymers 53
2.2.2 Block Copolymers 53
2.2.2.1 General 53
2.2.2.2 Block Copolymers and Inorganic Moieties 53
2.2.2.3 Amphiphilic Block Copolymers 54
2.2.2.4 Stimuli-Responsive Block Copolymers 54
2.3 Star Polymers 55
2.4 Active Esters at the End Groups 55
2.5 Controlled Positioning of Active Ester Moieties 57
2.6 Summary 58
References 59
3 Thiol–ene Based Functionalization of Polymers 65
Nikhil K. Singha and Helmut Schlaad
3.1 Introduction 65
3.2 General Considerations and Mechanisms 66
3.2.1 Radical Thiol–ene Addition 66
3.2.2 Nucleophilic Thiol–ene Addition 68
3.3 Functionalization of Polymers 69
3.3.1 Endfunctionalization 69
3.3.1.1 Polymer–ene/Thiol 70
3.3.1.2 Polymer–SH/Olefin 72
3.3.2 Polymer-Analog Reactions 75
3.3.2.1 Polyene/Thiol 75
3.3.2.2 Polythiol/Olefin 80
3.3.3 Bioconjugation 81
3.4 Summary 83
Acknowledgments 83
References 84
4 Thiol–yne Chemistry in Polymer and Materials Science 87
Andrew B. Lowe and Justin W. Chan
4.1 Introduction 87
4.2 The Thiol–yne Reaction in Small-Molecule Chemistry 88
4.3 The Thiol–yne Reaction in Polymer and Material Synthesis 95
4.3.1 Network Polymers 96
4.3.2 Surface-Initiated Polymerizations and Modifications 98
4.3.3 Polymer Beads 103
4.3.4 Hyperbranched Polymers 104
4.3.5 Dendrimers and Dendritic Polymers 108
4.3.6 Main chain α- and ω-Functional (co)Polymers 110
4.3.7 Nonradical Thiol–yne Click Polymerization 114
4.3.8 Summary and Outlook 115
References 116
5 Design and Synthesis of Maleimide Group Containing Polymeric Materials via the Diels-lder/Retro Diels-Alder Strategy 119
Tugce Nihal Gevrek, Mehmet Arslan, and Amitav Sanyal
5.1 Introduction 119
5.2 Maleimide Functional Group Containing Polymeric Materials 120
5.3 The Diels-Alder/Retro Diels-Alder Cycloaddition-Cycloreversion Reactions 120
5.4 Application of Diels-Alder/Retro Diels-Alder Reaction to Synthesize Maleimide-Containing Polymers 122
5.4.1 Synthesis of Polymers Containing the Maleimide Group at the Chain Termini 122
5.4.2 Polymers Containing Maleimide Groups as Side Chains 141
5.4.3 Synthesis of Maleimide-Containing Hydrogels Obtained Using the Diels–Alder/Retro Diels–Alder Reaction-Based Strategy 147
5.5 Conclusions 150
References 150
6 The Synthesis of End-Functional Ring-Opening Metathesis Polymers 153
Andreas F. M. Kilbinger
6.1 Introduction 153
6.2 End-Functionalization Methods in General 156
6.3 Functionalization during Initiation 159
6.4 Functionalization after Propagation 160
6.4.1 Reaction with Carbonyl Groups 161
6.4.2 Reaction with Molecular Oxygen 162
6.4.3 Reaction with Functional Vinyl Ethers 162
6.4.4 Reaction with Functional Vinyl Esters 163
6.4.5 Reaction with Nondeactivating Olefins 165
6.5 Functionalization during Propagation 166
6.5.1 Using Chain-Transfer Agents 166
6.5.2 Sacrificial Synthesis 167
6.6 Conclusions and Outlook 168
Acknowledgments 168
References 169
7 Functional Polymers with Controlled Microstructure Based on Styrene and N-Substituted Maleimides 173
Delphine Chan-Seng, Mirela Zamfir, and Jean-Fran¸cois Lutz
7.1 Introduction 173
7.2 Background on Radical Copolymerization of Styrene and Maleimides 174
7.2.1 Conventional Radical Polymerization 175
7.2.2 Controlled Radical Polymerization 177
7.3 Precise Incorporation of Maleimide Units on Polystyrene Backbone 179
7.3.1 Strategy 179
7.3.2 Maleimides 180
7.3.3 Styrene Derivatives 181
7.4 Tuning a Simple Technique for the Preparation of Sequence-Controlled Polymers to the Elaboration of Functionalized Well-Defined Macromolecules 182
7.4.1 Incorporation of Different Functionalities on the Same Polymer Backbone of a Well-Defined Polymer Possessing a Controlled Microstructure 183
7.4.2 Designing 1D Periodic Molecular Arrays 183
7.4.3 Elaboration of New Materials by Post-polymerization Modification 185
7.4.3.1 Activated Esters as Precursor of Post-polymerization Modification 186
7.4.3.2 Formation of Positionable Covalent Bridges 186
7.5 Summary and Outlook 189
References 189
8 Temperature-Triggered Functionalization of Polymers 193
Bongjin Moon
8.1 Introduction 193
8.2 Temperature-Triggered Alteration of Polymer Property 194
8.2.1 Thermolysis of t-Butyl Esters, Carbonates, and Carbamates 194
8.2.2 Thermolysis of Miscellaneous Esters, Carbonates, and Carbamates 197
8.2.3 Thermolysis of Acetals 199
8.3 Temperature-Triggered Generation of Reactive Groups 201
8.3.1 Thermolytic Generation of Anhydride Group in Polymers 201
8.3.2 Thermolytic Generation of Ketenes in Polymers 206
8.3.3 Thermolytic Generation of Transient Reactive Groups 211
8.4 Conclusions 213
References 215
9 New Functional Polymers Using Host–Guest Chemistry 217
Ryosuke Sakai and Toyoji Kakuchi
9.1 Introduction 217
9.2 Polymers with Responsive Three-Dimensional Structures 218
9.2.1 Helicity Induction 218
9.2.2 Helix Inversion 220
9.3 Polymer Probes for Specific Chemical Sensing 222
9.3.1 Colorimetric Probes 222
9.3.2 Fluorescent Probes 226
9.4 Responsive Soft Materials 228
9.4.1 Responsive Smart Gels 228
9.4.2 Thermoresponsive Materials with Molecular Recognition Ability 230
9.5 Functional Polyrotaxanes 232
References 234
10 Glycopolymers via Post-polymerization Modification Techniques 237
James A. Burns, Matthew I. Gibson, and C. Remzi Becer
10.1 Introduction 237
10.2 Synthesis and Controlled Polymerization of Glycomonomers 238
10.3 Post-polymerization Modification of Polymer Scaffolds to Synthesize Glycopolymers 240
10.4 Azide–Alkyne Click Reactions 243
10.5 Utilizing Thiol-Based Click Reactions 252
10.6 Thiol–ene Click Reactions 253
10.7 Thiol–yne Click Reactions 254
10.8 Thiol–Halogen Substitution Reactions 255
10.9 Alkyne/Alkene Glycosides: ‘‘Backward’’ Click Reactions 258
10.10 Post-polymerization Glycosylation of Nonvinyl Backbone Polymers 259
10.11 Conclusions and Outlook 260
Acknowledgments 262
References 262
11 Design of Polyvalent Polymer Therapeutics 267
Jacob T. Martin and Ravi S. Kane
11.1 Introduction 267
11.2 Polyvalent Polymer Therapeutics 268
11.2.1 Polymer Micelles 269
11.2.2 Controlled-Molecular-Weight Linear Polymers 273
11.2.3 Controlled Ligand Spacing 276
11.2.4 Matching Valency to the Target 280
11.2.5 Biocompatible Polymer Scaffolds 284
11.2.6 Bioengineered Polymer Scaffolds 285
11.3 Conclusions 287
References 288
12 Posttranslational Modification of Proteins Incorporating Nonnatural Amino Acids 291
Haresh More, Ching-Yao Yang, and Jin Kim Montclare
12.1 Posttranslational Modification of Existing Amino Acids within Protein Chain 291
12.1.1 Phosphorylation 291
12.1.2 Acetylation 292
12.1.3 Methylation 292
12.1.4 Glycosylation 293
12.1.5 Hydroxylation 293
12.1.6 Sulfation 294
12.2 Exploiting Biosynthetic Machinery: Cotranslational Approach 294
12.2.1 Site-Specific Incorporation (SSI) 294
12.2.1.1 In vitro SSI 294
12.2.1.2 In vivo SSI 298
12.2.1.3 Applications 306
12.2.2 Residue-Specific Incorporation (RSI) 308
12.2.2.1 Endogenous AARS 310
12.2.2.2 Overexpression of Endogenous AARS 310
12.2.2.3 Shrinking the AARS Editing Pocket 311
12.2.2.4 Enlarging the AARS Binding Pocket 312
12.2.2.5 Applications 312
12.3 Intein-Inspired Ligation Approach 315
12.3.1 Native Chemical Ligation (NCL) 316
12.3.1.1 Sulfur-Based N-Terminal Residue 316
12.3.1.2 Selenocysteine-Based N-Terminal Residue 316
12.3.2 Expressed Protein Ligation (EPL) 318
12.4 Combined Approach 319
12.4.1 RSI and EPL 319
12.4.2 SSI and Intein-Mediated Ligation 319
12.5 Protein and Polymer Conjugates 320
12.5.1 PEGlyation of Proteins via NAA 321
12.6 Modulating the Physicochemical Properties of Protein Polymers via NAA Incorporation 322
12.7 Future in Combined Technologies to Fabricate Tailored Protein-Polymer Conjugates as New Materials 322
12.8 Conclusion and Future Perspectives 323
Acknowledgments 324
References 324
13 Functionalization of Porous Polymers from High-Internal-Phase Emulsions and Their Applications 333
Linda Kircher, Patrick Theato, and Neil R. Cameron
13.1 Introduction 333
13.1.1 Preparation Method of polyHIPEs 334
13.2 Functionalization of polyHIPEs 335
13.2.1 Functionalization of polyHIPEs Based on Copolymerization with Functional Comonomers 337
13.2.2 Functionalization of polyHIPEs by Post-polymerization Modification 342
13.2.3 Functionalization of polyHIPEs Based on Grafting Modification of Porous Materials 343
13.2.3.1 ATRP to Functionalize polyHIPEs 345
13.2.4 Click Chemistry for Functionalization of polyHIPEs 346
13.2.5 Thiol-ene-based polyHIPEs 347
13.2.6 Dicyclopentadiene polyHIPEs 347
13.3 Applications 347
13.3.1 Tissue Engineering 348
13.3.2 Support Materials 348
13.4 Conclusions 349
References 350
14 Post-polymerization Modification of Polymer Brushes 353
Sara Orski, Gareth Sheppard, Rachelle Arnold, Joe Grubbs, and Jason Locklin
14.1 Introduction 353
14.2 Synthesis and Strategies for Functional Polymer Brushes 357
14.2.1 Preparation of Active Ester Polymer Brushes by SI-ATRP 357
14.2.2 Synthesis of Poly(NHS4VB) Block Copolymer Brushes with 2-Hydroxyethyl Acrylate, tert-Butyl Acrylate, or Styrene 360
14.2.3 Functionalization of Poly(NHS4VB) Brushes with Primary Amines 360
14.2.4 Quantification of Active Ester Post-polymerization Modification 361
14.3 Applications of Polymer Brush Modification: Multifunctional Surfaces via Photopatterning 362
14.3.1 Polymer Brush Functionalization with Photoactivated Dibenzocyclooctyne for Catalyst-Free Azide Cycloaddition 362
14.3.2 Copper-Free Click of Dibenzocyclooctyne and Azido-FL/Azido-RB 365
14.4 Conclusions and Future Outlook 366
References 366
15 Covalent Layer-by-Layer Assembly Using Reactive Polymers 371
Adam H. Broderick and David M. Lynn
15.1 Introduction 371
15.2 Overview of Layer-by-Layer Assembly: Conventional versus Covalent Assembly 371
15.3 Scope and Organization 375
15.4 Covalent LbL Assembly Based on ‘‘Click Chemistry’’ 375
15.5 Reactive LbL Assembly Using Azlactone-Functionalized Polymers 387
15.6 Other Reactions and Other Approaches 396
15.7 Concluding Remarks 401
Acknowledgments 402
References 402
Index 407
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