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Materials scientists are often faced with the problem of modifying surfaces of objects, yet keeping their shape and properties. This book provides a detailed survey on the new technology of adsorption from solution for the fabrication of molecularly ordered multicomposite films in order to replace and expand on the well known Langmuir-Blodgett technology and to open the field of molecular self-assembly to materials and biosciences.
The book is aimed at scientists who want to integrate several different functional entities in a single device. To this audience it presents the technique of layer-by-layer assembly as today's most powerful key technology, which is low cost, solution based and very robust. It is already beginning to make the transition from academic research into industrial mass production.

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CONTENTS
Foreword = Ⅴ
Preface = XV
List of Contributors = XVII
1 Polyelectrolyte Multilayers, an Overview / G. Decher = 1
 1.1 Why is the Nanoscale so Interesting = 1
 1.2 From Self-Assembly to Directly Assembly = 1
 1.3 The Layer-by-Layer Deposition Technique = 3
  1.3.1 LbL Deposition is the Synthesis of Polydisperse Supramolecular Objects = 4
  1.3.2 Reproducibility and Deposition Conditions = 6
  1.3.3 Monitoring Multilayer Buildup = 7
   1.3.3.1 Ex-situ Characterisation = 7
   1.3.3.2 In-situ Characterisation = 9
  1.3.4 Multilayers by Solution Dipping, Spraying or Spin Coating = 12
  1.3.5 Post-preparation Treatment of Multilayer Films = 12
   13.5.1.1 Annealing = 12
   13.5.1.2 Photopatterning = 15
 1.4 Multilayer Structure = 16
  1.4.1 The Zone Model for Polyelectrolyte Films = 17
  1.4.2 Layered or Amorphous : What Makes Multilayers Unique Supramolecular Species? = 20
 1.5 Multimaterial Films = 24
 1.6 Toward Compartmentalized Films : Barrier Layers and Nanoreactors = 26
 1.7 Commercial Applications = 30
 1.8 References = 31
2 Fundamentals of Polyelectrolyte Complexes in Solution and the Bulk / V. Kabanov = 47
 2.1 Introduction = 47
 2.2 Interpolyelectrolyte Reactions and Solution Behavior of Interpolyelectrolyte Complexes = 48
  2.2.1 Kinetics and Mechanism of Polyelectrolyte Coupling and Interchange Reactions = 52
  2.2.2 Solution Properties of Equilibrated Nonstoichiometric Interpolyelectrolyte Complexes = 61
  2.2.3 Transformation of Interpolyelectrolyte Complexes in External Salt Solutions = 66
 2.3 Complexation of Polyelectrolytes with Oppositely Charged Hydrogels = 74
 2.4 Structural and Mechanical Properties of Interpolyelectrolyte Complexes in the Bulk = 76
 2.5 Conclusion = 82
 2.6 References = 83
3 Polyelectrolyte Adsorption and Multilayer Formation / J. -F. Joanny ; M. Castelnovo = 87
 3.1 Introduction = 87
 3.2 Polyelectrolytes in Solution = 89
 3.3 Polyelectrolytes at Interfaces = 90
 3.4 Polyelectrolyte Complexes = 92
 3.5 Multilayer Formation = 94
 3.6 Concluding Remarks = 96
 3.7 References = 97
4 Charge Balance and Transport in Polyelectrolyte Multilayers / J. B. Schlenoff = 99
 4.1 Introduction = 99
 4.2 Interactions = 101
  4.2.1 Mechanism : Competitive Ion Pairing = 101
  4.2.2 Intrinsic vs. Extrinsic Charge Compensation = 103
   4.2.2.1 Key Equilibria = 103
   4.2.2.2 Swelling and Smoothing : Estimating Interaction Energies = 105
   4.2.2.3 Multilayer Decomposition = 108
 4.3 Excess Charge = 109
  4.3.1 Surface vs. Bulk Polymer Charge = 109
  4.3.2 Distribution of Surface Charge in Layer-by-Layer Buildup : Mechanism = 113
  4.3.3 Equilibrium vs. non-Equilibrium Conditions for Salt and Polyer Sorption = 117
 4.4 Equilibria and Transport = 118
  4.4.1 Ion Transport through Multilayers : the "Reluctant" Exchange Mechanism = 118
  4.4.2 Practical Consequences : Trapping and Self-Trapping = 126
 4.5 Conclusions = 127
 4.6 References = 130
5 pH-Controlled Fabrication of Polyelectrolyte Multilayers : Assembly and Applicaitons / M. F. Rubner = 133
 5.1 Introduction = 133
 5.2 Layer-by-Layer Assembly of Weak Polyelectrolyte Multilayers = 134
 5.3 Light Emitting Thin Film Devices = 137
 5.4 Microporous Thin Films = 139
 5.5 Nanoreactors, Electroless Plating and Ink-jet Printing = 141
 5.6 Surface Modification via Selective Adsorption of Block Copolymers = 144
 5.7 Patterning of Weak Polyelectrolyte Multilayers = 145
  5.7.1 Micro-Contact Printing = 146
  5.7.2 Ink-jet Printing of Hydrogen-Bonded Multilayers = 148
 5.8 Conclusions and Future Prospects = 152
 5.9 References = 153
6 Recent Progress in the Surface Sol-Gel Process and Protein Multilayers / I. Ichinose ; K. Kuroiwa ; Y. Lvov ; T. Kunitake = 155
 6.1 Alternating Adsorption = 155
  6.1.1 Surface Sol-Tel Process = 155
  6.1.2 Adsorption of Cationic Compounds on Metal Oxide Gels = 157
  6.1.3 Multilayer Assembly of Metal Oxides and Proteins = 162
  6.1.4 Protein／Polyelectrolyte Multilayer Assembly = 166
 6.2 Recent Topics in Biological Applications = 167
  6.2.1 Biosensors = 168
  6.2.2 Nano-filtration = 169
  6.2.3 Bioreactors = 171
  6.2.4 Protein Capsule and Protein Shell = 173
 6.3 References = 174
7 Internally Structured Polyelectrolyte Multilayers / K. Glinel ; A. M. Jonas ; A. Laschwesky ; P. Y. Vuillaume = 177
 7.1 Introduction = 177
 7.2 Experimental Considerations = 179
 7.3 Stratified Binary$${(A／B)}_n$$ Organic Multilayers = 182
 7.4 Stratified Binary$${(A／B)}_n$$ Hybrid Organic／Inorganic Multilayers = 188
  7.4.1 Initial Studies on Hybrid Assemblies = 189
  7.4.2 Layered Assemblies from Analogous Poly(diallyl ammonium) Salt Derivatives and Hectorite Platelets = 190
   7.4.2.1 General Structural Observations = 190
   7.4.2.2 Detailed Analysis of the Structure of Laponite-Based Hybrid LBL Films = 192
  7.4.3 Ordering in Hybrid Assemblies Employing Functional Polyions = 194
   7.4.3.1 Photocrosslinkable Polyelectrolytes = 194
   7.4.3.2 The Use of Mesomorphic Polyions = 195
 7.5 Hybrid Superlattices of the $${$$(A／B)_m$$／$$(C／D)_p$$}_n$$ Type = 196
  7.5.1 Literature Survey = 197
  7.5.2 Hybrid Organic／Inorganic Compartmentalized Multilayers from Clay Platelets = 198
 7.6 Conclusions = 201
 7.7 References = 202
8 Layer-by-Layer Assembly of Nanoparticles and Nanocolloids : Intermolecular Interactions, Structure and Materials Perspectives / N. A. Kotov = 207
 8.1 Introduction = 207
 8.2 Layer-by-Layer Assembly of Nanoparticles and Nanocolloids = 208
 8.3 Structural Factors of Individual Adsorption Layers = 217
  8.3.1 Intermolecular Interactions in the LBL Process = 217
  8.3.2 Ionic Conditions = 222
  8.3.3 Effect of Particle Shape on the Density of the Adsorption Layer = 224
 8.4 Stratified LBL Assemblies of Nanoparticles and Nanocolloids = 225
  8.4.1 Self-standing LBL Films = 227
  8.4.2 Magnetic Properties of the Stratified LBL Assemblies of Nanoparticles = 229
  8.4.3 Nanorainbows : Graded Semiconductor Films from Nanoparticles = 231
 8.5 Conclusion = 235
 8.6 References = 236
9 Layer-by-Layer Self-assembled Polyelectrolytes and Nanoplatelets / J. H. Fendler = 245
 9.1 Introduction = 245
 9.2 Self-assembled Polyelectrolytes and Clay Nanoplatelets = 246
 9.3 Self-assembled Polyelectrolytes and Graphite Oxide Nanoplatelets = 250
 9.4 Potential Applications = 256
  9.4.1 Pollutant Photodestruction = 256
  9.4.2 Electronic Applications = 259
  9.4.3 Charge Storage = 263
 9.5 References = 268
10 Chemistry Directed Deposition via-Electrostatic and Secondary Interactions : A Nonlithographic Approach to Patterned Polyelectrolyte Multilayer Systems / P. T. Hammond = 271
 10.1 Introduction and Overview = 272
 10.2 Selective Deposition of Polyelectrolyte Multilayer Systems = 273
  10.2.1 Selective Deposition of Strong Polyelectrolytes = 273
   10.2.1.1 Basis of Selective Adsorption and Ionic Strength Effects = 273
   10.2.1.2 Formation of Complex Multilayer Structures = 276
  10.2.2 Understanding and Utilizing Secondary Interactions in Selective Deposition = 277
   10.2.2.1 Establishing the Rules for Weak Polyamine Deposition = 277
   10.2.2.2 Confirming the Rules of Selective Adsorption : SFM Investigations = 279
   10.2.2.3 Using the Rules : Side-by-Side Structures = 280
   10.2.2.4 The Next Steps : Surface Sorting of Multilayers and Other Elements = 281
 10.3 Polymer-on-Polymer Stamping = 282
  10.3.1 Fundamental Studies of Polymer-on-Polymer Stamping = 284
   10.3.1.1 Stamping of Ionic Polymers = 285
   10.3.1.2 Stamping of Block Copolymers = 285
  10.3.2 POPS as a Template for Other Materials Deposition = 287
 10.4 Directed Assembly of Colloidal Particles = 289
  10.4.1 Selective Deposition and Controlled Cluster Size on Multilayer Templates = 290
  10.4.2 Surface Sorting with Particles on Multilayer Surfaces = 292
  10.4.3 Selective Electroless Plating of Colloidal Particle Arrays = 293
 10.5 Functional Polymer Thin Films for Electrochemical Device and Systems Applications = 294
  10.5.1 Electrochromic Polyelectrolyte Multilayer Device Construction = 295
  10.5.2 Ionically Conducting Multilayers for Electrochemical Device Applications = 296
 10.6 Summary = 297
 10.7 References = 298
11 Layered Nanoarchitectures Based on Electro- and Photo-active Building Blocks / X. Zhang ; J. Sun ; J. Shen = 301
 11.1 Introduction = 301
 11.2 Multilayer Asemblies of Electroactive Species of Chemically Modified Electrodes = 304
  11.2.1 Controlled Fabrication of Multilayers with a Single Active Component = 305
  11.2.2 Controlled "Cascade" Modification with Binary Active Components = 309
   11.2.2.1 Bienzyme Assemblies of Glucose Oxidase and Glucoamylase = 310
   11.2.2.2 Alternating Assemblies of Glucose Osidase and Polycationic Electron Transfer = 313
  11.2.3 The Incorporation of Conductive Species to Improve the Performance of the Modified Electrodes = 314
 11.3 Ionic Self-assembly of Photoactive Materials and the Fabrication of "Robust" Multilayer = 318
  11.3.1 Ways to Fabricate Covalently Attached Multilayer Asemblies = 319
  11.3.2 Stable Entrapment of Oligo-charged Molecules Bearing Sulfonate Groups in Multilayer Assemblies = 323
  11.3.3 Covalently Attached Multilayer Assemblies of Polycationic Diazo-resins and Polyanionic Poly(Acrylic Acid) = 324
  11.3.4 Robust Nanoassemblies with Complex and Hybrid Structures = 326
 11.4 Summary and Outlook = 328
 11.5 References = 328
12 Coated Colloids : Preparation, Characterization, Assembly and Utilization / F. Caruso ; G. Sukhorukov = 331
 12.1 Introduction = 331
 12.2 Preparation and Characterization of Coated Colloids = 333
  12.2.1 Layer-by-Layer Adsorption = 334
   12.2.1.1 Multilayered Coatings = 337
   12.2.1.2 Coating of Specific Cores = 344
  12.2.2 Colloid Precipitation = 349
 12.3 Assembly and Utilization of Coated Colloids = 351
  12.3.1 Mesoscopic Arrangement = 351
   12.3.1.1 Colloidal Crystals = 351
   12.3.1.2 Macro- and Mesoporous Materials = 351
  12.3.2 Enzymatic Catalysis = 354
   12.3.2.1 Dispersions = 354
   12.3.2.2 Thin Films = 355
  12.3.3 Optical Properties = 356
  12.3.4 Further Applications = 357
 12.4 Summary and Outlook = 358
 12.5 References = 359
13 Smart Capsules / H. M$$\ddot o$$hwald ; E. Donath ; G. Sukhorukov = 363
 13.1 Preparation and Structure = 364
  13.1.1 General Aspects = 364
   13.1.1.1 Core Materials = 364
   13.1.1.2 Wall Materials = 365
   13.1.1.3 Molecular Dynamics = 368
  13.1.2 Physics and Chemistry of Core Removal = 369
   13.1.2.1 Core Destruction = 369
   13.1.2.2 Core Material Release = 372
  13.1.2 Modification of Walls = 375
 13.2 Properties and Utilization = 376
  13.2.1 Permeability Control = 376
   13.2.1.1 Permeation Mechanisms = 377
   13.2.1.2 Controlled Release Profiles = 378
   13.2.1.3 Switchable Release = 379
  13.2.2 Stability and Mechanical Properties = 380
   13.2.2.1 Temperature Dependent Structures = 381
   13.2.2.2 Capsule Elasticity = 382
   13.2.2.3 Plasticity, Viscosity and Rupture Strength = 385
  13.2.3 Chemistry and Physics in Nanovolumes = 385
   13.2.3.1 Chemical Gradients from Inside to Outside = 386
   13.2.3.2 Precipitation and Dissolution = 387
   13.2.3.3 Chemistry in Capsules = 389
 13.3 Summary and Outlook = 390
 13.4 References = 391
14 Multilayers on Solid Planar Substrates : From Structure to Function / D. G. Kurth ; D. Volkmer ; R. v. Klitzing = 393
 14.1 Introduction = 393
 14.2 Formations and Structure of LbL Multilayers = 395
  14.2.1 Adsorption Kinetics of Polyelectrolytes = 395
  14.2.2 LbL Multilayer Formation = 397
  14.2.3 ζ-potential = 398
  14.2.4 Effect of Polymer Charge = 398
  14.2.5 Influence of Ionic Strength = 400
  14.2.6 Permeability of Polyelectrolyte Multilayer = 401
  14.2.7 Internal Structure = 403
 14.3 Implementing Metallsupramolecular Devices in Thin Layered Films = 405
  14.3.1 Introduction = 405
  14.3.2 Metallosupramolecular Coordination Polyelectrolytes = 408
  14.3.3 Polyoxometalate Clusters = 415
 14.4 Conclusions = 421
 14.5 References = 423
15 Functional Layer-by-Layer Assemblies with Photo- and Electrochemical Response and Selective Transport of Small Molecules and Ions / B. Tieke ; M. Pyrasch ; A. Toutianoush = 427
 15.1 Introduction = 427
 15.2 Photoreactive Assemblies = 428
  15.2.1 Diacetylene Derivatives = 429
  15.2.2 Azobenzene Derivatives = 434
 15.3 Diphenyldiketopyrrolopyrrole Derivatives = 438
 15.4 Electroactive Assemblies = 441
  15.4.1 Poly(metal tetrathiooxalates) = 441
  15.4.2 Prussian Blue and Analogues = 442
 15.5 Transport of Small Molecules and Ions Across Polyelectrolyte Multilayers = 446
  15.5.1 Transport of Small Molecules = 446
   15.5.1.1 Gas Permeation = 446
   15.5.1.2 Pervaporation Separation of Alcohol／Water Mixtures = 447
  15.5.2 Transport of Ions = 451
   15.5.2.1 Uptake of Ions = 454
 15.6 Summary and Conclusions = 456
 15.7 References = 458
16 Self-assembly and Characterization of Electro-optic Materials / R. Claus ; Y. -X. Wang ; L. Zhang ; K. Copper = 461
 16.1 Nonlinear Optical Polymers = 462
  16.1.1 Design, Synthesis and Characterization of Polydyes = 462
  16.1.2 ESA Fabrication of NLO Thin Films and Their Characterization = 464
  16.1.3 Nonlinear Optical Measurements = 467
 16.2 Electrostatic Self-assembly of CLD-1 Thin Films = 471
  16.2.1 Modification of CLD-1 and Fabrication of CLD-1 Thin Films = 471
  16.2.2 Measurements of Electro-optic Properties = 472
 16.3 Electrostatic Self-assembly of CdSe／PDDA Thin Films = 474
  16.3.1 Fabrication and Characterization = 475
  16.3.2 Electro-optic Modulation Measurements = 477
   16.3.2.1 Linear Electro-optic Modulation Measurement = 477
   16.3.2.2 Quadratic Electro-optic Modulation = 481
 16.4 Summary = 484
 16.5 References = 485
17 Controlling the Ion-Permeability of Layered Polyelectrolyte Films and Membranes / M. Bruening = 487
 17.1 Introduction = 487
 17.2 Electrochemical Studies of the Permeability of MPFs = 488
  17.2.1 As-deposited MPFs = 488
  17.2.2 Cross-linked PAA／PAH Films = 490
  17.2.3 Derivatized Polyelectrolyte Films = 493
 17.3 MPFs as Ion-Separation Membranes = 495
  17.3.1 Membrane Formation = 495
  17.3.2 Permeability of PAH／PSS and PAH／PAA Membranes = 496
  17.3.3 Cross-linked PAA／PAH Membranes = 499
  17.3.4 Hybrid PSS／PAH+PAA／PAH Membranes = 500
  17.3.5 Controlling the Charge Density in MPMs = 503
   17.3.5.1 Use of C$$u^2+$$ Complexes to Imprint Charged Sites into PAA／PAH Films = 503
   17.3.5.2 Control of Intrinsically Compensated Charge Through Derivatization and Photocleavage = 504
  17.3.6 Highly Selective Ultrathin Polyimide Membranes Formed from Layered Polyelectrolytes = 505
  17.3.7 Modeling of Selective Transport Through Layered Polyelectrolyte Membranes = 506
 17.4 Conclusions = 508
 17.5 References = 509
Index = 511