Geckeler K.E., Nishide H. (Eds.) Advanced Nanomaterials

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Contents IX

7.4 CNT–Metal Nanoparticle Composites 254

7.5 CNT–AuNP Composites 255

7.5.1 Filling of CNTs with AuNPs 255

7.5.2 Deposition of AuNPs Directly on the CNT Surface 256

7.5.3 Interaction Between Modiﬁ ed AuNPs and CNTs 267

7.5.3.1 Covalent Linkage 268

7.5.3.2 Supramolecular Interaction Between AuNPs and CNTs 271

7.6 Applications 288

7.7 Merits and Demerits of Synthetic Approaches 289

7.8 Conclusions 291

Acknowledgments 292

References 292

8 Recent Advances in Metal Nanoparticle-Attached Electrodes 297

Munetaka Oyama, Akrajas Ali Umar, and Jingdong Zhang

8.1 Introduction 297

8.2 Seed-Mediated Growth Method for the Attachment and Growth of

AuNPs on ITO 298

8.3 Electrochemical Applications of AuNP-Attached ITO 300

8.4 Improved Methods for Attachment and Growth of AuNPs on ITO 302

8.5 Attachment and Growth of AuNPs on Other Substrates 306

8.6 Attachment and Growth of Au Nanoplates on ITO 308

8.7 Attachment and Growth of Silver Nanoparticles (AgNPs) on ITO 309

8.8 Attachment and Growth of Palladium Nanoparticles PdNPs on

ITO 311

8.9 Attachment of Platinum Nanoparticles PtNPs on ITO and GC 312

8.10 Electrochemical Measurements of Biomolecules Using AuNP/

ITO Electrodes 315

8.11 Nonlinear Optical Properties of Metal NP-Attached ITO 315

8.12 Concluding Remarks 316

References 316

9 Mesoscale Radical Polymers: Bottom-Up Fabrication of Electrodes in

Organic Polymer Batteries 319

Kenichi Oyaizu and Hiroyuki Nishide

9.1 Mesostructured Materials for Energy Storage Devices 319

9.2 Mesoscale Fabrication of Inorganic Electrode-Active Materials 322

9.3 Bottom-Up Strategy for Organic Electrode Fabrication 323

9.3.1 Conjugated Polymers for Electrode-Active Materials 323

9.3.2 Mesoscale Organic Radical Polymer Electrodes 324

9.4 Conclusions 330

References 330

10 Oxidation Catalysis by Nanoscale Gold, Silver, and Copper 333

Zhi Li, Soorly G. Divakara, and Ryan M. Richards

X Contents

10.1 Introduction 333

10.2 Preparations 334

10.2.1 Silver Nanocatalysts 335

10.2.2 Copper Nanocatalysts 335

10.2.3 Gold Nanocatalysts 335

10.3 Selective Oxidation of Carbon Monoxide (CO) 337

10.3.1 Gold Catalysts 337

10.3.2 Silver Catalysts 342

10.3.3 Gold–Silver Alloy Catalysts 342

10.3.4 Copper Catalysts 343

10.4 Epoxidation Reactions 344

10.4.1 Gold Catalysts 344

10.4.2 Silver Catalysts 346

10.5 Selective Oxidation of Hydrocarbons 347

10.5.1 Gold Catalysts 349

10.5.2 Silver Catalysts 350

10.5.3 Copper Catalysts 350

10.6 Oxidation of Alcohols and Aldehydes 350

10.6.1 Gold Catalysts 351

10.6.2 Silver Catalysts 351

10.7 Direct Synthesis of Hydrogen Peroxide 353

10.8 Conclusions 354

References 355

11 Self-Assembling Nanoclusters Based on Tetrahalometallate Anions:

Electronic and Mechanical Behavior 365

Ishenkumba A. Kahwa

11.1 Introduction 365

11.2 Preparation of Key Compounds 366

11.3 Structure of the [(A(18C6))

(MX

)] [BX

]

· nH

O Complexes 367

11.4 Structure of the [(Na(15C5))

Br] [TlBr

]

Complex 368

11.5 Spectroscopy of the Cubic F23 [(A(18C6))

(MX

)] [BX

]

· nH

O 368

11.6 Unusual Luminescence Spectroscopy of Some Cubic

[(A(18C6))

(MnX

)] [TlCl

]

· nH

O Compounds 372

11.7 Luminescence Decay Dynamics and 18C6 Rotations 374

11.8 Conclusions 375

Acknowledgments 377

References 377

12 Optically Responsive Polymer Nanocomposites Containing Organic

Functional Chromophores and Metal Nanostructures 379

Andrea Pucci, Giacomo Ruggeri, and Francesco Ciardelli

12.1 Introduction 379

12.2 Organic Chromophores as the Dispersed Phase 380

Contents XI

12.2.1 Nature of the Organic Dye 380

12.2.2 Polymeric Indicators to Mechanical Stress 381

12.2.2.1 Oligo(p-Phenylene Vinylene) as Luminescent Dyes 381

12.2.2.2 Bis(Benzoxazolyl) Stilbene as a Luminescent Dye 383

12.2.2.3 Perylene Derivatives as Luminescent Dyes 384

12.2.3 Polymeric Indicators to Thermal Stress 385

12.2.3.1 Oligo(p-Phenylene Vinylene) as Luminescent Dyes 385

12.2.3.2 Bis(Benzoxazolyl) Stilbene as Luminescent Dye 387

12.2.3.3 Anthracene Triaryl Amine-Terminated Diimide as Luminescent

Dye 388

12.3 Metal Nanostructures as the Dispersed Phase 389

12.3.1 Optical Properties of Metal Nanoassemblies 389

12.3.2 Nanocomposite-Based Indicators to Mechanical Stress 391

12.3.2.1 The Use of Metal Nanoparticles 391

12.3.2.2 The Use of Metal Nanorods 395

12.4 Conclusions 397

Acknowledgments 398

References 398

13 Nanocomposites Based on Phyllosilicates: From Petrochemicals to

Renewable Thermoplastic Matrices 403

Maria-Beatrice Coltelli, Serena Coiai, Simona Bronco, and Elisa Passaglia

13.1 Introduction 403

13.1.1 Structure of Phyllosilicates 404

13.1.1.1 Clays 404

13.1.2 Morphology of Composites 408

13.1.3 Properties of Composites 411

13.2 Polyoleﬁ n-Based Nanocomposites 411

13.2.1 Overview of the Preparation Methods 412

13.2.2 Organophilic Clay and Compatibilizer: Interactions with the Polyoleﬁ n

Matrix 414

13.2.3 The One-Step Process 426

13.3 Poly(Ethylene Terephthalate)-Based Nanocomposites 429

13.3.1 In Situ Polymerization 430

13.3.2 Intercalation in Solution 433

13.3.3 Intercalation in the Melt 434

13.4 Poly(Lactide) (PLA)-Based Nanocomposites 439

13.4.1 Overview of Preparation Methods 439

13.4.1.1 In Situ Polymerization 439

13.4.1.2 Intercalation in Solution 442

13.4.1.3 Intercalation in the Melt 443

13.5 Conclusions 447

Acknowledgments 449

References 450

XII Contents

Volume 2

14 Amphiphilic Poly(Oxyalkylene)-Amines Interacting with Layered Clays:

Intercalation, Exfoliation, and New Applications 459

Jiang-Jen Lin, Ying-Nan Chan, and Wen-Hsin Chang

15 Mesoporous Alumina: Synthesis, Characterization,

and Catalysis 481

Tsunetake Seki and Makoto Onaka

16 Nanoceramics for Medical Applications 523

Besim Ben-Nissan and Andy H. Choi

17 Self-healing of Surface Cracks in Structural Ceramics 555

Wataru Nakao, Koji Takahashi, and Kotoji Ando

18 Ecological Toxicology of Engineered Carbon Nanoparticles 595

Aaron P. Roberts and Ryan R. Otter

19 Carbon Nanotubes as Adsorbents for the Removal of Surface

Water Contaminants 615

Jose E. Herrera and Jing Cheng

20 Molecular Imprinting with Nanomaterials 651

Kevin Flavin and Marina Resmini

21 Near-Field Raman Imaging of Nanostructures and Devices 677

Ze Xiang Shen, Johnson Kasim, and Ting Yu

22 Fullerene-Rich Nanostructures 699

Fernando Langa and Jean-François Nierengarten

23 Interactions of Carbon Nanotubes with Biomolecules: Advances

and Challenges 715

Dhriti Nepal and Kurt E. Geckeler

24 Nanoparticle-Cored Dendrimers and Hyperbranched Polymers:

Synthesis, Properties, and Applications 743

Young-Seok Shon

25 Concepts in Self-Assembly 767

Jeremy J. Ramsden

26 Nanostructured Organogels via Molecular Self-Assembly 791

Arjun S. Krishnan, Kristen E. Roskov, and Richard J. Spontak

Contents XIII

27 Self-assembly of Linear Polypeptide-based Block Copolymers 835

Sébastien Lecommandoux, Harm-Anton Klok, and Helmut Schlaad

28 Structural DNA Nanotechnology: Information-Guided

Self-Assembly 869

Yonggang Ke, Yan Liu, and Hao Yan

Index 881

Advanced Nanomaterials. Edited by Kurt E. Geckeler and Hiroyuki Nishide

ISBN: 978-3-527-31794-3

Nanotechnology has found an incredible resonance and a vast number of applica-

tions in many areas during the past two decades. The resulting deep paradigm

shift has opened up new horizons in materials science, and has led to exciting

new developments. Fundamentally, nanotechnology is dependent on the existence

or the supply of new nanomaterials that form the prerequisite for any further

progress in this new and interdisciplinary area of science and technology. Evi-

dently, nanomaterials feature speciﬁ c properties that are characteristic of this class

of materials, and which are based on surface and quantum effects.

Clearly, the control of composition, size, shape, and morphology of nanomateri-

als is an essential cornerstone for the development and application of nanomateri-

als and nanoscale devices. The complex functions of nanomaterials in devices and

systems require further advancement in the preparation and modiﬁ cation of nano-

materials. Such advanced nanomaterials have attracted tremendous interest

during recent years, and will form the basis for further progress in this area. Thus,

the major classes of novel materials are described in the twenty - eight chapters of

this two - volume monograph.

The initializing concept of this book was developed at the 3rd IUPAC Interna-

tional Symposium on Macro - and Supramolecular Architectures and Materials (MAM -

06): Practical Nanochemistry and Novel Approaches , held in in Tokyo, Japan, 2006,

within the framework of the biannual MAM symposium series. This monograph

provides a detailed account of the present status of nanomaterials, and highlights

the recent developments made by leading research groups. A compilation of state -

of - the - art review chapters, written by over sixty contributors and well - known

experts in their ﬁ eld from all over the world, covers the novel and important

aspects of these materials, and their applications.

The different classes of advanced nanomaterials, such as block copolymer

systems including block copolymer nanoﬁ bers and nanotubes, smart nanoassem-

blies of block copolymers for drug and gene delivery, aligned and ordered

block copolymers, helical polymer - based supramolecular ﬁ lms, as well as novel

composite materials based on gold nanoparticles and carbon nanotubes, are

covered in the book. Other topics include the synthesis of inorganic nanotubes,

metal nanoparticle - attached electrodes, radical polymers in organic polymer

batteries, oxidation catalysis by nanoscale gold, silver, copper, self - assembling

Preface

XVI Preface

nanoclusters, optically responsive polymer nanocomposites, renewable thermo-

plastic matrices based on phyllosilicate nanocomposites, amphiphilic polymer –

clay intercalation and applications, the synthesis and catalysis of mesoporous

alumina, and nanoceramics for medical applications.

In addition, this book highlights the recent progress in the research and applica-

tions of structural ceramics, the ecological toxicology of engineered carbon

nanoparticles, carbon nanotubes as adsorbents for the removal of surface water

contaminants, molecular imprinting with nanomaterials, near - ﬁ eld Raman

imaging of nanostructures and devices, fullerene - rich nanostructures, nanoparti-

cle - cored dendrimers and hyperbranched polymers, as well as the interactions

of carbon nanotubes with biomolecules. The book is completed with a series of

chapters featuring concepts in self - assembly, nanostructured organogels via

molecular self - assembly, the self - assembly of linear polypeptide - based block copol-

ymers, and information - guided self - assembly by structural DNA nanotechnology.

The variety of topics covered in this book make it an interesting and valuable

reference source for those professionals engaged in the fundamental and applied

research of nanotechnology. Thus, scientists, students, postdoctoral fellows,

engineers, and industrial researchers, who are working in the ﬁ elds of nanomateri-

als and nanotechnology at the interface of materials science, chemistry, physics,

polymer science, engineering, and biosciences, would all beneﬁ t from this

monograph.

The advanced nanomaterials presented in this book are expected to result in

commercial applications in many areas. As the science and technology of nano-

materials is still in its infancy, further research will be required not only to develop

this new area of materials science, but also to explore the utilization of these novel

materials. All new developments impart risks, and here also it is important to

evaluate the risks and beneﬁ ts associated with the introduction of such materials

into the biosphere and ecosphere.

On behalf of all contributors to we thank the publishers and authors on behalf

of all contributors for granting copyright permissions to use their illustrations in

this book. It is also very much appreciated that the authors devoted their time and

efforts to contribute to this monograph. Last, but not least, the major prerequisite

for the success of this comprehensive book project was the cooperation, support,

and understanding of our families, which is greatly acknowledged.

The Editors

List of Contributors

XVII

Advanced Nanomaterials. Edited by Kurt E. Geckeler and Hiroyuki Nishide

ISBN: 978-3-527-31794-3

Kotoji Ando

Yokohama National University

Department of Material Science

and Engineering

79 - 1 Tokiwadai

Hohogaya - ku

Yokohama 240-8501

Japan

Besim Ben - Nissan

University of Technology

Faculty of Science

Broadway

P.O. Box 123

Sydney

NSW 2007

Australia

Simona Bronco

CNR - INFM - PolyLab c/o

Dipartimento di Chimica e

Chimica Industriale

Universit à di Pisa

Via Risorgimento 35

56126 Pisa

Italy

Horacio Cabral

The University of Tokyo

Department of Materials Engineering

Graduate School of Engineering

7 - 3 - 1 Hongo, Bunkyo - ku

Tokyo 113 - 8656

Japan

Ying - Nan Chan

National Taiwan University

Institute of Polymer Science and

Engineering

Taipei 10617

Taiwan

and

National Chung Hsing University

Department of Chemical Engineering

Taichung 40227

Taiwan

Wen - Hsin Chang

National Taiwan University

Institute of Polymer Science and

Engineering

Taipei 10617

Taiwan

XVIII List of Contributors

Jing Cheng

The University of Western

Ontario

Department of Civil and

Environmental Engineering

London, ON N6A 5B9

Canada

Andy H. Choi

University of Technology

Faculty of Science

Broadway

P.O. Box 123

Sydney

NSW 2007

Australia

Francesco Ciardelli

University of Pisa

CNR - INFM - PolyLab

c/o Department of Chemistry,

and Industrial Chemistry

Via Risorgimento 35

56126 Pisa

Italy

Serena Coiai

Centro Italiano Packaging and

Dipartimento di Chimica e

Chimica Industriale

Universit à di Pisa

Via Risorgimento 35

56126 Pisa

Italy

Maria - Beatrice Coltelli

Centro Italiano Packaging and

Dipartimento di Chimica e

Chimica Industriale

Universit à di Pisa

Via Risorgimento 35

56126 Pisa

Italy

Claudio De Rosa

University of Napoli “ Federico II ”

Department of Chemistry

Complesso Monte S. Angelo

Via Cintia

80126 Napoli

Italy

Soorly G. Divakara

Colorado School of Mines

Department of Chemistry and

Geochemistry

1500 Illinois St.

Golden, CO 80401

USA

Kevin Flavin

Queen Mary University of London

School of Biological and Chemical

Sciences

Mile End Road

London E1 4NS

Michiya Fujiki

Nara Institute of Science and

Technology

Graduate School of Materials Science

8916 - 5 Takayama

Ikoma

Nara 630 - 0101

Japan

Kurt E. Geckeler

Gwangju Institute of Science and

Technology (GIST)

Department of Materials Science and

Engineering

1 Oryong - dong, Buk - gu

Gwangju 500 - 712

South Korea