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Bücher | Dezember 2007 | Bio-inorganic Hybrid Nanomaterials | Inhaltsverzeichnis
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  Contents  
 
  Preface XIII
  Contributors XV
1 An Introduction to Bio-nanohybrid Materials
Eduardo Ruiz-Hitzky, Margarita Darder, Pilar Aranda 		1
1.1 Introduction: The Assembly of Biological Species to Inorganic Solids 1
1.2 Bio-nanohybrids Based on Silica Particles and Siloxane Networks 4
1.3 Calcium Phosphates and Carbonates in Bioinspired and Biomimetic Materials 9
1.4 Clay Minerals and Organoclay Bio-nanocomposites 13
1.5 Bio-Nanohybrids Based on Metal and Metal Oxide Nanoparticles 20
1.6 Carbon-based Bio-nanohybrids 22
1.7 Bio-nanohybrids Based on Layered Transition Metal Solids 28
1.8 Trends and Perspectives 31
References 32
2 Biomimetic Nanohybrids Based on Organosiloxane Units
Kazuko Fujii, Jonathan P. Hill, Katsuhiko Ariga 		41
2.1 Introduction 41
2.2 Monolayer on Solid Support 45
2.3 Layered Alkylsiloxane 53
2.4 Organic-Inorganic Hybrid Vesicle "Cerasome" 59
2.5 Mesoporous Silica Prepared by the Lizard Template Method 65
2.6 Future Perspectives 69
References 71
3 Entrapment of Biopolymers into Sol-Gel-derived Silica Nanonocomposites
Yury A. Shchipunov 		75
3.1 Introduction 75
3.2 Sol-Gel Processes 77
3.2.1 Chemistry 77
3.2.1.1 Hydrolysis 77
3.2.1.2 Condensation 78
3.2.1.3 Sol-Gel Transition 78
3.2.2 Silica Precursors 79
3.2.2.1 Orthosilicic Acid 80
3.2.2.2 Sodium Metasilicate 80
3.2.2.3 Alkoxides 80
3.2.3 Two-Stage Approach to Biopolymer Entrapment 82
3.3 Biocompatible Approaches 84
3.3.1 Modified Sol-Gel Processing 84
3.3.1.1 Method of Gill and Ballesteros 84
3.3.1.2 Low-Molecular and Polymeric Organic Additives 85
3.3.2 Organically-modified Precursors 86
3.3.3 Biocompatible Precursors by Brennan et al. 87
3.4 One-Stage Approach Based on a Silica Precursor with Ethylene Glycol Residues 88
3.4.1 Precursor 88
3.4.2 Role of Biopolymers in Sol-Gel Processing 89
3.4.3 Advantages of One-Stage Processes 96
3.4.4 Hybrid Biopolymer-Silica Nanocomposite Materials 98
3.4.5 Enzyme Immobilization 99
3.5 Perspectives 102
References 103
4 Immobilization of Biomolecules on Mesoporous Structured Materials
Ajayan Vinu, Narasimhan Gokulakrishnan, Toshiyuki Mori, Katsuhiko Ariga 		113
4.1 Introduction 113
4.2 Immobilization of Protein on Mesoporous Silica 116
4.3 Immobilization of Protein on Mesoporous Carbon and Related Materials 124
4.4 Immobilization of Other Biopolymers on Mesoporous Materials 133
4.5 Immobilization of Small Biomolecules on Mesoporous Materials 137
4.6 Advanced Functions of Nanohybrids of Biomolecules and Mesoporous Materials 141
4.7 Future Perspectives 149
References 150
5 Bio-controlled Growth of Oxides and Metallic Nanoparticles
Thibaud Coradin, Roberta Brayner, Fernand Fiévet, Jacques Livage 		159
5.1 Introduction 159
5.2 Biomimetic Approaches 160
5.3 In vitro Synthesis of Hybrid Nanomaterials 165
5.3.1 Polysaccharides 165
5.3.1.1 Alginates 165
5.3.1.2 Carrageenans 169
5.3.1.3 Chitosan 171
5.3.2 Proteins 174
5.3.2.1 Gelatin 174
5.3.2.2 Collagen 175
5.3.2.3 Protein Cages and Viral Capsids 177
5.3.3 Lipids 180
5.3.4 DNA Scaffolds 181
5.4 Perspectives: Towards a "Green Nanochemistry" 183
References 184
6 Biomineralization of Hydrogels Based on Bioinspired Assemblies for Injectable Biomaterials
Junji Watanabe, Mitsuru Akashi 		193
6.1 Introduction 193
6.1.1 Biominerals as Nanomaterials 193
6.1.2 Nanomaterials for Biofunctions 196
6.2 Fundamental Concept of Bioinspired Approach 197
6.2.1 Bioinspired Approach to Materials 197
6.2.2 Concrete Examples of the Bioinspired Approach 198
6.3 Alternate Soaking Process for Biomineralization and their Bio-functions 199
6.3.1 Nanoassembly by Polyelectrolytes 199
6.3.2 Alternate Soaking Process for Biomineralization 200
6.3.3 Biomineralization of Hydrogels for Bio-functions 201
6.4 Electrophoresis Process for Biomineralization 203
6.4.1 Innovative Methodology of Electrophoresis Process for Biomineralization 203
6.4.2 Application for Injectable Materials 204
6.5 Conclusions 206
References 206
7 Bioinspired Porous Hybrid Materials via Layer-by-Layer Assembly
Yajun Wang, Frank Caruso 		209
7.1 Introduction 209
7.2 Porous Materials 209
7.2.1 Microporous Materials 210
7.2.2 Mesoporous Material 210
7.2.3 Macroporous Materials 211
7.3 LbL Assembly 213
7.4 LbL Assembly on MS Substrates 214
7.4.1 Encapsulation of Biomolecules in MS Particles 214
7.4.2 MS Spheres as Templates for the Preparation of Hollow Capsules 218
7.4.3 Preparation of Protein Particles via MS Sphere Templating 220
7.4.4 Template Synthesis of Nanoporous Polymeric Spheres 221
7.5 LbL Assembly on Macroporous Substrates 225
7.5.1 LbL Assembly on Tubular Substrates 226
7.5.2 LbL Assembly on 3DOM Materials 229
7.5.3 LbL Assembly on Naturally Occurring Porous Substrates 231
7.6 Summary and Outlook 232
References 233
8 Bio-inorganic Nanohybrids Based on Organoclay Self-assembly
AvinashJ. Patil, Stephen Mann 		239
8.1 Introduction 239
8.2 Synthesis and Characterization of Organically Functionalized 2:1 Magnesium Phyllosilicates 240
8.3 Magnesium Organophyllosilicates with Higher-order Organization 243
8.4 Intercalation of Biomolecules within Organically Modified Magnesium Phyllosilicates 246
8.4.1 Protein-Organoclay Lamellar Nanocomposites 247
8.4.2 DNA-Organoclay Lamellar Nanostructures 252
8.4.3 Drug-Organoclay Layered Nanocomposites 253
8.5 Hybrid Nanostructures Based on Organoclay Wrapping of Single Biomolecules 254
8.5.1 Organoclay-wrapped Proteins and Enzymes 254
8.5.2 Organoclay-wrapped DNA 258
8.6 Functional Mesolamellar Bio-inorganic Nanocomposite Films 260
8.7 Summary 262
References 262
9 Biodegradable Polymer-based Nanocomposites: Nanostructure Control and Nanocomposite Foaming with the Aim of Producing Nano-cellular Plastics
Masami Okamoto 		271
9.1 Introduction 271
9.2 Nano-structure Development 272
9.2.1 Melt Intercalation 272
9.2.2 Interlayer Structure of OMLFs and Intercalation 273
9.2.2.1 Nano-fillers 273
9.2.2.2 Molecular Dimensions and Interlayer Structure 274
9.2.2.3 Correlation of Intercalant Structure and Interlayer Opening 277
9.2.2.4 Nanocomposite Structure 278
9.3 Control of Nanostructure Properties 282
9.3.1 Flocculation Control and Modulus Enhancement 282
9.3.2 Linear Viscoelastic Properties 284
9.3.3 Elongational Flow and Strain-induced Hardening 288
9.4 Physicochemical Phenomena 290
9.4.1 Biodegradability 290
9.4.2 Photodegradation 295
9.5 Foam Processing using Supercritical CO2 296
9.5.1 PLA-based Nanocomposite 296
9.5.2 Temperature Dependence of Cellular Structure 298
9.5.3 CO2 Pressure Dependence 301
9.5.4 TEM Observation 305
9.5.5 Mechanical Properties of Nanocomposite Foams 307
9.6 Porous Ceramic Materials via Nanocomposites 307
9.7 Future Prospects 309
References 310
10 Biomimetic and Bioinspired Hybrid Membrane Nanomaterials
Mihail Barboiu 		313
10.1 Introduction 313
10.2 Molecular Recognition-based Hybrid Membranes 314
10.2.1 Multiple Molecular Recognition Principles 314
10.3 Self-organized Hybrid Membrane Materials 318
10.3.1 Ionic-conduction Pathways in Hybrid Membrane Materials 318
10.3.1.1 Ionic-conduction Pathways in Macrocyclic Hybrid Materials 319
10.3.1.2 Ionic-conduction Pathways in Peptido-mimetic Hybrid Materials 319
10.3.2 Self-organization in Hybrid Supramolecular Polymers 324
10.3.2.1 Self-organization by Base Pairing in Hybrid Supramolecular Polymers 325
10.3.2.2 Self-Organization of the Guanine Quadruplex in Hybrid Supramolecular Polymers 328
10.4 Dynamic Site Complexant Membranes 330
10.5 Conclusions 333
References 334
11 Design of Bioactive Nano-hybrids for Bone Tissue Regeneration
Masanobu Kamitakahara, Toshiki Miyazaki, Chikara Ohtsuki 		339
11.1 Introduction 339
11.2 Composite of Bioactive Ceramic Particles and Polymers 340
11.3 Bone-bonding Mechanism of Bioactive Materials 341
11.3.1 Interface between Bone and Bioactive Material 341
11.3.2 Simulated Body Fluid 342
11.3.3 Hydroxyapatite Formation on Bioactive Materials 343
114 Sol-Gel-derived Bioactive Nano-hybrids 345
11.4.1 Silicate-based Nano-hybrids 345
11.4.2 Nano-hybrids Starting from Methacryloxy Compounds 347
11.4.3 Nano-hybrids Based on Other than Silicate 349
11.4.4 Nano-hybrids Combined with Calcium Phosphates 353
11.5 Nano-hybrid Consisting of Bone-like Hydroxyapatite and Polymer 354
11.5.1 Biomimetic Process 354
11.5.2 Hydroxyapatite Deposition on Polymers Modified with Silanol Groups 356
11.5.3 Hydroxyapatite Deposition on Natural Polymers 357
11.5.4 Hydroxyapatite Deposition on Synthetic Polymers 358
11.5.5 Control of the Structure of Hydroxyapatite 359
11.6 Nano-hybrid Consisting of Hydroxyapatite and Protein 360
11.7 Conclusion 361
References 361
12 Nanostructured Hybrid Materials for Bone Implants Fabrication
María Vallet-Regí, Daniel Arcos 		367
12.1 Introduction 367
12.2 Bone: A Biological Hybrid Nanostructured Material 369
12.3 Biomimetic Materials for Bone Repair. The Hybrid Approach 372
12.3.1 The Hybrid Approach 374
12.4 Synthesis and Properties of Organic-Inorganic Hybrid Materials for Bone and Dental Applications 375
12.4.1 Class I Hybrid Materials 375
12.4.1.1 BG-Poly(vinyl Alcohol) 375
12.4.1.2 Silica Particles-pHEMA 378
12.4.2 Class II Hybrid Materials 378
12.4.2.1 PMMA-SiO2 Ormosils 380
12.4.2.2 PEG-SiO2 Ormosils 380
12.4.2.3 PDMS-CaO-SiO2-TiO2 Ormosils 380
12.4.2.4 PTMO-CaO-SiO2-TiO2 Hybrid Materials 383
12.4.2.5 MPS-HEMA Ormosils 383
12.4.2.6 Gelatine-SiO2 Systems 384
12.4.2.7 Poly(-Caprolactone)-Silica Ormosils 385
12.4.2.8 Bioactive Star Gels 387
12.4.2.9 The Synthesis of Bioactive Star Gels 388
12.4.2.10 How to Characterize Bioactive Star Gels? 389
12.4.2.11 The Bioactivity of the Star Gels 389
12.4.2.12 The Mechanical Properties of Bioactive Star Gels 391
12.5 Conclusion 392
References 393
13 Bio-inorganic Conjugates for Drug and Gene Delivery
Jin-Ho Choy, Jae-Min Oh, Soo-Jin Choi 		401
13.1 Introduction 401
13.2 Synthesis of Bio-inorganic Conjugates 403
13.3 Bio-inorganic Conjugate for Efficient Gene Delivery 407
13.3.1 Cellular Uptake Kinetics of LDH-FITC Into Cells 407
13.3.2 Effect of As-myc-LDH Hybrid on the Suppression of Cancer Cells 408
13.4 Bio-inorganic Conjugate for Efficient Drug Delivery 409
13.4.1 Cellular Uptake of MTX-LDH Hybrid 409
13.4.2 Effect of MTX-LDH on Cell Proliferation and Viability 409
13.4.3 Effect of MTX-LDH Hybrid on the Cell Cycle 410
13.4.4 Potential of Bio-inorganic Conjugates for Gene and Drug Delivery 411
13.5 Cellular Uptake Mechanism of LDH 412
13.5.1 EndocytosisofLDH 412
13.5.2 Endocytic Pathway of LDH 413
13.6 Conclusion 415
References 415
14 Halloysite Nanotubules, a Novel Substrate for the Controlled Delivery of Bioactive Molecules 419
Yuri M. Lvov, Ronald R. Price
14.1 Halloysite Structural Characterization 419
14.2 Macromolecule Loading and Sustained Release 422
14.2.1 Nanotubule Loading Procedure 422
14.2.2 Drugs and Biocides 423
14.2.3 Globular Proteins 427
14.3 Nanoassembly on Tubules and at the Lumen Opening 428
14.4 Catalysis in a Nanoconstrained Volume of the Tubule Lumen 431
14.5 Multilayer Halloysite Assembly for Organized Nanofilms. Forming Low Density Tubule Nanoporous Materials 436
14.5.1 Tubule-Polycation Multilayer 436
14.5.2 Assembly of Tubule/Sphere Multilayer Nanocomposites 437
14.6 Applications: Current and Potential 438
References 439
15 Enzyme-based Bioinorganic Materials
Claude Forano, Vanessa Prévot 		443
15.1 Introduction 443
15.2 Enzymes versus Inorganic Host Properties 445
15.2.1 Enzyme Properties 445
15.2.2 Inorganic Host Structures 446
15.3 Immobilization Strategy 446
15.3.1 Adsorption Process 448
15.3.2 Encapsulation Processes 449
15.3.3 Nanostructuring of Enzyme-based Films 450
15.3.4 Covalent Grafting 452
15.4 Bioinorganic Nanohybrids 454
15.4.1 Immobilization of Enzymes in 2-D Inorganic Hosts 454
15.4.1.1 Immobilization in Clay Minerals and Related Materials 454
15.4.1.2 Immobilization in Layered Double Hydroxides 457
15.4.1.3 Immobilization in Layered Metal Oxides 460
15.4.1.4 Immobilization in Layered Zirconium Phosphate and Phosphonate 461
15.4.2 Immobilization of Enzymes in 3-D Inorganic Hosts 464
15.4.2.1 Immobilization in SiO2 464
15.4.2.2 Immobilization on Alumina 467
15.4.2.3 Immobilization in Zeolite 469
15.4.2.4 Immobilization in Hydroxyapatite and Tricalciumphosphate 471
15.5 Enzyme-Host Structure Interactions 471
References 476
  Index 485

 
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