Multilayer Thin Films

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 Films
Conclusion and Outlook

TAILORING THE MECHANICS OF FREESTANDING MULTILAYERS
Introduction
Measurements of Mechanical Properties of Flat LbL Films
Mechanical Properties of LbL Microcapsules
Prospective Applications Utilizing Mechanical Properties

DESIGN AND TRANSLATION OF NANOLAYER ASSEMBLY PROCESSES: ELECTROCHEMICAL ENERGY TO PROGRAMMABLE PHARMACIES
Introduction
Controlling Transport and Storing Charge in Multilayer Thin Films: Ions, Electrons and Molecules
LbL Films for Multi-Agent Drug Delivery - Opportunities for Programmable Release
Automated Spray-LbL - Enabling Function and Translation
Concluding Remarks

SURFACE-INITIATED POLYMERIZATION AND LAYER-BY-LAYER FILMS
Introduction
Overview of Surface-Grafted Polymer Brushes
Layer-by-Layer (LbL) Self-Assembly
Combined LbL-SIP Approach
Applications of the Combined LbL-SIP Approach
Concluding Remarks

QUARTZ CRYSTAL RESONATOR AS A TOOL FOR FOLLOWING THE BUILD-UP OF POLYELECTROLYTE MULTILAYERS
Introduction
Basic Concepts
Growth Processes
Experimental Techniques
Analysis of QCR Data

VOLUME 2

PART II: Applications

ELECTROSTATIC AND COORDINATIVE SUPRAMOLECULAR ASSEMBLY OF FUNCTIONAL FILMS FOR ELECTRONIC APPLICATION AND MATERIALS SEPARATION
Introduction
Polyelectrolyte Multilayer Membranes
Summary and Conclusions

OPTOELECTRONIC MATERIALS AND DEVICES INCORPORATING POLYELECTROLYTE MULTILAYERS
Introduction
Second Order Nonlinear Optics
Plasmonic Enhancement of Second Order Nonlinear Optical Response
Nonlinear Optical Fibers
Optical Fiber Biosensors
Antireflection Coatings
Electrochromic Devices
Electromechanical Actuators

NANOSTRUCTURED ELECTRODES ASSEMBLED FROM METAL NANOPARTICLES AND QUANTUM DOTS IN POLYELECTROLYTES
Introduction
Nanostructured Pt Electrodes from Assemblies of Pt Nanoparticles in Polyelectrolytes
Nanostructured Photoelectrodes from Assemblies of Q-CdS in Polyelectrolytes
Conclusions

RECORD PROPERTIES OF LAYER-BY-LAYER ASSEMBLED COMPOSITES
Introduction
LbL Assemblies of Clays
LBL Assemblies of Carbon Nanotubes
Conclusions and Perspectives

CARBON NANOTUBE-BASED MULTILAYERS
Introduction
Characteristics of Carbon Nanotube Layer-by-Layer Assemblies
Applications of Carbon Nanotube Layer-by-Layer Assemblies
Conclusions

NANOCONFINED POLYELECTROLYTE MULTILAYERS: FROM NANOSTRIPES TO MULTISEGMENTED FUNCTIONAL NANOTUBES
Introduction
Estimation of the Size of Polyelectrolyte Chains in Dilute Solutions
Confining LbL Assembly on Flat Surfaces
Confining LbL Assembly in Nanopores
Conclusions

THE DESIGN OF POLYSACCHARIDE MULTILAYERS FOR MEDICAL APPLICATIONS
Introduction
Polysaccharides as Multilayered film Components: An Overview of Their Structure and Properties
Multilayers Formed by Assembly of Weak Polyanions and Chitosan or Chitosan Derivatives
Multilayers Formed by Assembly of Strong Polyanions and Chitosan or Chitosan Derivatives
Cardiovascular Applications of Polysaccharide Multilayers
Conclusions

POLYELECTROLYTE MULTILAYER FILMS BASED ON POLYSACCHARIDES: FROM PHYSICAL CHEMISTRY TO THE CONTROL OF CELL DIFFERENTIATION
Introduction
Film Internal Composition and Hydration
Film Cross-Linking: Relation Between Composition and Mechanical Properties
Cell Adhesion onto Cross-Linked Films: Cell Adhesion, Cytoskeletal Organization and Comparison with Other Model Materials
Cell Differentiation: ESC and Myoblasts
Conclusions

DIFFUSION OF NANOPARTICLES AND BIOMOLECULES INTO POLYELECTROLYTE MULTILAYER FILMS: TOWARDS NEW FUNCTIONAL MATERIALS
Introduction
LBL Films in Which Nanoparticles are Incorporated Step-By-Step
LBL Films Made Uniquely From Nanoparticles
Nanoparticles Produced by Post-treatment of Deposited Films
Diffusion of Colloids in Already Deposited Films
Emerging Properties of Films Filled with Nanoparticles by the Post-incubation Method
Conclusions and Perspectives

COUPLING CHEMISTRY AND HYBRIDIZATION OF DNA MOLECULES ON LAYER-BY-LAYER MODIFIED COLLOIDS
Introduction
Materials and Methods
Results
Summary

A 'MULTILAYERED' APPROACH TO THE DELIVERY OF DNA: EXPLOITING THE STRUCTURE OF POLYELECTROLYTE MULTILAYERS TO PROMOTE SURFACE-MEDIATED CELL TRANSFECTION AND MULTI-AGENT DELIVERY
Introduction
Surface-Mediated Delivery of DNA: Motivation and Context, Opportunities and Challenges
Films Fabricated Using Hydrolytically Degradable Cationic Polymers
Toward Spatial Control: Release of DNA from the Surfaces of Implants and Devices
Toward Temporal Control: Tunable Release and Sequential Release
Concluding Remarks

DESIGNING LBL CAPSULES FOR DRUG LOADING AND RELEASE
Introduction
Engineering Microparticulate Templates to Design LbL Capsules for Controlled Drug Release
Engineering the Shell to Design LbL Capsules for Controlled Drug Release
Interaction of LbL Capsules with Living Cells In Vitro and In Vivo
Conclusions

STIMULI-SENSITIVE LBL FILMS FOR CONTROLLED DELIVERY OF PROTEINS AND DRUGS
Introduction
Avidin-Containing LbL Films
Concanavalin A-containing LbL Films
Dendrimer-Containing LbL Films
Insulin-Containing LbL Films
Conclusions

ASSEMBLY OF MULTILAYER CAPSULES FOR DRUG ENCAPSULATION AND CONTROLLED RELEASE
Introduction
Magnetically Sensitive Release
Ultrasound-Stimulated Release
Photo-Stimulated Release
Thermo-Stimulated Release
pH-Sensitive Release
Redox-Controlled Release
Bio-Responsive Release
Extension
Concluding Remarks

ENGINEERED LAYER-BY-LAYER ASSEMBLED CAPSULES FOR BIOMEDICAL APPLICATIONS
Introduction
Template Selection
Material Assembly
Loading
Degradation and Release
Applications
Conclusions

ASSEMBLY OF POLYMER MULTILAYERS FROM ORGANIC SOLVENTS FOR BIOMOLECULE ENCAPSULATION
Introduction
Limitations of LbL-Based Biomolecule Encapsulation in Aqueous Phase
LbL Biomolecule Encapsulation in the Organic Phase
Conclusion and Outlook

STIMULI-RESPONSIVE POLYMER COMPOSITE MULTILAYER MICROCAPSULES AND MICROCHAMBER ARRAYS
Introduction
Fabrication of Stimuli-Responsive LbL Microcapsules
Microchamber Arrays
Conclusion

DOMAIN-CONTAINING FUNCTIONAL POLYELECTROLYTE FILMS: APPLICATIONS TO ANTIMICROBIAL COATINGS AND ENERGY TRANSFER
Introduction
Polyelectrolyte Films Incorporating Randomly Distributed Hydrophobic Nanodomains for Antimicrobial Applications
Multicompartmentalized Stratified Polyelectrolyte Films for Control of Energy Transfer
Conclusions and Perspectives

CREATING FUNCTIONAL MEMBRANES THROUGH POLYELECTROLYTE ADSORPTION
Introduction
Functionalization of the Interior of Membranes
LBL Films as Membrane Skins
Challenges

REMOTE AND SELF-INDUCED RELEASE FROM POLYELECTROLYTE MULTILAYER CAPSULES AND FILMS

CONTROLLED ARCHITECTURES IN LBL FILMS FOR SENSING AND BIOSENSING
Introduction
LbL-Based Sensors and Biosensors
Special Architectures for Sensing and Biosensing
Statistical and Computational Methods to Treat the Data
Conclusions and Perspectives

PATTERNED MULTILAYER SYSTEMS AND DIRECTED SELF-ASSEMBLY OF FUNCTIONAL NANO-BIO MATERIALS
New Approaches and Materials for Multilayer Film Patterning Techniques
Cell Adhesion and Patterning Using PEMs
PEMs Incorporating Proteins and Their Patterning
Metal/Graphene Conductive Patterning via PEM Films
Ordered and Disordered Particles on PEMs
Mechanical Aspects of PEM Films and Degradable Films

ELECTROCHEMICALLY ACTIVE LBL MULTILAYER FILMS: FROM BIOSENSORS TO NANOCATALYSTS 1003
Introduction
Electrochemical Response
Dynamics of Charge Exchange
Conclusions

MULTILAYER POLYELECTROLYTE ASSEMBLY IN FEEDBACK ACTIVE COATINGS AND FILMS
Introduction. The Concept of Feedback Active Coatings
Polyelectrolyte-Based Self-Healing Anticorrosion Coatings
Coatings with Antibacterial Activity
Conclusions and Outlook

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.

G. Decher, Institut Charles Sadron, Strasbourg, France; J. B. Schlenoff, Florida State University, Tallahassee, FL, USA