Multilayer Thin Films

This second, comprehensive edition of the pioneering book in this field 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. List of Contributors XXV

Volume 1

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

Part I Preparation and Characterization 23

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Index 1053

Preface
Foreword

PART I: PREPARATION AND CHARACTERIZATION

Layer-by-Layer Processed Multilayers: Challenges and Opportunities
From Conventional to Unconventional Layer-by-Layer Assembly Methods
Hierarchic Multilayer Thin Films
Layer-by-Layer Assembly Using Host-Guest Interactions
LbL Assemblies Using van der Waals or Affinity Interaction and Their Applications
Layer-by-Layer Assembly of Polymeric Complexes
Making Aqueous Nanocolloids from Low Soluble Materials: LbL Shells on Nanocores
Cellulose Fibres and Fibrils as Templates for the Layer-by-Layer (LbL) Technology
Freely Standing LbL Films
Neutron Reflectrometry at Polyelectrolyte Multilayers
Molecular Conformation in and Structural Properties of Polyelectrolyte Multilayers
Ion Doping in Polyelectrolyte Multilayers
Conductivity Spectra of Polyelectrolyte Multilayers Revealing Ion Transport Processes
Layer-by-Layer Assemblies of pH- and Temperature-Responsive Polymers: Molecular Interactions, Exchange with Solution, Film Structure and Response
Tailoring Mechanics of Free-Standing Multilayers
Design and Translation of Nanolayer Assembly Processes: Electrochemical Energy to Programmable Pharmacies
Surface Initiated Polymerization and Layer-by-Layer Films
Quartz Crystal Resonator as a Tool for Following the Buildup of Polyelectrolyte Multilayers

PART II: APPLICATIONS

Electrostatic and Coordinative Supramolecular Assembly of Functional Films for Electronic Applications and Materials Separation
Optoelectronic Materials and Devices Incorporating Polyelectrolyte Multilayers
Nanostructured Electrodes Assembled from Metal Nanoparticles and Quantum Dots in Polyelectrolytes
Advanced Nanoscale Composite Materials with Record Properties by Layer-by-Layer Assembly
Carbon Nanotube Based Assemblies
Nanoconfined Polyelectrolyte Multilayers: From Chain Crowding to Biological Applications
The Design of Polysaccharide Multilayers for Medical Applications
Polyelectrolyte Multilayer Films Based on Polysaccharides: From Physical Chemistry to the Control of Cell Differentiation
Diffusion of Nanoparticles in LbL Films as a New Tool to Produce Multifunctional Coatings
Biological Active Surfaces on Colloids by Means of the Layer-by-Layer Technology
A 'Multilayered' Approach to the Delivery of DNA: Exploiting the Structure of Polyelectrolyte Multilayers to Promote Surface-Mediated Cell Transfection and Multi-Agent Delivery
Designing LbL Capsules for Drug Loading and Release
Stimuli-Sensitive LbL Films for Controlled Delivery of Proteins and Drugs
Assembly of Multilayer Capsules for Drug Encapsulation and Controlled Release
Engineered Thin Films and Capsules for Biomedical Applications
Assembly of Polymer Multilayers from Organic Solvents for Biomolecule Encapsulation
Stimuli-Responsive LbL Capsules
Domain-Containing Polyelectrolyte Films for the Entrapment of Active Compounds
Ion Transport through Polyelectrolyte Multilayers
Remote Release from Multilayer Capsules and Films
Controlled Architectures in LbL Films for Sensing and Biosensing
Patterned Multilayer Systems and Directed Self-Assembly of Functional Nano-Bio Materials
Electrochemically Active LbL Multilayer Films: From Biosensors to Nanocatalysts
Multilayer Polyelectrolyte Assembly in Feedback Active Coatings and Films 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.

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.