SELF-ASSEMBLY AND NANOTECHNOLOGY A Force Balance Approach
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1 SELF-ASSEMBLY AND NANOTECHNOLOGY A Force Balance Approach Yoon S. Lee Scientific Information Analyst Chemical Abstracts Service A Division of the American Chemical Society Columbus, Ohio WILEY A JOHN WILEY & SONS, INC., PUBLICATION
2 CONTENTS Preface and Acknowledgments xv PART I. SELF-ASSEMBLY 1 1. UNIFIED APPROACH TO SELF-ASSEMBLY Self-Assembly through Force Balance General Scheme for the Formation of Self-Assembled Aggregates General Scheme for Self-Assembly Process Concluding Remarks 17 References INTERMOLECULAR AND COLLOIDAL FORCES Van der Waals Force Electrostatic Force: Electric Double-Layer Steric and Depletion Forces Solvation and Hydration Forces Solvation Force Hydration Force Hydrophobie Effect Hydrogen Bond 42 References MOLECULAR SELF-ASSEMBLY IN SOLUTION I: MICELLES Surfactants and Micelles Physical Properties of Micelles Micellization Critical Micellar Concentration and Aggregation Number Counterion Binding 53 vii i.
3 1 VIII CONTENTS 3.3. Thermodynamics of Micellization Mass-Action Model Pseudo-phase Separation Model Hydrophobie Effect and Enthalpy-Entropy Compensation Micellization versus General Scheme of Self-Assembly Change of Micelle Structures General Scheme of Micellization Concept of Force Balance and Surfactant Packing Parameter / Multicomponent Micelles Micellar Solubilization Applications of Surfactants and Micelles Micellar Catalysis 69 References MOLECULAR SELF-ASSEMBLY IN SOLUTION II: BILAYERS, LIQUID CRYSTALS, AND EMULSIONS Bilayers Bilayer-Forming Surfactants Bilayerization Physical Properties of Bilayers Vesicles, Liposomes, and Niosomes Physical Properties of Vesicles Micellar Catalysis on Vesicles Liquid Crystals Thermotropic Liquid Crystals Lyotropic Liquid Crystals Concentration-Temperature Phase Diagram Ternary Surfactant-Water-Oil (or Co-surfactant) Phase Diagram Emulsions Microemulsions Reverse Micelles Macroemulsions Micellar Catalysis on Microemulsions 99 References COLLOIDAL SELF-ASSEMBLY Forces Induced by Colloidal Phenomena Surface Tension and Capillarity Contact Angle and Wetting 108
4 CONTENTS IX Adhesion Gravity and Diffusion Pressures by Osmotic and Donnan Effects Electrokinetic Force Magnetophoretic Force Force by Flow Force Balance for Colloidal Self-Assembly General Scheme for Colloidal Self-Assembly Micelle-like Colloidal Self-Assembly: Packing Geometry Summary 122 References SELF-ASSEMBLY AT INTERFACES General Scheme for Interfacial Self-Assembly Surfaces and Interfaces Force Balance with Interfaces Control of Intermolecular Forces at Interfaces Packing Geometry: Balance with Attractive and Repulsive Forces Packing with Functional Groups: Balance with Directional Force Building Units with Multifunctional Sites Building Units with Single Functional Sites Packing of Nonamphiphilic Building Units Self-Assembly at the Gas-Liquid Interface Langmuir Monolayer Surface Micelles Self-Assembly at the Liquid-Solid Interface Self-Assembly at the Liquid-Liquid Interface Self-Assembly at the Gas-Solid Interface Interface-Induced Chiral Self-Assembly 142 References BIO-MIMETIC SELF-ASSEMBLY General Picture of Bio-mimetic Self-Assembly Force Balance Scheme for Bio-mimetic Self-Assembly Origin of Morphological Chirality and Diversity Chirality of Building Units Asymmetrie Structure of Building Units Multiple Hydrogen Bonds Cooperative Balance of Geometry and Bonding Induced Asymmetrie Packing 160
5 * CONTENTS 7.4. Symmetrie Bio-mimetic Self-Assembled Aggregates H- and J-Aggregates Molecular Capsules Gels: Networked Bio-mimetic Self-Assembled Aggregates Properties of Bio-mimetic Self-Assembled Aggregates Directionality, Site-Specificity, and Chirality Hierarchicality Complementarity Chiroptical Properties Future Issues 168 References 168 PART II. NANOTECHNOLOGY IMPLICATIONS OF SELF-ASSEMBLY FOR NANOTECHNOLOGY General Concepts and Approach to Nanotechnology Self-Assembly and Nanotechnology Share the Same Building Units Self-Assembly and Nanotechnology Are Governed by the Same Forces Self-Assembly versus Manipulation for the Construction of Nanostructures Self-Aggregates and Nanotechnology Share the Same General Assembly Principles Concluding Remarks 180 References NANOSTRUCTURED MATERIALS What Are Nanostructured Materials? Intermolecular Forces During the Formation of Nanostructured Materials Sol-Gel Chemistry General Self-Assembly Schemes for the Formation of Nanostructured Materials Micro-, Meso-, and Macroporous Materials Mesostructured and Mesoporous Materials Formation of Mesoporous Silica with Hexagonal Structure Structural Control of Mesostructured and Mesoporous Materials 195
6 CONTENTS XI Epitaxial Analysis at the Micelle-Silica Interface Charge Matching at the Micelle-Silica Interface Characterization of Mesostructured and Mesoporous Materials Organic-Inorganic Hybrid Mesostructured and Mesoporous Materials Microporous and Macroporous Materials Co-Self-Assembly for the Formation of Microporous Materials Emulsions for the Formation of Macroporous Materials Colloidal Self-Assembly for the Formation of Macroporous Materials Applications of Nanostructured and Nanoporous Materials Summary and Future Issues 214 References NANOPARTICLES: METALS, SEMICONDUCTORS, AND OXIDES What are Nanoparticles? Intermolecular Forces During the Synthesis of Nanoparticles Synthesis of Nanoparticles Direct Synthesis: Confmement-by-Adsorption Synthesis within Preformed Nanospace Surfactant Self-Assembled Aggregates Bio-mimetic Self-Assembled Aggregates Dendritic Polymers Nanoporous Solids Directed Growth by Soft Epitaxy Directed Growth by Hard Epitaxy Nanoparticle Synthesis with Nonconventional Media Supercritical Fluids IonicLiquids Properties of Nanoparticles Quantum Size Effect Optical Properties of Semiconductors Optical Properties of Noble Metals Electromagnetic Properties of Noble Metals Electric Properties of Metals Surface Atom Effect Applications of Nanoparticles Chemical and Biological Sensors Optical Sensors Nanocomposites and Hybrid Materials 245
7 * XÜ CONTENTS Catalysis Functional Fluids Summary and Future Issues 246 References NANOSTRUCTURED FILMS What Is Nanostructured Film? General Scheme for Nanostructured Films Preparation and Structural Control of Nanostructured Films Self-Assembled Monolayer (SAM) Layer-by-Layer Assembly Vapor-Deposited Films Sol-Gel Processed Films Langmuir-Blodgett (LB) Films Properties and Applications of Nanostructured Films Nanoporous Films Nanolayered Films Nanopatterned Films Monolayer: Model Membrane Summary and Future Issues 266 References NANOASSEMBLY BY EXTERNAL FORCES Force Balance and the General Scheme of Self-Assembly Under External Forces Colloidal Self-Assembly Under External Forces Capillary Force Electric Force Magnetic Force Flow Mechanical Force Force by Spatial Confmement Other Forces Laser-Optical Force Ultrasound Gravity and Centrifugal Forces Molecular Self-Assembly Under External Forces Flow Magnetic Field Concentration Gradient Confmement Gravity and Centrifugal Forces 287
8 CONTENTS XIII Applications of Colloidal Aggregates Optical Band Gap Nanostructured Materials Summary and Future Issues 288 References NANOFABRICATION Self-Assembly and Nanofabrication Unit Fabrications Jointing Crossing and Curving Alignment and Stacking Reconstruction, Deposition, and Coating Symmetry Breaking Templating and Masking Hybridization Nanointegrated Systems Summary and Future Issues 308 References NANODEVICES AND NANOMACHINES General Scheme of Nanodevices Nanocomponents: Building Units for Nanodevices Interlocked and Interwinded Molecules DNA Carbon Nanotubes and Fullerenes Three Element Motions: Force Balance at Work Unit Operations Gating and Switching Directional Rotation and Oscillation Shafting, Shuttling, and Elevatoring Contraction-and-Extension Walking Tweezering or Fingering Rolling and Bearing Pistoning, Sliding, or Conveyoring Self-Directional Movement Capture-and-Release Sensoring Directional Flow Nanodevices: Fabricated Nanocomponents to Operate Delivery Systems Nanoelectronics 329
9 XIV CONTENTS Nanomachines: Integrated Nanodevices to Work Power Source Synchronization Packing Communication with the Macroworld Summary and Future Issues 331 References 332 Index 335
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