Preface xiii
List of Contributors xv
Acknowledgments xix
1 Click Chemistry: A Universal Ligation Strategy for Biotechnology and Materials Science 1
Joerg Lahann
1.1 Introduction 1
1.2 Selected Examples of Click Reactions in Materials Science and Biotechnology 2
1.3 Potential Limitations of Click Chemistry 5
1.4 Conclusions 5
References 6
2 Common Synthons for Click Chemistry in Biotechnology 9
Christine Schilling, Nicole Jung and Stefan Brase
2.1 Introduction - Click Chemistry 9
2.2 Peptides and Derivatives 10
2.3 Peptoids 12
2.4 Peptidic Dendrimers 13
2.5 Oligonucleotides 14
2.6 Carbohydrates 18
2.7 Conclusion 25
References 26
3 Copper-free Click Chemistry 29
Jeremy M. Baskin and Carolyn R. Bertozzi
3.1 Introduction 29
3.2 Bio-orthogonal Ligations 30
3.2.1 Condensations of Ketones and Aldehydes with Heteroatom-bound Amines 31
3.2.2 Staudinger Ligation of Phosphines and Azides 32
3.2.3 Copper-free Azide-Alkyne Cycloadditions 35
3.2.4 Bioorthogonal Ligations of Alkenes 37
3.3 Applications of Copper-free Click Chemistries 38
3.3.1 Activity-based Profiling of Enzymes 38
3.3.2 Site-specific Labeling of Proteins 39
3.3.3 Metabolic Labeling of Glycans 41
3.3.4 Metabolic Targeting of Other Biomolecules with Chemical Reporters 44
3.4 Summary and Outlook 45
References 46
4 Protein and Peptide Conjugation to Polymers and Surfaces Using Oxime Chemistry 53
Heather D. Maynard, Rebecca M. Broyer and Christopher M. Kolodziej
4.1 Introduction 53
4.2 Protein/Peptide-Polymer Conjugates 54
4.3 Immobilization of Proteins and Peptides on Surfaces 60
4.4 Conclusions 66
References 67
5 The Role of Click Chemistry in Polymer Synthesis 69
Jean-François Lutz and Brent S. Sumerlin
5.1 Introduction 69
5.2 Polymerization via CuAAC 70
5.3 Post-polymerization Modification via Click Chemistry 72
5.4 Polymer-Biomacromolecule Conjugation 76
5.5 Functional Nanomaterials 81
5.6 Summary and Outlook 83
References 85
6 Blocks, Stars and Combs: Complex Macromolecular Architecture Polymers via Click Chemistry 89
Sebastian Sinnwell, Andrew J. Inglis, Martina H. Stenzel and Christopher Barner-Kowollik
6.1 Introduction 89
6.2 Block Copolymers 91
6.2.1 Preparing Polymers for Click Conjugations 92
6.2.2 The Click Reaction: Methodologies and Isolation 96
6.2.3 Polymer Characterization 99
6.3 Star Polymers 101
6.3.1 Star polymers An 101
6.3.2 Dentritic Star Polymers 107
6.4 Graft Copolymers 107
6.4.1 'Grafting-to' Azide Main Chains 109
6.4.2 'Grafting-to' Alkyne Main Chains 111
6.4.3 Non-CuAAC Routes 113
6.5 Concluding Remarks 113
References 113
7 Click Chemistry on Supramolecular Materials 119
Wolfgang H. Binder and Robert Sachsenhofer
7.1 Introduction 119
7.2 Click Reactions on Rotaxanes, Cyclodextrines and Macrocycles 123
7.2.1 Click with Rotaxanes 123
7.2.2 Click on Cyclodextrines 126
7.2.3 Click on Macrocycles 128
7.3 Click Reactions on DNA 131
7.4 Click Reactions on Supramolecular Polymers 138
7.5 Click Reactions on Membranes 143
7.6 Click Reactions on Dendrimers 147
7.7 Click Reactions on Gels and Networks 147
7.8 Click Reactions on Self-assembled Monolayers 153
References 164
8 Dendrimer Synthesis and Functionalization by Click Chemistry for Biomedical Applications 177
Daniel Q. McNerny, Douglas G. Mullen, Istvan J. Majoros, Mark M. Banaszak Holl and James R. Baker Jr
8.1 Introduction 177
8.2 Dendrimer Synthesis 181
8.2.1 Divergent Synthesis 181
8.2.2 Convergent Synthesis 183
8.3 Dendrimer Functionalization 184
8.4 Conclusions and Future Directions 189
References 191
9 Reversible Diels-Alder Cycloaddition for the Design of Multifunctional Network Polymers 195
Amy M. Peterson and Giuseppe R. Palmese
9.1 Introduction 195
9.2 Design of Polymer Networks 198
9.3 Application of Diels-Alder Linkages to Polymer Systems 199
9.3.1 Molecular Weight Control of Linear Polymers 200
9.3.2 Remoldable Crosslinked Materials 202
9.3.3 Thermally Removable Encapsulants 203
9.3.4 Reversibly Crosslinked Polymer-Solvent Gels 203
9.3.5 Remendable Materials 204
9.3.6 Recyclable Thermosets 206
9.3.7 Smart Materials 207
9.4 Conclusions 209
References 209
10 Click Chemistry in the Preparation of Biohybrid Materials 217
Heather J. Kitto, Jan Lauko, Floris P. J. T. Rutjes and Alan E. Rowan
10.1 Introduction 217
10.2 Polymer-containing Biohybrid Materials 218
10.2.1 Polymers from Controlled Techniques 218
10.2.2 Bio-inspired Polymers via Click Chemistry 220
10.3 Biohybrid Structures based on Protein Conjugates 228
10.4 Biohybrid Amphiphiles 232
10.5 Glycoconjugates 236
10.5.1 Carbohydrate Clusters 236
10.5.2 Glycopeptides 238
10.5.3 Glycopolymers 244
10.6 Conclusions 247
References 247
11 Functional Nanomaterials using the Cu-catalyzed Huisgen Cycloaddition Reaction 255
Sander S. van Berkel, Arnold W.G. Nijhuis, Dennis W.P.M. Lowik and Jan C.M. van Hest
11.1 Introduction 255
11.2 Inorganic Nanoparticles 256
11.2.1 Silicon-based Nanoparticles 256
11.2.2 Cadmium Selenide-based Nanoparticles 257
11.2.3 Ferric Oxide-based Nanoparticles 257
11.2.4 Gold-based Nanoparticles 261
11.3 Carbon-based Nanomaterials 266
11.3.1 Fullerenes 267
11.3.2 Carbon Nanotubes 269
11.4 Self-assembled Organic Structures 272
11.4.1 Liposomes 274
11.4.2 Polymersomes 275
11.4.3 Micelles and Cross-linked Nanoparticles 278
11.5 Virus Particles 281
11.6 Conclusions 284
References 285
12 Copper-catalyzed 'Click' Chemistry for Surface Engineering 291
Himabindu Nandivada and Joerg Lahann
12.1 Introduction 291
12.2 Synthesis of Alkyne or Azide-functionalized Surfaces 292
12.2.1 Self-assembled Monolayers of Alkanethiolates 292
12.2.2 Self-assembled Monolayers of Silanes and Siloxanes 292
12.2.3 Block Copolymers 294
12.2.4 Layer-by-layer Films 296
12.2.5 Chemical Vapor Deposition Polymerization 297
12.2.6 Fiber Networks 298
12.3 Spatially Controlled Click Chemistry 299
12.4 Copper-catalyzed Click Chemistry for Bioimmobilization 300
12.5 Summary 305
References 305
13 Click Chemistry in Protein Engineering, Design, Detection and Profiling 309
Daniela C. Dieterich and A. James Link
13.1 Introduction 309
13.2 Posttranslational Functionalization of Proteins with Azides and Alkynes 310
13.3 Cotranslational Functionalization of Proteins with Azides and Alkynes 314
13.4 BONCAT: Identification of Newly Synthesized Proteins via Noncanonical Amino Acid Tagging 318
13.5 Conclusions and Future Prospects 321
References 322
14 Fluorogenic Copper(I)-catalyzed Azide-Alkyne Cycloaddition Reactions Reactions and their Applications in Bioconjugation 327
Celine Le Droumaguet and Qian Wang
14.1 Click Reaction for Bioconjugation Applications 327
14.2 Significance of Fluorogenic Reactions in Bioconjugation 328
14.3 CuAAC-based Fluorogenic Reaction 332
14.4 Applications of CuAAC in Bioconjugation 337
14.4.1 Fluorogenic Probing of Cellular Components 339
14.4.2 Fluorogenic Conjugation of DNA 341
14.4.3 Fluorogenic Conjugation of Viruses 344
14.4.4 Fluorogenic Conjugation of Nanoparticles/Polymers 345
14.5 Conclusions 348
References 349
15 Synthesis and Functionalization of Biomolecules via Click Chemistry 355
Christine Schilling, Nicole Jung and Stefan Brase
15.1 Introduction 355
15.2 Labeling of Macromolecular Biomolecules 356
15.2.1 Fluorescent Labeling 356
15.2.2 Labeling of Bovine Serum Albumin 360
15.2.3 Biotin-labeling of Biomolecules: ABPP 361
15.2.4 Fluorine Labeling 364
15.3 Syntheses of Natural Products and Derivatives 365
15.4 Enzymes and Click Chemistry 368
15.5 Synthesis of Glycosylated Molecular Architectures 371
15.6 Synthesis of Nitrogen-rich Compounds: Polyazides and Triazoles 373
15.7 Conclusions 374
References 375
16 Unprecedented Electro-optic Properties in Polymers and Dendrimers Enabled by Click Chemistry Based on the Diels-Alder Reactions 379
Jingdong Luo, Tae-Dong Kim and Alex K.-Y. Jen
16.1 Introduction 379
16.2 Diels-Alder Click Chemistry for Highly Efficient Side-chain E-O Polymers 380
16.3 Diels-Alder Click Chemistry for Crosslinkable E-O Polymers Containing Binary NLO Chromophores 388
16.4 Diels-Alder Click Chemistry for NLO Dendrimers 392
16.5 Conclusions 394
References 397
Index 399
