Multilayer Thin Films (eBook)

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.

VOLUME 1

LAYER-BY-LAYER ASSEMBLY (PUTTING MOLECULES TO WORK)
The Whole is More than the Sum of its Parts
From Self-Assembly to Directed Assembly
History and Development of the Layer-by-Layer Assembly Method
LbL-Assembly is the Synthesis of Fuzzy Supramolecular Objects
Reproducibility and Choice of Deposition Conditions
Monitoring Multilayer Build-up
Spray- and Spin-Assisted Multilayer Assembly
Recent Developments
Final Remarks

PART I: Preparation and Characterization

LAYER-BY-LAYER PROCESSED MULTILAYERS: CHALLENGES AND OPPORTUNITIES
Introduction
Fundamental Challenges and Opportunities
The Path Forward

LAYER-BY-LAYER ASSEMBLY: FROM CONVENTIONAL TO UNCONVENTIONAL METHODS
Introduction
Conventional LbL Methods
Unconventional LbL Methods
Summary and Outlook

NOVEL MULTILAYER THIN FILMS: HIERARCHIC LAYER-BY-LAYER (HI-LBL) ASSEMBLIES
Introduction
Hi-LbL for Multi-Cellular Models
Hi-LbL for Unusual Drug Delivery Modes
Hi-LbL for Sensors
Future Perspectives

LAYER-BY-LAYER ASSEMBLY USING HOST-GUEST INTERACTIONS
Introduction
Supramolecular Layer-by-Layer Assembly
3D Patterned Multilayer Assemblies on Surfaces
3D Supramolecular Nanoparticle Crystal Structures
Porous 3D Supramolecular Assemblies in Solution
Conclusions

LBL ASSEMBLIES USING VAN DER WAALS OR AFFINITY INTERACTIONS AND THEIR APPLICATIONS
Introduction
Stereospecific Template Polymerization of Methacrylates by Stereocomplex Formation in Nanoporous LbL Films
Preparation and Properties of Hollow Capsules Composed of Layer-by-Layer Polymer Films Constructed through van der Waals Interactions
Fabrication of Three-Dimensional Cellular Multilayers Using Layer-by-Layer Protein Nanofilms Constructed through Affinity Interaction
Conclusion

LAYER-BY-LAYER ASSEMBLY OF POLYMERIC COMPLEXES
Introduction
Concept of LbL Assembly of Polymeric Complexes
Structural Tailoring of LbL-Assembled Films of Polymeric Complexes
LbL-Assembled Functional Films of Polymeric Complexes
Summary

MAKING AQUEOUS NANOCOLLOIDS FROM LOW SOLUBILITY MATERIALS: LBL SHELLS ON NANOCORES
Introduction
Formation of Nanocores
Ultrasonication-Assisted LbL Assembly
Solvent-Assisted Precipitation Into Preformed LbL-Coated Soft Organic Nanoparticles
Washless (Titration) LbL Technique
Formation of LbL Shells on Nanocores
Drug Release Study
Conclusions

CELLULOSE FIBERS AND FIBRILS AS TEMPLATES FOR THE LAYER-BY-LAYER (LBL) TECHNOLOGY
Background
Formation of LbLs on Cellulose Fibers
The use of LbL to Improve Adhesion between Wood Fibers
The Use of LbL to Prepare Antibacterial Fibers
The use of NFC/CNC to Prepare Interactive Layers Using the LbL Approach
Conclusions

FREELY STANDING LBL FILMS
Introduction
Fabrication of Freely Standing Ultrathin LbL Films
Porous and Patterned Freely Standing LbL Films
Freely Standing LbL Films with Weak Interactions

NEUTRON REFLECTOMETRY AT POLYELECTROLYTE MULTILAYERS
Introduction
Neutron Reflectometry
Preparation Techniques for Polyelectrolyte Multilayers
Types of Polyelectrolytes
Preparation Parameters
Influence of External Fields After PEM Assembly
PEM as a Structural Unit
Conclusion and Outlook

POLYELECTROLYTE CONFORMATION IN AND STRUCTURE OF POLYELECTROLYTE MULTILAYERS
Introduction
Results
Conclusion and Outlook

CHARGE BALANCE AND TRANSPORT IN ION-PAIRED POLYELECTROLYTE MULTILAYERS
Introduction
Association Mechanism: Competitive Ion Pairing
Surface versus Bulk Polymer Charge
Polyelectrolyte Interdiffusion
Ion Transport Through Multilayers: the "Reluctant" Exchange Mechanism
Concluding Remarks

CONDUCTIVITY SPECTRA OF POLYELECTROLYTE MULTILAYERS REVEALING ION TRANSPORT PROCESSES
Introduction to Conductivity Studies of LbL Films
PEM Spectra: Overview
DC Conductivities of PEMs
Modeling of PEM Spectra
Ion Conduction in Polyelectrolyte Complexes
Scaling Principles in Conductivity Spectra: From Time - Temperature to Time - Humidity Superposition

RESPONSIVE LAYER-BY-LAYER ASSEMBLIES: DYNAMICS, STRUCTURE AND FUNCTION
Introduction
Chain Dynamics and Film Layering
Responsive Swellable LbL Fil 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