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  • Novel Nanoscale Hybrid Materials

  • Novel Nanoscale Hybrid Materials

    Edited by

    Bhanu P. S. Chauhan Department of Chemistry William Paterson University Wayne, NJ, USA

  • This edition first published 2018 © 2018 John Wiley & Sons, Inc.

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    Library of Congress Cataloging‐in‐Publication Data

    Names: Chauhan, Bhanu P. S., editor. Title: Novel nanoscale hybrid materials / edited by Bhanu P. S. Chauhan. Description: Hoboken, NJ : John Wiley & Sons, 2018. | Includes bibliographical references and index. | Identifiers: LCCN 2017036464 (print) | LCCN 2017046280 (ebook) | ISBN 9781119156277 (pdf) | ISBN 9781119156260 (epub) | ISBN 9781119156246 (cloth) Subjects: LCSH: Nanostructured materials. | Composite materials. Classification: LCC TA418.9.N35 (ebook) | LCC TA418.9.N35 N675 2018 (print) | DDC 620.1/18–dc23 LC record available at

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    10 9 8 7 6 5 4 3 2 1

  • Om Shree Guruve Namah

    to my life lines bholu, doujal, and shati and to my big brother a hero of all heros in my life

  • vii

    List of Contributors xi

    1 Silanols as Building Blocks for Nanomaterials 1 Masafumi Unno and Hisayuki Endo

    1.1 Introduction 1 1.2 Synthesis and Applications of Silanols 2 1.2.1 Silanetriols and Disiloxanetetraols 2 1.2.2 Cyclotetrasiloxanetetraol (Cyclic Silanols, All‐cis Isomer) 5 1.2.3 Cyclotetrasiloxanetetraol (Cyclic Silanols, Other Isomers) 14 1.2.4 Cyclotrisiloxanetriol 15 1.3 Structures and Properties of Nanomaterials Obtained

    from Silanols 20 1.3.1 Structure of Laddersiloxanes 20 1.3.2 Thermal Property of Laddersiloxanes 23 1.3.3 Thermal Property of Other Silsesquioxanes 26 1.3.4 Refractive Indices of Silsesquioxanes 28 1.4 Summary and Outlook 29 References 29

    2 Biomacromolecule‐Enabled Synthesis of Inorganic Materials 33 Kristina L. Roth and Tijana Z. Grove

    2.1 Introduction 33 2.2 DNA 34 2.3 Proteins and Peptides 36 2.3.1 Cage Proteins 37 2.3.2 Bovine Serum Albumin (BSA) 38 2.3.3 Engineered Peptides 40 2.3.4 Engineered Protein Scaffolds 42 2.4 Polysaccharides 44 2.5 Methods of Characterization 46 2.6 Conclusion 50 References 50


  • Contentsviii

    3 Multilayer Assemblies of Biopolymers: Synthesis, Properties, and Applications 57 Jun Chen, Veronika Kozlovskaya, Daniëlle Pretorius, and Eugenia Kharlampieva

    3.1 Introduction 57 3.2 Assembly of Biopolymer Multilayers 58 3.2.1 Biopolymers and Their Properties 58 3.2.2 Growth and Thickness of Biopolymer Multilayers 59 3.2.3 Stability in Solutions and Enzymatic Degradation of

    Biopolymer Multilayers 74 3.2.4 Hydration and Swelling of Biopolymer Multilayers 81 3.3 Properties of Biopolymer Multilayers 83 3.3.1 Surface Properties of Biopolymer Multilayers and Their

    Interaction with Cells 83 3.3.2 Antibacterial Properties 84 3.3.3 Immunomodulatory Properties 85 3.3.4 Mechanical Properties of Biopolymer Multilayers 87 3.3.5 Other Properties 90 3.4 Applications 91 3.5 Conclusion and Outlook 95 Acknowledgment 96 References 96

    4 Functionalization of P3HT‐Based Hybrid Materials for Photovoltaic Applications 107 Michèle Chevrier, Riccardo Di Ciuccio, Olivier Coulembier, Philippe Dubois, Sébastien Richeter, Ahmad Mehdi, and Sébastien Clément

    4.1 Introduction 107 4.2 Design and Synthesis of Regioregular Poly(3‐Hexylthiophene) 109 4.2.1 Metal‐Catalyzed Cross‐Coupling Reactions 114 4.2.2 Functionalization of P3HT 126 4.3 Morphology Control of P3HT/PCBM Blend by

    Functionalization 132 4.3.1 Introduction 132 4.3.2 End‐Group Functionalization 134 4.3.3 Side‐Chain Functionalization 144 4.4 Polymer–Metal Oxide Hybrid Solar Cells 154 4.4.1 Anchoring Method 156 4.4.2 Surface Modification Using End‐ and 

    Side‐Chain‐Functionalized P3HT 158 4.5 Conclusion 163 Acknowledgments 164 References 164

  • Contents ix

    5 Insights on Nanofiller Reinforced Polysiloxane Hybrids 179 Debarshi Dasgupta, Alok Sarkar, Dieter Wrobel , and Anubhav Saxena

    5.1 Properties of Silicone (Polysiloxane) 179 5.2 Nanofiller Composition and Chemistry 183 5.2.1 Fumed Silica 183 5.2.2 Aerogel Silica 185 5.2.3 Carbon Black 187 5.3 Polymer [Poly(dimethylsiloxane)]–Filler Interaction 187 5.4 Polymer–Filler Versus Filler–Filler Interactions 190 5.5 PDMS Nanocomposite with Anisotropic Fillers 194 5.6 PDMS–Molecular Filler Nanocomposite 196 Acknowledgments 198 References 198

    6 Nanophotonics with Hybrid Nanostructures: New Phenomena and New Possibilities 201 Noor Eldabagh, Jessica Czarnecki, and Jonathan J. Foley IV

    6.1 Introduction 202 6.2 Theoretical Nanophotonics 204 6.2.1 Mie Theory for Spherical Nanostructures 205 6.2.2 Transfer Matrix Methods for Planar Structures 208 6.2.3 The Finite‐Difference Time‐Domain Method 214 6.2.4 The Discrete Dipole Approximation 215 6.3 Hybrid Nanostructures 216 6.3.1 Emergent Electrodynamics Phenomena: Inhomogeneous Surface

    Plasmon Polaritons 216 6.3.2 Advancing Imaging Beyond the Diffraction Limit with ISPPs 220 6.3.3 Emergent Material‐Dependent Optical Response in Hybrid

    Nanostructures 222 6.3.4 Perspective on the Horizon of Health Applications of Hybrid

    Nanostructures 228 6.3.5 Photodynamic Therapy 228 6.3.6 In Vivo Light Sources 231 6.4 Concluding Remarks 233 References 233

    7 Drug Delivery Vehicles from Stimuli‐Responsive Block Copolymers 239 Prajakta Kulkarni and Sanku Mallik

    7.1 Introduction 239 7.2 Block Copolymers for Drug Delivery 241 7.3 Polymeric Nanoparticles 241 7.3.1 Micelles 241 7.3.2 Hydrogels 243 7.3.3 Polymersomes 244

  • Contentsx

    7.4 Stimuli‐Responsive Drug Delivery 245 7.4.1 Physical/External Stimuli‐Responsive Polymers 246 7.4.2 Chemical/Internal Stimuli‐Responsive Polymers 248 7.5 Challenges and Prospects 252 7.6 Summary 252 References 253

    8 Mechanical Properties of Rubber‐Toughened Epoxy Nanocomposites 263 B. Zewde, I. J. Zvonkina, A. Bagasao, K. Cassimere, K. Holloway, A. Karim, and D. Raghavan

    8.1 Introduction 263 8.2 Epoxy Resins 265 8.3 Rubber‐Toughened Epoxy Resin 266 8.4 Nanoparticle Filled Epoxy Nanocomposites 269 8.5 Carbon Nanotubes 270 8.6 Rubber‐Toughened CNT Filled Epoxy Nanocomposites 275 8.7 Nanoclay Filled Epoxy Nanocomposites 277 8.8 Rubber‐Toughened Nanoclay Filled Epoxy Nanocomposites 282 8.9 Silicon Dioxide Nanoparticles 284 8.10 Rubber‐Toughen