Smart polymers

SMART POLYMERS: Applications in Biotechnology and Biomedicine, Second Edition......Page 3
Table of Contents......Page 6
Preface......Page 8
Introduction......Page 10
About the Editors......Page 14
Contributors......Page 16
CONTENTS......Page 19
1.1 Introduction......Page 20
1.2 Solubility Phase Transitions and Liquid–Liquid Coexistence Curves......Page 22
1.3 Light Scattering in Macromolecular Solutions......Page 27
1.3.1 Static Light Scattering......Page 28
1.3.1.2 Scattering in Polymer Systems......Page 29
1.3.1.3 Light Scattering from Large Particles......Page 31
1.3.1.4 Zimm Plots......Page 34
1.3.2 Dynamic Light Scattering......Page 35
1.3.2.1 Photon Correlation Spectroscopy......Page 36
1.3.2.3 Effect of Polydispersity......Page 38
1.3.2.4 Effect of Size and Shape of Larger Particles......Page 39
1.3.2.5 Effect of Concentration......Page 40
1.3.2.7 Some Applications......Page 41
1.3.3 Combining Static and Dynamic Light Scattering......Page 43
1.3.3.1 Aggregates......Page 44
1.3.3.2 Nonergodic Systems......Page 47
1.4.1 Transition-Point Determination (Cloud Point)......Page 49
1.4.2 Sizes, Shape, and Conformations of Smart Polymers in the Course of Phase Transition......Page 54
1.4.3.1 Smart-Polymer–Protein Conjugates......Page 55
1.4.3.2 Smart Polymers Modified by Bioaffinity Ligands......Page 57
1.4.4 Hydrogels, Microgels, and Nanogels......Page 58
1.4.4.1 Drug-Delivery Systems......Page 59
1.4.4.2 Frozen Inhomogeneities and Dynamic Fluctuations......Page 60
1.5 Closing Remarks: Perspectives on Future Light Scattering Studies in Biotechnology and Biomedicine......Page 62
References......Page 63
Glossary......Page 71
2.1 Introduction......Page 73
2.2 Theory of Polymer Brushes......Page 74
2.2.1 Alexander-de Gennes Scaling Theory......Page 75
2.2.2 Mean-Field Boxlike Model......Page 76
2.2.3 Self-Consistent Field Theory......Page 77
2.3 Collapse-to-Swelling Transition in Nonionic Brush......Page 79
2.4 Polymer Brush in Solvent Mixture......Page 83
2.5 Complexation of Grafted Polymers with Amphiphiles......Page 85
2.6 Polyelectrolyte Brushes......Page 89
2.7 Conformational Transitions in pH-Responsive Brushes......Page 92
Acknowledgments......Page 94
References......Page 95
Abbreviations......Page 99
3.1 Introduction: First Steps......Page 100
3.2.1 First Reason for the Appearance of Two Minima in the Free-Energy Profile......Page 102
3.2.2 Theory of Swelling and Collapse of Charged Networks: a General Case......Page 103
3.3 Polyampholytes......Page 106
3.4 Second Reason for the Appearance of Two Minima in the Profile of the Free Energy: Collapse Due to Ionomer Effect......Page 109
3.5 Other Effects Due to Counterions......Page 113
3.6 New Polymers......Page 116
3.7 Smart Polymer-Colloid Composite Gels......Page 119
3.8.1 Biotechnology-Related Applications of Smart Gels......Page 122
3.8.2 Application of Smart Gels in Technology......Page 123
References......Page 125
4.1 Polymers with Temperature-Dependent Solubility in Water......Page 133
4.2.1 Amphiphilic Macromonomers......Page 136
4.2.2 Emulsion Polymerization......Page 139
4.2.3 Microemulsion Polymerization......Page 140
4.2.4 Solution Copolymerization......Page 141
4.3.1 Thermosensitive Properties of the Microgels......Page 142
4.3.2 Colloidal Stability of the Microgels......Page 143
4.4 Amphiphilic Graft Copolymers......Page 144
4.4.1 Self-Association below the LCST......Page 145
4.4.2 Heat Induced-Phase Transition......Page 146
4.4.3 Formation of Stable Mesoglobules......Page 147
4.5 Conclusions......Page 149
References......Page 150
CONTENTS......Page 155
5.1 Introduction......Page 156
5.2.1 Emulsion Polymerization......Page 158
5.2.3 Radiation Polymerization......Page 159
5.2.4 Living Free-Radical Polymerization......Page 160
5.3 Properties of Microgels......Page 162
5.3.1 Swelling Behavior of Microgels......Page 163
5.3.4 Effect of Monomer on Microgel Properties......Page 165
5.3.5 pH Sensitivity......Page 167
5.3.7 Swelling and Elasticity of Polyelectrolyte Microgels......Page 169
5.4.1 Static Light Scattering......Page 170
5.4.2 Dynamic Light Scattering......Page 173
5.4.3 NMR Spectroscopy......Page 174
5.4.4 Small-Angle Neutron Scattering......Page 175
5.4.5 Turbidimetric Analysis......Page 177
5.4.6 Transmission Electron Microscopy......Page 178
5.4.7 Scanning Electron Microscopy......Page 179
5.6 Applications of Microgels......Page 180
5.6.2 Drug Delivery Systems (DDS)......Page 182
5.6.4 Molecular Imprinting......Page 187
5.7 Future Areas of Research......Page 188
References......Page 189
6.1 Introduction......Page 195
6.2 Genetically Engineered Protein-Based Polymers......Page 196
6.3 Elastinlike Polymers (ELPs)......Page 197
6.4 The Fundaments of the Inverse Temperature Transition (ITT): The Thermal Response......Page 198
6.5 Measuring the ITT......Page 199
6.6 Designing the ELP with a Desired Tt......Page 201
6.7 Separating Components in the ITT......Page 203
6.8 (VPAVG)n, an Unconventional ELP......Page 205
6.9 The ΔTt Mechanism: Energy Transductions......Page 208
6.10 pH-Responsive ELPs......Page 209
6.11 Photoresponsive ELPs......Page 210
6.12 Self-Assembling Behavior......Page 215
6.13 ELPs for Biomedical Applications: Introducing Tailored Biofunctionality......Page 219
References......Page 223
7.1 Introduction......Page 229
7.1.1 Approaches to Molecular Imprinting......Page 230
7.1.2 Imprinting in Gels......Page 233
7.2 The Tanaka Equation......Page 234
7.2.1 Theoretical Considerations......Page 236
7.2.2 Experimental Assessment of the Tanaka Equation......Page 242
7.3 Temperature-Sensitive Imprinted Hydrogels......Page 246
7.4 pH-Sensitive Imprinted Gels......Page 255
References......Page 259
8.1 Introduction......Page 265
8.2 Progress in Synthesis of Fast-Responsive Hydrogels from Smart Polymers......Page 266
8.2.1 Use of Additives......Page 267
8.2.2 Utilization of Special Solvents......Page 269
8.2.3 Cross-Linking Polymerization......Page 270
8.2.4 Control of Preparation Temperature......Page 272
8.3.1 Reversible Immobilization and Separation of (Bio)macromolecules......Page 273
8.3.2 Molecular Recognition......Page 275
8.3.3.1 Flow Control......Page 277
8.3.3.2 Controlled Drug Release......Page 279
8.3.3.3 Artificial Muscles......Page 281
References......Page 282
9.1 Introduction......Page 287
9.2.2 Formation Mechanism of Macroporous Structures by Reaction-Induced Phase Separation......Page 290
9.2.2.2 Heterogeneous Gels Formed by ν-Induced Syneresis......Page 291
9.2.3 Macroporous Hydrogels Prepared by Reaction-Induced Phase Separation......Page 292
9.2.4 Formation of Macroporous Structures by Cryogelation......Page 304
9.3 Concluding Remarks......Page 310
References......Page 311
CONTENTS......Page 317
10.1 Introduction......Page 318
10.2 Boronate-Containing Copolymers as Polyelectrolytes......Page 319
10.3 Boronate-Containing Copolymer Gels as Components of Biosensors and Drug-Delivery Systems......Page 321
10.3.1 BCG for Self-Regulated Insulin Delivery......Page 322
10.3.2 Glucose-Sensitive Gels and Soluble Polymers......Page 324
10.3.3.1 BCG as Sugar Sensors Based on Vinyl Polymers......Page 325
10.3.3.2 Poly(Aniline Boronic Acid) as a Sugar-Sensitive Electrode Coating......Page 330
10.4 Interaction of Boronate-Containing Copolymers with Polysaccharide Gels, Cells, and Tissues......Page 332
10.4.1 Interaction of BCC with Oligosaccharides and Polysaccharide Gels......Page 333
10.4.2.1 Red Blood Cells and Epithelial Cells......Page 335
10.4.2.2 Proliferating Response of Lymphocytes on BCC......Page 336
10.4.2.3 Effect of BCC on Endothelium Cell Surface Glycocalix......Page 337
10.4.3 Mucoadhesive Properties of BCC and BCG......Page 339
10.5 Conclusions......Page 342
References......Page 343
11.1 Introduction......Page 349
11.2 Molecular Structure of Smart Polymers......Page 350
11.3 Mechanical Behavior of Smart Polymers......Page 353
11.3.1 Determination of the Mesh Size......Page 354
11.3.2 Effect of Molecular Structure on Drug- and Protein-Release Behavior......Page 357
11.3.3 Diffusion-Controlled Delivery Systems......Page 363
11.3.4 Chemically Controlled Delivery Systems......Page 364
11.3.5 Swelling-Controlled Release Systems......Page 366
11.4 Smart Delivery from Complexation Polymers......Page 367
11.5 Conclusions and the Future of Smart Hydrogels......Page 371
References......Page 372
CONTENTS......Page 377
12.1 Introduction......Page 378
12.2 Diseases Demanding Regional Therapy......Page 380
12.2.1 Cancer......Page 381
12.2.3 Vascular Disorders......Page 383
12.2.4 Bone Infections......Page 384
12.2.5 Retinal Disorders......Page 385
12.3.1 Nonbiodegradable Polymers......Page 386
12.3.2 Biodegradable Polymers......Page 387
12.3.2.1.2 Alginates......Page 388
12.3.2.1.3 Hyaluronic Acid (HA)......Page 390
12.3.2.1.4 Gelatin......Page 391
12.3.2.2.1 Polyesters......Page 392
12.3.2.2.3 Poly(ortho esters)......Page 395
12.4.1 Implants......Page 398
12.4.2 Microspheres......Page 401
12.4.3 In Situ-Forming Drug-Delivery Systems......Page 403
12.4.3.1 Thermoplastic Pastes......Page 404
12.4.3.2 In Situ Cross-Linked Systems......Page 405
12.4.3.3 In Situ Polymer Precipitation......Page 406
12.4.3.4 Thermally Induced Gelling Systems......Page 407
12.4.4 Hydrogels......Page 410
12.5 Conclusion and Future Prospects......Page 411
References......Page 412
Abbreviations......Page 419
13.1 Introduction......Page 420
13.2 Affinity Precipitation: Homo- and Heterobifunctional Modes......Page 421
13.3 Smart Polymers......Page 424
13.3.1 pH-Responsive Smart Polymers......Page 425
13.3.2 Thermoresponsive Smart Polymers......Page 430
13.4 Properties of Polymer Precipitates during Affinity Precipitation......Page 432
13.5 Ligands Used in Affinity Precipitation......Page 434
13.6.1 Metal Chelate Affinity Precipitation......Page 435
13.6.2 Elastinlike Polymers for Affinity Precipitation......Page 441
13.6.3 Affinity Precipitation Using Polyelectrolytes......Page 443
13.6.4 Other Applications......Page 445
13.7 Conclusion......Page 447
References......Page 448
14.1 Introduction......Page 455
14.2 Microfluidics......Page 456
14.3 Hydrogels......Page 457
14.3.1 Fabrication......Page 458
14.4.1 Sensor......Page 461
14.4.2 Valve......Page 463
14.4.3 Pump......Page 465
14.4.4 Clutch......Page 466
14.4.6 Active Assembly......Page 467
14.4.7 Separation......Page 468
14.5 Integrated Device......Page 470
14.6 Conclusion......Page 471
References......Page 472
Index......Page 477