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1 Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from

2 Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from GOLD NANOPARTICLES FOR PHYSICS, CHEMISTRY AND BIOLOGY

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4 Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from GOLD NANOPARTICLES FOR PHYSICS, CHEMISTRY AND BIOLOGY Catherine Louis Olivier Pluchery Université Pierre et Marie Curie, France ICP Imperial College Press

5 Published by Imperial College Press 57 Shelton Street Covent Garden London WC2H 9HE Distributed by Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from World Scientific Publishing Co. Pte. Ltd. 5 Toh Tuck Link, Singapore USA office: 27 Warren Street, Suite , Hackensack, NJ UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. GOLD NANOPARTICLES FOR PHYSICS, CHEMISTRY AND BIOLOGY Copyright 2012 by Imperial College Press All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means, electronic or mechanical, including photocopying, recording or any information storage and retrieval system now known or to be invented, without written permission from the Publisher. For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to photocopy is not required from the publisher. ISBN Typeset by Stallion Press enquiries@stallionpress.com Printed in Singapore.

6 Contents Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from Preface Chapter 1. Chapter 2. Gold Nanoparticles for Physics, Chemistry and Biology Gold Nanoparticles in the Past: Before the Nanotechnology Era 1 Catherine Louis Introduction to the Physical and Chemical Properties of Gold 29 Geoffrey C. Bond Chapter 3. Optical Properties of Gold Nanoparticles 43 Olivier Pluchery Chapter 4. Photothermal Properties of Gold Nanoparticles 75 Bruno Palpant Chapter 5. Synthesis of Gold Nanoparticles in Liquid Phase 103 Daeha Seo and Hyunjoon Song vii Chapter 6. Chemical Preparation of Gold Nanoparticles on Surfaces 139 Catherine Louis v

7 Contents Chapter 7. Catalytic Properties of Gold Nanoparticles 171 Geoffrey C. Bond Chapter 8. Surface Structures of Gold Nanoparticles 199 Shamil Shaikhutdinov Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from Chapter 9. Chapter 10. Theoretical Studies of Gold Nanoclusters in Various Chemical Environments: When the Size Matters 233 Hannu Häkkinen Optical and Thermal Properties of Gold Nanoparticles for Biology and Medicine 273 Romain Quidant Chapter 11. Gold Nanoparticles for Sensors and Drug Delivery 299 Christian Villiers Chapter 12. What About Toxicity and Ecotoxicity of Gold Nanoparticles? 333 Marie Carrière Chapter 13. Technological Applications of Gold Nanoparticles 355 Michael Cortie Biographies of the Authors 379 Index 389 vi

8 Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from Preface Gold Nanoparticles for Physics, Chemistry and Biology The fascination with gold is a story which spans millennia and this metal has played a role in almost every area of human existence. It has been a way of expressing wealth, it has been the cause of battles and wars, it has often been related to religious devotion, and has been linked with our most intimate feelings as a way of expressing love. These meanings are still important today. However, in recent years, a new type of fascination with gold has emerged in the scientific community that is not linked to any greed or emotion but to more rational concerns. Scientists have found a new interest in gold when it is divided into miniscule grains, such as gold nanoparticles. This scientific enthusiasm started in various fields of science over the last three decades. For instance, gold was thought to be chemically inactive, but it was discovered in 1987 that gold nanoparticles with sizes smaller than 5 nm are excellent catalysts. Bulk gold was thought to exhibit its eternal yellow shining colour; it turns out, however, that gold nanoparticles are red or blue due to the so-called plasmon resonance, a property that has excited the interest of physicists since 1990 with biologists having now also joined the move. This statement that various scientific communities are working on the same object with low awareness of each other is actually at the origin of the publication of this book. It is also backed up by the success of the French Network Or-nano (Gold-Nano) that we founded in 2006 ( This French network is sponsored by the CNRS (Centre National pour vii

9 Preface Gold Nanoparticles for Physics, Chemistry and Biology Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from la Recherche Scientifique) and gathers researchers and PhD students working on gold nanoparticles with various motives: from very fundamental studies of the properties of gold nanoparticles to more applied topics, such as catalysis, biosensors or medical imaging. Or-nano has organized annual meetings, a summer school in 2008 and specialized discussions, all of which keep attracting a great audience proving the need for the scientific survey of gold nanoparticles proposed by the present book. Gold Nanoparticles for Physics, Chemistry and Biology provides a broad introduction to the fascinating and intriguing world of gold nanoparticles. Chapter 1 relates the history of gold nanoparticles, which begins in remote times with red ruby glass and reached a peak at the end of the seventeenth century. This section is an original work that has never been treated in other scientific books. Basic properties of gold as an element are surveyed in Chapter 2 with a special emphasis on the relativistic effect that is responsible of many unusual properties of this metal. Chapters 3 and 4 lead the reader into the optical and thermal properties of gold nanoparticles by detailing the plasmon resonance and giving the basis necessary to understand the applications of these nano-objects as ultra small light emitters: nano-heaters or nano-antennas. The preparation of gold nanoparticles with sometimes fascinating shapes is reviewed in Chapter 5. Very often applications demand, however, that nanoparticles are deposited on a substrate and the preparation methods have to be adapted or completely revisited. This crucial aspect is treated in Chapter 6. The preparation of such supported gold nanoparticles is the key to the catalytic properties of gold and Chapter 7 reviews the present knowledge on these aspects with the emblematic reaction of carbon monoxide oxidation and many other hot topics. Fundamental studies of the formation and reactivity of gold nanoparticles in a highly controlled environment such as ultra-high vacuum are treated in Chapter 8. Chapter 9 goes into more fundamental questions and presents state of the art ab initio calculations to reveal the geometry of gold clusters made with ten or so gold atoms and their non-metallic behaviour with the onset of a semiconductorlike gap. Applications in the fields of biology and medicine are treated in two chapters with two complementary approaches: Chapter 10 reviews the approach of physicists who engineer the plasmonic properties to design smart biosensors and Chapter 11 presents the approach of biologists who seek in gold nanoparticles a new method for drug delivery and therapeutic viii

10 Preface Gold Nanoparticles for Physics, Chemistry and Biology Gold Nanoparticles for Physics, Chemistry and Biology Downloaded from treatments. However nanoparticles also inspire fear because they can be considered as invasive and uncontrollable nano-objects and may lead to unpredictable consequences on health and the environment. That is the reason why the potential toxicity of gold nanoparticles is reviewed in Chapter 12. The book concludes in Chapter 13 with a survey of the promises of gold nanoparticles and the technological applications that could become a part of everyday life in the future. The book may be used as an advanced textbook by graduate students and young scientists who need an introduction to gold nanoparticles. It is also suitable for experts in the related areas of chemistry, biology, material science, optics and physics, who are interested in broadening their knowledge and gaining an overview of the subject. Each chapter gradually leads the reader from the basis of a topic to some selected scientific challenges in the area. It provides the necessary up-to-date background material and scientific literature to go further. Finally, we are grateful to all who contributed to this work: first to the ten authors who have always been very responsive and enthusiastic about the idea of the book. We thank Imperial College Press for its strong support of the proposition of publishing such an interdisciplinary book based on gold nanoparticles. A special thanks goes to Catharina Weijman and Sarah Haynes who made the task of assembling the book easier. Thanks to Richard Holliday of the World Gold Council for his suggestions and advice. We also want to acknowledge particularly the help from Rachel Doherty and Philip Campbell for their contribution in improving the quality of the English of some parts of the text. Catherine Louis Olivier Pluchery Paris, 20 June, 2012 ix