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A fundamental resource for understanding and developing effective Self-Assembly and Nanotechnology Systems Systematically integrating self-assembly, nanoassembly, and nanofabrication into one easy-to-use source, Self-Assembly and Nanotechnology Systems effectively helps students, professors, and researchers comprehend and develop applicable techniques for use in the field. Through case studies, countless examples, clear questions, and general applications, this book provides experiment-oriented techniques for designing, applying, and characterizing Self-Assembly and Nanotechnology Systems. Self-Assembly and Nanotechnology Systems includes: * Techniques for identifying assembly building units * Practical assembly methods to focus on when developing nanomaterials, nanostructures, nanoproperties, nanofabricated systems, and nanomechanics * Algorithmic diagrams in each chapter for a general overview * Schematics designed to link assembly principles with actual systems * Hands-on lab activities This informative reference also analyzes the diverse origins and structures of assembly building units, segmental analysis, and selection of assembly principles, methods, characterization techniques, and predictive models. Complementing the author's previous conceptually based book on this topic, Self-Assembly and Nanotechnology Systems is a practical guide that grants practitioners not only the skills to properly analyze assembly building units but also how to work with applications to exercise and develop their knowledge of this rapidly advancing scientific field.
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Table of Contents
Title Page
Copyright
Dedication Page
Preface
Abbreviations
Part 1: Building Units
Chapter 1: Self-Assembly Systems
1.1 Self-Assembly
1.2 Identification of Building Units
1.3 Implication of Building Unit Structures for Self-Assemblies
1.4 General Assembly Diagram
1.5 Collection of Building Units
1.6 Concluding Remarks
References
Chapter 2: Nanotechnology Systems
2.1 Nanoassembly
2.2 Identification of Building Units
2.3 Nanoelements
2.4 Implication of Building Unit Structures for Nanoassemblies
2.5 General Assembly Diagram
2.6 Self-Assembly, Nanoassembly, and Nanofabrication
2.7 Collection of Building Units
2.8 Concluding Remarks
References
Part 2: Design
Chapter 3: Identification of Self-Assembly Capability
3.1 Assembly Issue
3.2 General Overview
3.3 Assembly Principles
3.4 Collection of Primary Self-Assembled Aggregates
3.5 Summary
References
Chapter 4: Identification of Multi-Step Self-Assemblies
4.1 Assembly Issue
4.2 General Overview
4.3 Assembly Principles
4.4 Collection of Higher-Order Self-Assembled Aggregates
4.5 Collection of Self-Assembled Aggregates within Biological Systems
4.6 Summary
References
Chapter 5: Control of the Structures of Self-Assembled Aggregates
5.1 Assembly Issue
5.2 General Overview
5.3 Assembly Principles
5.4 Collection of the Structures of Self-Assembled Aggregates
5.5 Summary
References
Chapter 6: Hierarchy and Chirality of Self-Assembled Aggregates
6.1 Assembly Issue
6.2 General Overview
6.3 Assembly Principles
6.4 Collection of Hierarchy within Self-Assembled Aggregates
6.5 Collection of Chirality Expressed by Self-Assembled Aggregates
6.6 Summary
References
Chapter 7: Assembly with Multiple Building Units
7.1 Assembly Issue
7.2 General Overview
7.3 Assembly Principles
7.4 Collection of Nanoassembled Systems I
7.5 Collection of Nanoporous Solids
7.6 Summary
References
Chapter 8: Directed and Forced Assemblies
8.1 Assembly Issue
8.2 General Overview
8.3 Assembly Principles
8.4 Techniques for Directed and Forced Assemblies
8.5 Surface-Induced Directed and Forced Assemblies
8.6 Collection of Nanoassembled Systems II
8.7 Summary
References
Part 3: Applications
Chapter 9: External Signal–Responsive Nanomaterials
9.1 Nanoissue
9.2 General Overview
9.3 Assembly Principles
9.4 Collection of External Signal–Responsive Assembly Systems
9.5 From Assembly Systems to Nanomaterials
9.6 Collection of External Signal–Responsive Nanomaterials
9.7 Summary
References
Chapter 10: Nanomaterials with Intrinsic Functionalities
10.1 Nanoissue
10.2 General Overview
10.3 Assembly Principles
10.4 From Assembled Systems to Nanomaterials
10.5 Collection of Nanomaterials with Intrinsic Functionalities
10.6 Summary
References
Chapter 11: Nanostructures: Designed to Perform
11.1 Nanoissue
11.2 General Overview
11.3 Assembly Principles
11.4 Collection of Common Nanostructure Names
11.5 Collection of Nanostructures and their Applications
11.6 Summary
References
Chapter 12: Nanoproperties: Controlled to Express
12.1 Nanoissue
12.2 General Overview
12.3 Assembly Principles
12.4 Collection of Nanoproperties and their Applications
12.5 Summary
References
Chapter 13: Nanofabricated Systems: Combined to Function
13.1 Nanoissue
13.2 General Overview
13.3 Fabrication Principles
13.4 Collection of Top-Down Techniques
13.5 Collection of Top-Down Bulk Materials and Functionalizing Agents
13.6 Collection of Nanofabricated Systems and their Applications
13.7 Summary
References
Chapter 14: Nanomechanical Movements: Combined to Operate
14.1 Nanoissue
14.2 General Overview
14.3 Fabrication Principles
14.4 Collection of Nanomechanical Movements
14.5 Summary
References
Part 4: Characterization
Chapter 15: Assembly Forces and Measurements
15.1 Intermolecular and Colloidal Forces
15.2 Collection of Intermolecular and Colloidal Forces
15.3 Measurements of Intermolecular and Colloidal Forces
15.4 Collection of Measurement Techniques
15.5 Implications of Building Unit Structures for Characterization
References
Chapter 16: Assembly Processes and Critical Behaviors
16.1 Critical Behaviors as the Characterization Guide of Assembly Processes
16.2 Characterization Principles
16.3 Collection of Physical Properties to Measure
16.4 Collection of Critical Assembly Parameters
References
Chapter 17: Assembled Systems and Structural Properties
17.1 Structural Properties for the Characterization of Assembled Systems
17.2 Characterization Principles
17.3 Collection of Structural Properties to Measure
References
Chapter 18: Modeling and Simulations
18.1 Assembly Systems are Big and Multi-Scaled
18.2 Classic Models
18.3 Simulations
18.4 Concluding Remarks
References
Epilogue
E.1 Background
E.2 Definition and Principle
E.3 Structure
E.4 Development and Benefits
E.5 Challenges
References
Index
Copyright © 2010 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
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Library of Congress Cataloging-in-Publication Data:
Lee, Yoon S. (Yoon Seob)
Self-assembly and nanotechnology systems : design, characterization, and applications / Yoon S. Lee.
p. ; cm.
Includes bibliographical references and index.
ISBN 978-1-118-08759-6 (hardback)
1. Nanostructured materials. 2. Nanostructures. 3. Nanotechnology. 4. Self-assembly (Chemistry) I. Title.
[DNLM: 1. Nucleic Acids-pharmacology. 2. Nucleic Acids-therapeutic use. QV 185]
TA418.9.N35L443 2011
620'.5–dc22
2011010969
I had my ear close to her lips.
She whispered, "My son, I missed you so much last night, so, I cried."
Those were the last words my mother left for me.
She was forty-six.
And I am now forty-six.
This is for my mother.
Preface
Nanotechnology is now experiencing a nice expansion toward its full potential. Early promises from scientific discoveries are being actualized in engineering stages, and diverse products are beginning to show up in the marketplace. This is possible because we now have some good methods for the assembly of nanotechnology systems and an improved understanding of how they behave at the nanoscale.
Self-assembly is a key scientific principle behind nanotechnology. Many of the seemingly complex self-assembly systems from different origins are well understood. They can help assemble nanotechnology systems effectively and efficiently, and provide practical tools to control the structures and properties of nanotechnology systems. This marriage of self-assembly and nanotechnology systems is important for the maturation of nanotechnology and promises fruitful outcomes. A main goal of this book is to offer comprehensive coverage of how to use self-assembly systems for the design, characterization, and applications of nanotechnology systems. The four key objectives are:
1. Show how to identify assembly building units.
2. Provide detailed assembly principles for the design of nanotechnology systems.
3. Establish practical assembly methods to focus on when developing nanomaterials, nanostructures, nanoproperties, nanofabricated systems, and nanomechanics.
4. Show how to characterize/model self-assembly and nanotechnology systems.
This book is divided into four parts. The first part shows the assembly building units, and how diverse their origins and structures can be. It also presents how to analyze the building unit structures in a systematic manner. This will be called segmental analysis, which is used as an underlying concept for the discussions throughout the book. The second and third parts show the design and applications of nanotechnology systems, respectively, and how to select proper assembly principles and methods. The last part shows how to select proper characterization techniques and predictive models. This book is structured as follows:
1. Clear questions at the beginning of each chapter help readers stay focused.
2. Each chapter offers an algorithmic diagram for a general overview.
3. Schematics are designed to link the assembly principles with actual systems.
4. Case studies are provided for the in-depth analysis of actual systems.
5. All chapters (except for the final one) provide a collection of examples.
6. All chapters in the second and third parts follow the same format, making it easy to understand different assembly principles and methods.
Those who are studying the disciplines of science and engineering with a general chemistry level of knowledge should not have too much difficulty using this book. Occasional trips to common biology, physics, or materials science textbooks might be necessary. This book will be useful for:
1. Students, researchers, and professionals who want to acquire a general picture of how self-assembly systems are used in nanotechnology systems.
2. College teachers who need a convenient source for teaching and for design of experiments for nanotechnology-related courses.
3. Nanoscientists and nanotechnologists who need a handbook for their daily activities and for publishing the results of their studies.
Acknowledgments
I am deeply grateful to all the reviewers. Their valuable advice greatly helped me shape this book. I can never thank enough professors Kyu Whan Woo at Seoul National University and James F. Rathman at Ohio State University. It was Professor Woo who introduced me the term self-assembly on my first day of graduate school. This word has been imprinted on my mind ever since. With the guidance of Professor Rathman, I widened my view on self-assembly and explored a good deal of nanotechnology. My deep thanks extend to Dr. Oksik Lee at Chemical Abstracts Service. Without her companionship, thoughtfulness, and all the discussions I have had with her over the years, it would have been much more difficult to write this book. As always, my deepest thanks go to my wife, Jee-a, and my son, Jong-hyeok, for their endless support and love. I always miss my parents and my parents-in-law, who live far away.
Yoon Seob Lee
Dublin, Ohio
Abbreviations
The following abbreviations are used in the figures and tables. Full terms are used in the text.
attractive segment: A
repulsive segment: R
directional segment: D
asymmetric packing segment: AP
external force-specific functional segment: EF-F
attractive force: AF
repulsive force: RF
directional force: DF
asymmetric packing process: APP
external force-induced directional factor: ED
self-assembly: SA
self-assembled aggregate: SAA
self-assembly building unit (primary): SA-BU
primary self-assembly process: P-SA
primary self-assembled aggregate: P-SAA
secondary self-assembly building unit: S-SA-BU
secondary self-assembly process: S-SA
secondary self-assembled aggregate: S-SAA
tertiary self-assembly building unit: T-SA-BU
tertiary self-assembly process: T-SA
tertiary self-assembled aggregate: T-SAA
nanoassembly: NA
nanoassembled system: NA-S
nanoassembly building unit: NA-BU
fabrication building unit: F-BU
reactive building unit: R-BU
nanostructural element: N-SE
nanoproperty element: N-PE
nanomechanical element: N-ME
nanocommunication element: N-CE
nanofabrication: NF
nanofabricated system: NF-S
nanointegrated system: NI-S
nanodevice: NaD
nanomachine: NaM
Part 1
BUILDING UNITS
Chapter 1
Self-Assembly Systems
My ten-year-old son loves building action figures using LEGO bricks (LEGO, please see References). He has many LEGO products, “which I bought for him, of course.” He first built the action figures that he was supposed to build by following the instructions. Once he built enough number of them in many different forms, he then began to build his own action figures by using the parts from the different boxes. Whenever I am watching him building new forms of action figures, in many cases with new functions, I am amazed by how an “unbiased” child's mind can do such a creative and fun thing. I love watching him doing that, and, of course, enjoy the new action figures so much. What is also amazing is the flexibility of those tiny parts. They are small and simple but at the same time so elegantly and functionally designed. It seems to me that their core structures are composed of just a couple of different basic segments. These basic segments are simple yet diverse, and easy to assemble. One segment from one part perfectly fits with the complementary segments from all other parts even from other types of action figures. By following this simple rule, my son keeps building his own action figures with a high variety and different size scales.
My approach to self-assembly begins with the segmental analysis of self-assembly building units. (The term building block is used roughly ten times more than the term building unit in the literature. But the term building block may bring an unintended implication that it is limited to sizable materials rather than encompassing a wide range of different entities. Thus, the term building unit will be used in this book with the intention that it includes any type of entity that can be assembled into any type of self-assembled system.) It does not totally come from my son's LEGO playing, but it has definitely helped me build up this concept. It is not about making self-assembly analysis more complicated. There is a very simple way to address self-assembly issues that are seemingly widely dispersed. And we can benefit from it, not just in nanotechnology but in other areas of modern technology as well. It may not look like a conventional scientific approach toward natural phenomena. But it is indeed possible to understand self-assembly with a very simple rule.
1.1 Self-Assembly
Figure 1.1 presents a schematic explanation of the self-assembly process based on the concept of force balance. A full description of this concept has been discussed elsewhere (Lee, 2008). For almost all of the self-assembly processes, major interactions between their building units, regardless of the types and sizes, occur through relatively weak intermolecular or colloidal forces. These include hydrogen bond, van der Waals interaction, hydrophobic force, π-π interaction, steric interaction, depletion force, solvation/hydration forces, and so forth. Strong bonds such as covalent bond, coordination bond, or ionic bond are rarely involved with self-assembly processes. These weak intermolecular or colloidal forces can be classified into three distinctive groups whose delicate balance determines the process and outcome of the self-assembly. They are attractive driving force, repulsive opposition force, and directional/functional forces. The attractive driving force acts to bring self-assembly building units together, thus initiating the self-assembly process. Once this attractive process takes place, the repulsive opposition force, which is originated by another segment within the self-assembly building unit, acts to balance the attractive process, which places the building units at a certain critical state. Self-assembly is established at this critical point and self-assembled aggregates begin to appear at this point as well. The third group, directional/functional forces, are the forces that can guide this balancing process between the attractive and repulsive forces. Depending on the nature of the self-assembly system, the directional/functional forces can act as either an attractive force or a repulsive force. In most cases, it is the directional/functional forces that give the self-assembly system (or self-assembled aggregate) unique structural functionalities.
Figure 1.1 The concept of force balance approach for self-assembly.
Self-assembly occurs through the delicate balance between at least any two groups of the forces. For example, it can be between the attractive force and repulsive force, between the attractive force and the directional force that has the capability of the repulsive force, between the repulsive force and the directional forces that have the capability of the attractive force, or between all three groups. But, to become a self-assembly, it always has to fulfill both the “self” aspect and the “assembly” aspect, and at the same time should have the actual outcomes, that is, “self-assembled aggregates.” Therefore, there always has to be the force that gives the “self” aspect to the self-assembly building units and the balance that can ensure both the structural integrity and dynamic flexibility of the self-assembled aggregates. On the other hand, this observation leads us to the justification that, once the conditions (intrinsic ones of the building unit and environmental ones) for this force balance are met between any building units, they will come close (“self” aspect) and form the aggregates (self-assembled aggregates) at a certain point of the process (“assembly” aspect) regardless of their types and sizes.
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