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Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials, 2nd Edition

Gero Decher (Editor), Joe B. Schlenoff (Editor)
ISBN: 978-3-527-31648-9
1112 pages
June 2012
Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials, 2nd Edition (3527316485) cover image
This second, comprehensive edition of the pioneering book in this fi eld has been completely revised and extended, now stretching to two
volumes. The result is a comprehensive summary of layer-by-layer assembled, truly hybrid nanomaterials and thin fi lms, covering organic,
inorganic, colloidal, macromolecular, and biological components, as well as the assembly of nanoscale fi lms derived from them on surfaces.
These two volumes are essential for anyone working in the field, as well as scientists and researchers active in materials development, who
needs the key knowledge provided herein for linking the field of molecular self-assembly with the bio- and materials sciences.
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List of Contributors XXV

Volume 1

1 Layer-by-Layer Assembly (Putting Molecules to Work) 1
Gero Decher

1.1 The Whole is More than the Sum of its Parts 1

1.2 From Self-Assembly to Directed Assembly 1

1.3 History and Development of the Layer-by-Layer Assembly Method 4

1.4 LbL-Assembly is the Synthesis of Fuzzy Supramolecular Objects 6

1.5 Reproducibility and Choice of Deposition Conditions 7

1.6 Monitoring Multilayer Build-up 10

1.7 Spray- and Spin-Assisted Multilayer Assembly 13

1.8 Recent Developments 14

1.9 Final Remarks 18

References 19

Part I Preparation and Characterization 23

2 Layer-by-Layer Processed Multilayers: Challenges and Opportunities 25
Michael F. Rubner and Robert E. Cohen

2.1 Introduction 25

2.2 Fundamental Challenges and Opportunities 25

2.3 Technological Challenges and Opportunities 31

2.4 The Path Forward 36

References 36

3 Layer-by-Layer Assembly: from Conventional to Unconventional Methods 43
Guanglu Wu and Xi Zhang

3.1 Introduction 43

3.2 Conventional LbL Methods 44

3.3 Unconventional LbL Methods 52

3.4 Summary and Outlook 64

References 64

4 Novel Multilayer Thin Films: Hierarchic Layer-by-Layer (Hi-LbL) Assemblies 69
Katsuhiko Ariga, Qingmin Ji, and Jonathan P. Hill

4.1 Introduction 69

4.2 Hi-LbL for Multi-Cellular Models 70

4.3 Hi-LbL for Unusual Drug Delivery Modes 72

4.4 Hi-LbL for Sensors 75

4.5 Future Perspectives 79

References 80

5 Layer-by-Layer Assembly Using Host-Guest Interactions 83
Janneke Veerbeek, David N. Reinhoudt, and Jurriaan Huskens

5.1 Introduction 83

5.2 Supramolecular Layer-by-Layer Assembly 84

5.3 3D Patterned Multilayer Assemblies on Surfaces 85

5.4 3D Supramolecular Nanoparticle Crystal Structures 88

5.5 Porous 3D Supramolecular Assemblies in Solution 90

5.6 Conclusions 95

References 95

6 LbL Assemblies Using van der Waals or Affinity Interactions and Their Applications 99
Takeshi Serizawa, Mitsuru Akashi, Michiya Matsusaki, Hioharu Ajiro, and Toshiyuki Kida

6.1 Introduction 99

6.2 Stereospecific Template Polymerization of Methacrylates by Stereocomplex Formation in Nanoporous LbL Films 100

6.3 Preparation and Properties of Hollow Capsules Composed of Layer-by-Layer Polymer Films Constructed through van der Waals Interactions 113

6.4 Fabrication of Three-Dimensional Cellular Multilayers Using Layer-by-Layer Protein Nanofilms Constructed through Affinity Interaction 120

6.5 Conclusion 129

References 129

7 Layer-by-Layer Assembly of Polymeric Complexes 135
Junqi Sun, Xiaokong Liu, and Jiacong Shen

7.1 Introduction 135

7.2 Concept of LbL Assembly of Polymeric Complexes 136

7.3 Structural Tailoring of LbL-Assembled Films of Polymeric Complexes 140

7.4 LbL-Assembled Functional Films of Polymeric Complexes 144

7.5 Summary 149

References 149

8 Making Aqueous Nanocolloids from Low Solubility Materials: LbL Shells on Nanocores 151
Yuri Lvov, Pravin Pattekari, and Tatsiana Shutava

8.1 Introduction 151

8.2 Formation of Nanocores 153

8.3 Ultrasonication-Assisted LbL Assembly 154

8.4 Solvent-Assisted Precipitation Into Preformed LbL-Coated Soft Organic Nanoparticles 159

8.5 Washless (Titration) LbL Technique 161

8.6 Formation of LbL Shells on Nanocores 163

8.7 Drug Release Study 165

8.8 Conclusions 168

References 168

9 Cellulose Fibers and Fibrils as Templates for the Layer-by-Layer (LbL) Technology 171
Lars Wågberg

9.1 Background 171

9.2 Formation of LbLs on Cellulose Fibers 172

9.3 The use of LbL to Improve Adhesion between Wood Fibers 176

9.4 The Use of LbL to Prepare Antibacterial Fibers 179

9.5 The use of NFC/CNC to Prepare Interactive Layers Using the LbL Approach 182

9.6 Conclusions 185

References 186

10 Freely Standing LbL Films 189
Chaoyang Jiang and Vladimir V. Tsukruk

10.1 Introduction 189

10.2 Fabrication of Freely Standing Ultrathin LbL Films 189

10.3 Porous and Patterned Freely Standing LbL Films 204

10.4 Freely Standing LbL Films with Weak Interactions 208

References 214

11 Neutron Reflectometry at Polyelectrolyte Multilayers 219
Ralf Köhler, Chloé Chevigny, and Regine von Klitzing

11.1 Introduction 219

11.2 Neutron Reflectometry 219

11.3 Preparation Techniques for Polyelectrolyte Multilayers 224

11.4 Types of Polyelectrolytes 233

11.5 Preparation Parameters 238

11.6 Influence of External Fields After PEM Assembly 242

11.7 PEM as a Structural Unit 259

11.8 Conclusion and Outlook 261

References 262

12 Polyelectrolyte Conformation in and Structure of Polyelectrolyte Multilayers 269
Stephan Block, Olaf Soltwedel, Peter Nestler, and Christiane A. Helm

12.1 Introduction 269

12.2 Results 270

12.3 Conclusion and Outlook 279

References 280

13 Charge Balance and Transport in Ion-Paired Polyelectrolyte Multilayers 281
Joseph B. Schlenoff

13.1 Introduction 281

13.2 Association Mechanism: Competitive Ion Pairing 283

13.3 Surface versus Bulk Polymer Charge 292

13.4 Polyelectrolyte Interdiffusion 301

13.5 Ion Transport Through Multilayers: the ‘‘Reluctant’’ Exchange Mechanism 305

13.6 Concluding Remarks 315

References 315

14 Conductivity Spectra of Polyelectrolyte Multilayers Revealing Ion Transport Processes 321
Monika Schönhoff and Cornelia Cramer

14.1 Introduction to Conductivity Studies of LbL Films 321

14.2 PEM Spectra: Overview 323

14.3 DC Conductivities of PEMs 324

14.4 Modeling of PEM Spectra 328

14.5 Ion Conduction in Polyelectrolyte Complexes 329

14.6 Scaling Principles in Conductivity Spectra: From Time–Temperature to Time–Humidity Superposition 332

References 335

15 Responsive Layer-by-Layer Assemblies: Dynamics, Structure and Function 337
Svetlana Sukhishvili

15.1 Introduction 337

15.2 Chain Dynamics and Film Layering 338

15.3 Responsive Swellable LbL Films 348

15.4 Conclusion and Outlook 358

References 359

16 Tailoring the Mechanics of Freestanding Multilayers 363
Andreas Fery and Vladimir V. Tsukruk

16.1 Introduction 363

16.2 Measurements of Mechanical Properties of Flat LbL Films 364

16.3 Mechanical Properties of LbL Microcapsules 372

16.4 Prospective Applications Utilizing Mechanical Properties 378

References 386

17 Design and Translation of Nanolayer Assembly Processes: Electrochemical Energy to Programmable Pharmacies 393
Md. Nasim Hyder, Nisarg J. Shah, and Paula T. Hammond

17.1 Introduction 393

17.2 Controlling Transport and Storing Charge in Multilayer Thin Films: Ions, Electrons and Molecules 395

17.3 LbL Films for Multi-Agent Drug Delivery – Opportunities for Programmable Release 406

17.4 Automated Spray-LbL – Enabling Function and Translation 422

17.5 Concluding Remarks 431

References 431

18 Surface-Initiated Polymerization and Layer-by-Layer Films 437
Nicel Estillore and Rigoberto C. Advincula

18.1 Introduction 437

18.2 Overview of Surface-Grafted Polymer Brushes 438

18.3 Layer-by-Layer (LbL) Self-Assembly 440

18.4 Combined LbL-SIP Approach 441

18.5 Applications of the Combined LbL-SIP Approach 449

18.6 Concluding Remarks 453

References 453

19 Quartz Crystal Resonator as a Tool for Following the Build-up of Polyelectrolyte Multilayers 455
Mikko Salomäki and Jouko Kankare

19.1 Introduction 455

19.2 Basic Concepts 456

19.3 Growth Processes 461

19.4 Experimental Techniques 463

19.5 Analysis of QCR Data 465

References 469

Volume 2

Part II Applications 471

20 Electrostatic and Coordinative Supramolecular Assembly of Functional Films for Electronic Application and Materials Separation 473
Bernd Tieke, Ashraf El-Hashani, Kristina Hoffmann, and Anna Maier

20.1 Introduction 473

20.2 Polyelectrolyte Multilayer Membranes 474

20.3 Summary and Conclusions 504

References 506

21 Optoelectronic Materials and Devices Incorporating Polyelectrolyte Multilayers 511
H.D. Robinson, Reza Montazami, Chalongrat Daengngam, Ziwei Zuo, Wang Dong, Jonathan Metzman, and Randy Heflin

21.1 Introduction 511

21.2 Second Order Nonlinear Optics 512

21.3 Plasmonic Enhancement of Second Order Nonlinear Optical Response 515

21.4 Nonlinear Optical Fibers 519

21.5 Optical Fiber Biosensors 521

21.6 Antireflection Coatings 525

21.7 Electrochromic Devices 527

21.8 Electromechanical Actuators 530

References 533

22 Nanostructured Electrodes Assembled from Metal Nanoparticles and Quantum Dots in Polyelectrolytes 539
Lara Halaoui

22.1 Introduction 539

22.2 Nanostructured Pt Electrodes from Assemblies of Pt Nanoparticles in Polyelectrolytes 540

22.3 Nanostructured Photoelectrodes from Assemblies of Q-CdS in Polyelectrolytes 552

22.4 Conclusions 558

References 559

23 Record Properties of Layer-by-Layer Assembled Composites 573
Ming Yang, Paul Podsiadlo, Bong Sup Shim, and Nicholas A. Kotov

23.1 Introduction 573

23.2 LbL Assemblies of Clays 574

23.3 LBL Assemblies of Carbon Nanotubes 582

23.4 Conclusions and Perspectives 589

References 590

24 Carbon Nanotube-Based Multilayers 595
Yong Tae Park and Jaime C. Grunlan

24.1 Introduction 595

24.2 Characteristics of Carbon Nanotube Layer-by-Layer Assemblies 596

24.4 Conclusions 609

References 609

25 Nanoconfined Polyelectrolyte Multilayers: From Nanostripes to Multisegmented Functional Nanotubes 613
Cécile J. Roy, Cédric C. Buron, Sophie Demoustier-Champagne, and Alain M. Jonas

25.1 Introduction 613

25.2 Estimation of the Size of Polyelectrolyte Chains in Dilute Solutions 614

25.3 Confining LbL Assembly on Flat Surfaces 618

25.4 Confining LbL Assembly in Nanopores 624

25.5 Conclusions 633

References 634

26 The Design of Polysaccharide Multilayers for Medical Applications 637
Benjamin Thierry, Dewang Ma, and Françoise M. Winnik

26.1 Introduction 637

26.2 Polysaccharides as Multilayered film Components: An Overview of Their Structure and Properties 638

26.3 Multilayers Formed by Assembly of Weak Polyanions and Chitosan or Chitosan Derivatives 642

26.4 Multilayers Formed by Assembly of Strong Polyanions and Chitosan or Chitosan Derivatives 647

26.5 Cardiovascular Applications of Polysaccharide Multilayers 650

26.6 Conclusions 654

References 655

27 Polyelectrolyte Multilayer Films Based on Polysaccharides: From Physical Chemistry to the Control of Cell Differentiation 659
Thomas Boudou, Kefeng Ren, Thomas Crouzier, and Catherine Picart

27.1 Introduction 659

27.2 Film Internal Composition and Hydration 660

27.3 Film Cross-Linking: Relation Between Composition and Mechanical Properties 666

27.4 Cell Adhesion onto Cross-Linked Films: Cell Adhesion, Cytoskeletal Organization and Comparison with Other Model Materials 671

27.5 Cell Differentiation: ESC and Myoblasts 679

27.6 Conclusions 684

References 685

28 Diffusion of Nanoparticles and Biomolecules into Polyelectrolyte Multilayer Films: Towards New Functional Materials 691
Marc Michel and Vincent Ball

28.1 Introduction 691

28.2 LBL Films in Which Nanoparticles are Incorporated Step-By-Step 693

28.3 LBL Films Made Uniquely From Nanoparticles 693

28.4 Nanoparticles Produced by Post-treatment of Deposited Films 694

28.5 Diffusion of Colloids in Already Deposited Films 698

28.6 Emerging Properties of Films Filled with Nanoparticles by the Post-incubation Method 705

28.7 Conclusions and Perspectives 706

References 707

29 Coupling Chemistry and Hybridization of DNA Molecules on Layer-by-Layer Modified Colloids 711
Jing Kang and Lars Dähne

29.1 Introduction 711

29.2 Materials and Methods 712

29.3 Results 716

29.4 Summary 727

References 729

30 A ‘‘Multilayered’’ Approach to the Delivery of DNA: Exploiting the Structure of Polyelectrolyte Multilayers to Promote Surface-Mediated Cell Transfection and Multi-Agent Delivery 731
David M. Lynn

30.1 Introduction 731

30.2 Surface-Mediated Delivery of DNA: Motivation and Context, Opportunities and Challenges 732

30.3 Films Fabricated Using Hydrolytically Degradable Cationic Polymers 734

30.4 Toward Spatial Control: Release of DNA from the Surfaces of Implants and Devices 736

30.5 Toward Temporal Control: Tunable Release and Sequential Release 739

30.6 Concluding Remarks 745

References 746

31 Designing LbL Capsules for Drug Loading and Release 749
Bruno G. De Geest and Stefaan C. De Smedt

31.1 Introduction 749

31.2 Engineering Microparticulate Templates to Design LbL Capsules for Controlled Drug Release 750

31.3 Engineering the Shell to Design LbL Capsules for Controlled Drug Release 753

31.4 Interaction of LbL Capsules with Living Cells In Vitro and In Vivo 759

31.5 Conclusions 761

References 761

32 Stimuli-Sensitive LbL Films for Controlled Delivery of Proteins and Drugs 765
Katsuhiko Sato, Shigehiro Takahashi, and Jun-ichi Anzai

32.1 Introduction 765

32.2 Avidin-Containing LbL Films 765

32.3 Concanavalin A-containing LbL Films 768

32.4 Dendrimer-Containing LbL Films 771

32.5 Insulin-Containing LbL Films 772

32.6 Conclusions 774

References 776

33 Assembly of Multilayer Capsules for Drug Encapsulation and Controlled Release 777
Jinbo Fei, Yue Cui, Qiang He, and Junbai Li

33.1 Introduction 777

33.2 Magnetically Sensitive Release 779

33.3 Ultrasound-Stimulated Release 780

33.4 Photo-Stimulated Release 781

33.5 Thermo-Stimulated Release 783

33.6 pH-Sensitive Release 785

33.7 Redox-Controlled Release 787

33.8 Bio-Responsive Release 788

33.9 Extension 792

33.10 Concluding Remarks 794

References 794

34 Engineered Layer-by-Layer Assembled Capsules for Biomedical Applications 801
Angus P.R. Johnston, Georgina K. Such, Sarah J. Dodds, and Frank Caruso

34.1 Introduction 801

34.2 Template Selection 801

34.3 Material Assembly 804

34.4 Loading 809

34.5 Degradation and Release 813

34.6 Applications 816

34.7 Conclusions 823

References 824

35 Assembly of Polymer Multilayers from Organic Solvents for Biomolecule Encapsulation 831
Sebastian Beyer, Jianhao Bai, and Dieter Trau

35.1 Introduction 831

35.2 Limitations of LbL-Based Biomolecule Encapsulation in Aqueous Phase 834

35.3 LbL Biomolecule Encapsulation in the Organic Phase 835

35.4 Conclusion and Outlook 847

References 849

36 Stimuli-Responsive Polymer Composite Multilayer Microcapsules and Microchamber Arrays 851
Maria N. Antipina, Maxim V. Kiryukhin, and Gleb B. Sukhorukov

36.1 Introduction 852

36.2 Fabrication of Stimuli-Responsive LbL Microcapsules 853

36.3 Microchamber Arrays 873

36.4 Conclusion 881

References 882

37 Domain-Containing Functional Polyelectrolyte Films: Applications to Antimicrobial Coatings and Energy Transfer 891
Aurélie Guyomard, Bernard Nysten, Alain M. Jonas, and Karine Glinel

37.1 Introduction 891

37.2 Polyelectrolyte Films Incorporating Randomly Distributed Hydrophobic Nanodomains for Antimicrobial Applications 893

37.3 Multicompartmentalized Stratified Polyelectrolyte Films for Control of Energy Transfer 898

37.4 Conclusions and Perspectives 903

References 904

38 Creating Functional Membranes Through Polyelectrolyte Adsorption 907
Merlin L. Bruening

38.1 Introduction 907

38.2 Functionalization of the Interior of Membranes 908

38.3 LBL Films as Membrane Skins 918

38.4 Challenges 922

References 922

39 Remote and Self-Induced Release from Polyelectrolyte Multilayer Capsules and Films 925
Andre G. Skirtach, Dmitry V. Volodkin, and Helmuth Möhwald

References 940

40 Controlled Architectures in LbL Films for Sensing and Biosensing 951
Osvaldo N. Oliveira Jr., Pedro H.B. Aoki, Felippe J. Pavinatto, and Carlos J.L. Constantino

40.1 Introduction 951

40.2 LbL-Based Sensors and Biosensors 952

40.3 Special Architectures for Sensing and Biosensing 964

40.4 Statistical and Computational Methods to Treat the Data 969

40.5 Conclusions and Perspectives 977

References 978

41 Patterned Multilayer Systems and Directed Self-Assembly of Functional Nano-Bio Materials 985
Ilsoon Lee

41.1 New Approaches and Materials for Multilayer Film Patterning Techniques 985

41.2 Cell Adhesion and Patterning Using PEMs 988

41.3 PEMs Incorporating Proteins and Their Patterning 990

41.4 Metal/Graphene Conductive Patterning via PEM Films 992

41.5 Ordered and Disordered Particles on PEMs 995

41.6 Mechanical Aspects of PEM Films and Degradable Films 997

References 999

42 Electrochemically Active LbL Multilayer Films: From Biosensors to Nanocatalysts 1003
Ernesto. J. Calvo

42.1 Introduction 1003

42.2 Electrochemical Response 1004

42.3 Dynamics of Charge Exchange 1012

42.4 Conclusions 1033

References 1034

43 Multilayer Polyelectrolyte Assembly in Feedback Active Coatings and Films 1039
Dmitry G. Shchukin and Helmuth Möhwald

43.1 Introduction. The Concept of Feedback Active Coatings 1039

43.2 Polyelectrolyte-Based Self-Healing Anticorrosion Coatings 1040

43.3 Coatings with Antibacterial Activity 1045

43.4 Conclusions and Outlook 1050

References 1050

Index 1053

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Gero Decher is a Distinguished Professor of Chemistry at the University of Strasbourg, France, a senior member of the Institut Universitaire de France (IUF) and a member of the International Center for Frontier Research in Chemistry. His research team is located at CNRS Institut Charles Sadron in Strasbourg where he continues to develop the layer-by-layer assembly method in collaboration with his colleagues Pierre Schaaf and Jean-Claude Voegel. This method is applied in many laboratories world-wide in various scientific disciplines, including chemistry, materials science and biotechnology. Gero Decher has received numerous awards, including the ECIS-Rhodia prize in 2010 and the Grand Prix of the French "Académie des Sciences" for Nanobiotechnology in 2009.

Joseph B. Schlenoff is Mandelkern Professor of Polymer Science of the Department of Chemistry and Biochemistry at the Florida State University, USA. His laboratory is engaged in multidisciplinary research centered on the use of novel structures made from polyelectrolytes that are deposited using the layer-by-layer technique. His work, supported by the National Science Foundation and the National Institutes of Health, among others, focuses on fundamental polymer science aspects of polyelectrolyte complexes and on their interactions with biological materials. In 2011, Joseph Schlenoff received a Gutenburg Chair at the University of Strasbourg.
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