Gold nanoparticles for physics, chemistry and biology (2nd ed)

Optical Properties of Gold Nanoparticles 51 3.1 Introduction... Photothermal Properties of Gold Nanoparticles 874.1 Introduction: Light to Heat Conversion at the Nanoscale.. Quantum Prop

Library of Congress Cataloging-in-Publication Data

Names: Louis, Catherine (Chemist) | Pluchery, Olivier.

Title: Gold nanoparticles for physics, chemistry and biology / Catherine Louis (Université Pierre et

Marie Curie, France), Olivier Pluchery (Université Pierre et Marie Curie, France).

Description: 2nd edition | New Jersey : World Scientific, 2017 |

Includes bibliographical references.

Identifiers: LCCN 2016034787 | ISBN 9781786341242 (hc : alk paper)

Subjects: LCSH: Nanoparticles | Gold.

Classification: LCC TA418.9.N35 L68 2017 | DDC 669/.22 dc23

LC record available at https://lccn.loc.gov/2016034787

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1 Gold Nanoparticles in the Past: Before the

1.1 The First Usage of Gold 1

1.1.1 Quest for Gold and Gold Production 1

1.1.2 The First Gold Jewels and Artefacts 3

1.1.3 Gold for Monetary Exchanges and the Gold Standard 5

1.1.4 Gold for Human Well-being: Food, Drinks and Medicine 6

1.1.5 Gilding Gold and Gold-like Lustre 7

1.2 The First Uses of Gold Nanoparticles 8

1.2.1 Introduction 8

1.2.2 The Lycurgus Cup 9

1.2.3 Medieval Period 11

1.2.4 Fifteenth and Sixteenth Centuries 12

1.2.5 Seventeenth Century 13

1.2.5.1 Purple of Cassius 14

1.2.5.2 Kunckel glass 15

1.2.5.3 Perrot glass 16

1.2.6 Gold Ruby Glass in the Eighteenth Century 17

1.2.7 Gold Ruby Glass and Cranberry Glass in the Nineteenth Century 18

1.2.8 Pink Enamel Porcelain: Rose Pompadour and

Famille Rose 19

1.3 Scientific Approach of the Preparation of the Gold Ruby Colour 20

1.3.1 Elucidation of the Constitution of the Purple of Cassius in the Nineteenth Century 20

1.3.2 Chemical Approach to the Formation of the Purple of Cassius 21

1.3.3 Chemical Approach to the Preparation of Gold Ruby Glass 22

1.4 Conclusion 25

2 Introduction to the Physical and Chemical Properties of Gold 29 2.1 Introduction 29

2.2 Physical Properties of Massive Gold 30

2.2.1 Crystal Structure 30

2.2.2 Density 31

2.2.3 Magnetic and Electrical Properties 32

2.2.4 Theoretical Calculations on Metallic Gold 32

2.2.5 Cohesive Properties 33

2.3 Relativistic Effects on the Properties of Gold 33

2.3.1 Why Relativity? 33

2.3.2 Optical Properties, Interband Transitions and Relativistic Effect 36

2.4 Chemical Properties of Gold in Relation to its Neighbours 37

2.5 More on Gold Chemistry 39

2.6 Surface Science and Cluster Studies 39

2.7 The Aurophilic Attraction 40

2.8 Dependence of Physical and Chemical Properties of Gold on Particle Size 41

2.9 Conclusion 44

3 Optical Properties of Gold Nanoparticles 51 3.1 Introduction 51

3.1.1 A Brief History of Plasmonics 52

3.1.2 What Is the Ambition of the Present Chapter? 53

3.2 Distinction between Localised Surface Plasmon Resonance and Surface Plasmon Resonance 54

3.2.1 Optical Properties of Metals 55

3.2.2 The Dielectric Function of Gold 56

3.2.3 Plasmon Resonance at Surfaces (SPR) 57

3.2.4 Localised Surface Plasmon Resonance in Nanoparticles 59

3.3 Theoretical Description of the Localised Plasmon Resonance 60

3.3.1 About Mie Theory 60

3.3.2 The Quasi-static Approximation for Describing the Localised Plasmon Resonance 60

3.3.3 Extinction and Scattering Cross-Sections 63

3.3.4 Experimental Illustrations 65

3.3.5 Local Field Enhancement and Nanoantennas 66

3.3.6 Beyond the Quasi-static and Dipolar Approximations 68

3.4 Factors Shifting the Plasmon Resonance of Gold Nanoparticles 69

3.4.1 What is the Dependence of the LSPR with the Nanoparticle? 70

3.4.2 Influence of the Surrounding Medium 71

3.4.3 Plasmon Resonance of Ellipsoids and Other Shapes 72

3.4.4 The Case of Very Small (Less than 5 nm) and Very Large Gold Nanoparticles (Greater than 60 nm) 77

3.5 Optical Response of Assemblies of Nanoparticles 78

3.5.1 Supported Gold Nanoparticles 79

3.5.2 Nanoparticle Coupling 79

3.5.3 Effective Medium Approximation Methods 81

3.6 Conclusion 83

4 Photothermal Properties of Gold Nanoparticles 87

4.1 Introduction: Light to Heat Conversion

at the Nanoscale 88

4.1.1 Electron–Phonon Scattering in Bulk Metal 88

4.1.2 The Localised Plasmon Resonance as an Effective Energy Input Channel 89

4.1.3 A Series of Energy Exchanges 89

4.2 Basic Plasmonic Photothermal Properties 91

4.2.1 Power Input in Nanoparticles 92

4.2.2 Basic Approach: Pure Diffusion, Perfect Contact 94

4.2.3 Accounting for Interface Thermal Resistance 95

4.2.4 Steady-state Photo-heating 96

4.2.4.1 Nanoparticle scale 97

4.2.4.2 Macroscopic scale 98

4.2.5 A Few Emblematic Applications 99

4.3 Transient Thermal Behaviour with Pulsed-Light Irradiation 102

4.3.1 Instantaneous Light Pulse Approximation 102

4.3.2 Athermal Regime 104

4.3.3 Thermal Regime 107

4.3.3.1 Analysis of the energy exchanges 108

4.3.3.2 Tuning the thermal spatial range with pulse duration 113

4.3.3.3 Cumulative thermal effect 113

4.3.4 When the Fourier Law Fails: What Occurs at Small Space and Time Scales 115

4.4 Influence of Morphological Parameters 117

4.4.1 Nanoparticle Environment 118

4.4.2 Nanoparticle Size 118

4.4.3 Nanoparticle Shape 120

4.4.4 Nanoparticle Density 121

4.5 Thermo-optical Properties of Gold Nanoparticles 121

4.5.1 Bulk Gold 122

4.5.2 Gold Nanoparticles 123

4.5.3 Melting Point Depression in Gold

Nanoparticles 124

4.6 Conclusion 126

5 Quantum Properties of Gold Nanoparticles 131 5.1 Introduction 131

5.2 Quantum Optical Properties 133

5.2.1 Single Nanoparticles — From Classical to Quantum 133

5.2.2 Many-nanoparticle Array 137

5.2.3 Single Nanoparticles Interacting with Emitters: Weak and Strong Coupling Regime 141

5.2.4 Nanoparticle Systems as Unit Cells in Metamaterials 144

5.2.5 Dealing with Metallic Loss 148

5.3 Quantum Electronic Properties 149

5.3.1 Quantum Size Effect: Analytical and Numerical 150

5.3.2 Quantum Tunnelling: Linear and Nonlinear Regimes 151

5.4 Conclusion 153

6 Synthesis of Gold Nanoparticles in Liquid Phase 165 6.1 Introduction 165

6.2 Chemical Properties and Characterisation of Gold Nanoparticles for Liquid Phase Synthesis 166

6.2.1 Structure and Size Range of Gold Nanoparticles 166

6.2.2 Electrochemical Potentials of Gold Precursors 168

6.2.3 Surface Energy and Particle Morphology 169

6.2.4 Characterisation of Nanoparticles 170

6.2.4.1 Morphology characterisation 170

6.2.4.2 Surface characterisation 170

6.2.4.3 Theoretical simulation 171

6.3 Synthetic Methods of Gold Nanoparticles in Liquid Phase 171

6.3.1 Kinetic Consideration for Highly Monodisperse

Nanoparticles 171

6.3.2 Chemical Reduction of Gold Precursors 172

6.3.2.1 Chemical reduction in aqueous media 173

6.3.2.2 Chemical reduction in organic media 176

6.3.2.3 Synthesis in micelles 177

6.3.2.4 Polyol process 177

6.3.3 Non-chemical Reduction for Preparation of Gold Nanoparticles 178

6.3.3.1 Photochemical and radiolytic methods 178

6.3.3.2 Electrochemical methods 180

6.3.3.3 Sonochemical method 180

6.3.3.4 Microwave-assisted methods 181

6.4 Shape Control of Gold Nanoparticles 181

6.4.1 Shaping Strategies with Seed-mediated Growth 182

6.4.2 Selective Binding of Capping Reagents 183

6.4.3 Underpotential Deposition of Heterometallic Additives 185

6.4.4 Template-directed Synthesis 186

6.5 Synthetic Methods of Gold–Metal Bimetallic Nanoparticles in Liquid Phase 187

6.5.1 Structure and Composition of Gold–Metal Bimetallic Nanoparticles 187

6.5.2 Synthetic Protocols of Gold–Metal Bimetallic Nanoparticles 189

6.5.2.1 Co-reduction 189

6.5.2.2 Seed-mediated growth 190

6.5.2.3 Galvanic replacement 192

6.6 Conclusion 193

7 Functionalisation of Gold Nanoparticles 201 7.1 Introduction 201

7.2 Geometric Considerations: Why Does the Size Matter? 203

7.2.1 Coordination and Arrangement of Surface Atoms 203

7.2.2 Particle Curvature Influence 205

7.3 Major Strategies for Organic Chemical Derivatisation 206

7.3.1 Self-Assembly of Monomeric Thiol and Amine Molecules on Gold Nanoparticles 206

7.3.2 Surface-regulating Polymers 209

7.3.3 Competitive Displacement 210

7.4 Silica Capping of Gold Nanoparticles 212

7.4.1 Primer-mediated Silica Coating 213

7.4.2 Direct Silica Coating 214

7.4.3 Other Protocols for Citrate-stabilised Nanoparticle Coating 215

7.4.4 Silica-capping of CTAB-stabilised Gold Nanoparticles 216

7.5 Biofunctionalisation of Gold Nanoparticles 217

7.5.1 Water-dispersible Gold Nanoparticles 219

7.5.2 Non-biofouling Gold Nanoparticles 220

7.5.3 Active Biofunctional Gold Nanoparticles 222

7.6 Conclusions 223

8 Chemical Synthesis of Gold Nanoparticles on Surfaces and in Matrices 229 8.1 Introduction 229

8.2 Gold Nanoparticles Supported on Powder Inorganic Supports 232

8.2.1 Deposition–Reduction (Deposition of Gold Precursor) 233

8.2.1.1 Impregnation and related methods 233

8.2.1.2 Deposition–precipitation and related methods 235

8.2.1.3 Less common preparation methods 239

8.2.1.4 Gold-based bimetallic catalysts prepared by deposition–reduction 241

8.2.2 Reduction in Liquid Phase 243

8.2.2.1 Chemical reduction 243

8.2.2.2 Chemical reduction assisted by

microwave irradiation 244

8.2.2.3 Photochemical deposition–reduction 244

8.2.2.4 Sonochemical deposition–reduction 245

8.2.2.5 Gold-based bimetallic catalysts obtained by reduction in liquid phase 245

8.2.3 Reduction–Deposition (Deposition of Preformed Gold Particles) 247

8.2.3.1 Gold colloids 248

8.2.3.2 Gold in micelles 251

8.2.3.3 Gold in dendrimers 252

8.2.3.4 Gold-based bimetallic catalysts prepared by reduction–deposition 253

8.2.4 Specific Methods for the Preparation of Supported Bimetallic Particles 258

8.2.4.1 Bimetallic clusters 258

8.2.4.2 Surface redox methods 258

8.3 Gold Nanoparticles Embedded into a Matrix 260

8.3.1 Gold Embedded into an Inorganic Matrix 261

8.3.1.1 Monometallic gold 261

8.3.1.2 Bimetallic systems 263

8.3.2 Gold in an Inorganic Matrix with Ordered Porosity 264

8.3.3 Gold on/in Organic Materials 265

8.3.4 Gold on/in Inorganic–Organic Materials 266

8.4 Gold Nanoparticles on Planar Surfaces 268

8.4.1 Non-ordered Deposition 268

8.4.2 Ordered Deposition 269

8.5 Conclusion 270

9 Catalytic Properties of Gold Nanoparticles 285 9.1 Introduction 285

9.2 CO Oxidation 286

9.3 Hydrocarbon Oxidation in the Presence of H2or Other Sacrificial Reductants 290

9.4 Oxidation Using Molecular O2 293

9.5 Hydrogenation 304

9.6 Conclusions 310

10 Plasmonic Photocatalysis 319 10.1 Introduction 319

10.2 Function of Gold and Mechanism of Plasmon-assisted Reactions 321

10.2.1 Under UV Irradiation: Activation of Semiconducting Support 324

10.2.2 Under Visible Irradiation: Activation of Plasmon Resonance 327

10.2.2.1 Charge transfer (plasmon-assisted photocatalysis) 328

10.2.2.2 Energy transfer (plasmon-assisted photocatalysis) 331

10.2.2.3 Plasmonic heating (plasmon-assisted catalysis) 332

10.2.3 Mechanism Dependence on Properties of Photocatalysts 335

10.2.3.1 Gold properties 335

10.2.3.2 Support properties 337

10.2.3.3 Interaction interface between gold and support 338

10.3 Application 340

10.3.1 Environmental Purification 340

10.3.1.1 Water and wastewater treatment 340

10.3.1.2 Gas phase purification (and artificial photosynthesis) 342

10.3.1.3 Self-cleaning of surfaces 343

10.3.2 Solar Energy Conversion 344

10.3.2.1 Photocurrent generation 344

10.3.2.2 Fuel generation 345

10.3.3 Synthesis of Organic Compounds 348

10.4 Strategies for Activity and Stability Enhancement 349

10.4.1 Nano-architecture Arrangement 349

10.4.1.1 Gold properties: Extension of action for

overall solar spectrum 34910.4.1.2 Support properties and interface between

gold and support 35110.4.2 Hybrid Nanostructures 35310.4.2.1 Heterogeneous nanostructures:

Plasmonic photocatalysts and othersolid materials 35310.4.2.2 Heterogeneous–homogeneous

photocatalysts (plasmonicphotocatalysts–metal complexes) 35410.4.2.3 Bimetallic plasmonic photocatalysts 35510.5 Conclusions 356

11 Electrical Generation of Light from Plasmonic

11.1 Introduction 365

11.2 Light from Electrons via Gold Nanoparticles: Mechanisms

and Experimental Set-ups 36611.2.1 Light from the Low-energy Electrical Excitation

of Gold: Biased Tunnel Junctions 36611.2.1.1 Excitation 36811.2.1.2 Emission 37011.2.1.3 Probe size and experimental

apparatus for the local electricalexcitation of gold nanoparticles withlow energy electrons 37111.2.2 Light from the High-energy Electrical Excitation

of Gold: Cathodoluminescence 37211.2.2.1 Excitation and emission 37211.2.2.2 Cathodoluminescence and

the radiative local electromagneticdensity of states 373

11.2.2.3 Probe size and experimental apparatus

for the local electrical excitation

of gold nanoparticles with high-energy

electrons 375

11.3 Recent Achievements in the Electrical Generation of Light from Gold Nanoparticles 375

11.3.1 A Probe of Nanoscale Electronic Phenomena 377

11.3.2 Selective Electrical Excitation and Imaging of the Plasmonic Modes of Gold Nanoparticles 378

11.3.3 A Single Gold Nanoparticle as an Electrically Driven Nanosource of Light 381

11.3.4 A Gold NanoparticleArray as an Electrically Driven Optical Antenna or Resonator 383

11.4 Towards On-chip Applications of Electron-to-photon Energy Conversion Using Gold Nanoparticles 384

11.5 Conclusion 386

12 Surface Structures of Gold and Gold-based Bimetallic Nanoparticles 393 12.1 Introduction 393

12.2 Background 395

12.3 Surface Structures of Gold Single Crystals 397

12.4 Morphology of Gold Nanoparticles: General Considerations 399

12.5 Planar Supports 403

12.6 Gold Deposition on Planar Supports 405

12.6.1 Physical Vapour Deposition 405

12.6.2 Cluster Deposition 407

12.6.3 Reactive Deposition Methods 411

12.6.4 Deposition from Solution 412

12.6.5 Deposition of Ordered Particles 413

12.7 Surface Science Studies of Gold Nanoparticles 415

12.7.1 Nucleation and Growth 415

12.7.2 Particle Size Effects 419

12.7.3 Environmental Effects 421

12.8 Two-dimensional Gold 423

12.9 Au-based Bimetallic Nanoparticles 425

12.10 Concluding Remarks 429

13 Theoretical Studies of Gold Nanoclusters in Various Chemical Environments: When the Size Matters 437 13.1 Introduction 437

13.2 Computational Methods 439

13.3 Clusters in Gas Phase 441

13.3.1 Cationic Clusters Au+N 441

13.3.2 Anionic Clusters Au−N 443

13.3.3 From Flakes to Cages to Tubes: Anionic Clusters with N = 13–24 447

13.3.4 Au−16 : The Smallest Golden Cage and the Manifestation of Shell Closing of 18 Delocalised Electrons 449

13.3.5 Anionic Clusters with N > 30 451

13.4 Ligand-protected Nanocluster 452

13.4.1 Synthesis of Ligand-protected Gold Nanoparticles 452

13.4.2 The Noble Metal–Thiolate Bond 455

13.4.3 Early Theoretical Models 457

13.4.4 The ‘Divide and Protect’ Concept 458

13.4.5 The Experimental Breakthroughs: X-Ray Crystallography for All-thiolate Protected Au102and Au25Clusters and the Success of the Superatom Model 460

13.4.6 Phosphine-stabilised Au11and Au39Clusters: Superatoms with 8 and 34 Electrons 465

13.4.7 The Unifying Superatom Concept 466

13.4.8 Use of the Superatom Concept to Understand the Reactivity of Gold Clusters: Dioxygen Activation and CO Oxidation 468

13.5 Gold-based Bimetallic Clusters 470

13.6 Outlook 473

14 Optical and Thermal Properties of Gold Nanoparticles

14.1 Introduction 483

14.2 Gold Nanoparticles for Biomolecule Sensing 484

14.2.1 LSP Sensing: Concept and Motivation 484

14.2.2 Sensitivity of LSPR Sensors 485

14.2.3 State of the Art in LSP Sensing: From Single Particle to Engineered Architectures 486

14.2.4 Towards Integrated Biosensing Platforms 489

14.3 Gold Nanoparticles as Contrast Agents for Bio-imaging: Application to Cancer Diagnosis 491

14.3.1 Linear Imaging Techniques 491

14.3.1.1 Reflectance microscopy 492

14.3.1.2 Dark-field microscopy 492

14.3.1.3 Enhanced-fluorescence microscopy 494

14.3.2 Nonlinear Imaging Techniques 496

14.3.2.1 Multiphoton imaging 496

14.3.2.2 SERS imaging 497

14.3.2.3 Two-photon induced luminescence 498

14.3.3 Photo-acoustic Imaging 498

14.4 Photothermal Properties of Gold Nanoparticles and their Application to Photothermal Cancer Therapy 500

14.4.1 Optimising Heat Generation in Gold Nanoparticles 501

14.4.2 Photothermal Therapy (Thermal Ablative Therapy) 504

14.5 Drug Delivery 505

14.6 Conclusion 506

15 Physical and Chemical Processes for Gold Nanoparticles and Ionising Radiation in Medical Contexts 509 15.1 Introduction 509

15.1.1 Radiobiology 513

15.1.2 Radiotherapy and Radiosensitisers 515

15.1.3 Basic Principles of the Interactions of Radiation with Matter 517

15.2 Physical Processes 521

15.2.1 Nanoscale Local Effect Description 522

15.2.2 Nanoparticle Imaging and the Role of the Photoelectrons 528

15.3 Chemical Processes 530

15.4 Conclusions and Future Outlook 532

16 Gold Nanoparticles for Sensors and Drug Delivery 537 16.1 Gold Nanoparticles for Health 537

16.1.1 Overview and Societal Issues 537

16.1.2 Surface Modification of Gold Nanoparticles 538

16.1.3 Gold Nanoparticles and Biocompatibility 540

16.2 Gold Nanoparticles for Diagnosis 542

16.2.1 Detection of Gold Nanoparticles Using Optical Techniques 543

16.2.1.1 SPR-based techniques 544

16.2.1.2 Fluorescence 547

16.2.1.3 Modification of absorbance 548

16.2.2 Tomography and Gold Nanoparticles 554

16.3 Gold Nanoparticles for Medical Treatment 556

16.3.1 Gold Nanoparticles as Delivery Vehicles 556

16.3.1.1 Problem for specific delivery 556

16.3.1.2 Gold nanoparticles and drug transport 557

16.3.2 Heat Reaction 559

16.4 Other Biological Applications of Gold Nanoparticles 562

16.4.1 Localisation of Proteins in Tissues 562

16.4.1.1 Electronic microscopy 562

16.4.1.2 Reflection/fluorescence 565

16.4.2 Immunisation Using Gene Gun 566

16.4.3 Gold Nanoparticles and Fingerprints 567

16.5 Conclusions 568

17 What About Toxicity and Ecotoxicity of Gold Nanoparticles? 575 17.1 Introduction 575

17.2 Impact of Gold Nanoparticles on Human Health 576

17.2.1 The Toxicological Approach, Applied

to Nanoparticles 576

17.2.2 Biokinetics and Target Organs of Gold Nanoparticles after Systemic Exposure 581

17.2.3 Translocation of Gold Nanoparticles through Physiological Barriers 584

17.2.4 Cellular Toxicity, In Vitro Studies 587

17.3 Environmental Impact of Gold Nanoparticles 590

17.3.1 What Can Make Nanoparticles Toxic for the Environment? 590

17.3.2 Impact of Gold Nanoparticles on Unicellular Organisms: Bacteria and Algae 591

17.3.3 Impact of Gold Nanoparticles on Aquatic Organisms: Daphnids, Bivalves, Fishes 595

17.3.4 Impact of Gold Nanoparticles on Plants 597

17.4 Conclusions 598

18 Technological Applications of Gold Nanoparticles 601 18.1 Introduction 601

18.2 Electronic and Opto-electronic Applications 602

18.2.1 Applications of the Optical and Electronic Properties of Gold 602

18.2.2 Sinter Inks 603

18.2.3 Spectrally Selective Coatings 605

18.2.4 Nonlinear Optical Applications 605

18.2.5 Data Storage 608

18.2.6 Single-Electron Conductivity and Quantum Devices 609

18.3 Catalytic Applications 610

18.4 Decorative Applications 610

18.4.1 Historic Uses in Ceramics and Glass 610

18.4.2 Colouring Textiles 611

18.4.3 Use in Paint and Polymers 611

18.5 Use in Sensors and Biomedical Diagnostics 612

18.5.1 Refractometric Sensors 612

18.5.2 Colorimetric Assays and Related DiagnosticTechniques 61318.5.3 Assays Based on Quartz Microbalance 61418.5.4 Contrast Enhancement in Electron and Optical

Microscopy 61618.5.5 Bifunctional Metallo-dielectric Hybrids

for Microscopy 61618.5.6 Surface-enhanced Raman Spectroscopy 61718.5.7 Two-photon Technologies 61718.6 Potential or Actual Therapeutic Applications 617

18.6.1 Drug Delivery 61818.6.2 Gene Therapy 61918.6.3 Radiotherapy 61918.6.4 Hyperthermal Techniques 62018.7 Environmental Remediation 621

18.8 Conclusions and Outlook 621

About the Authors

Chapters 1 and 8

Catherine Louis is a Research Director at the

Laboratoire de Réactivité de Surface of theUniversity Pierre et Marie Curie She has beenwith the academic group since 1982, when shewas appointed by the French National Centre

of Research (CNRS) She received her PhD inChemistry in 1985 (prepared under the direc-tion of Prof Michel Che) From 1986 to 1988,she was a post-doctoral fellow at the Uni-versity of Berkeley with Prof Alex Bell She

is a specialist in catalyst preparation and hasworked on gold-based monometallic and bimetallic catalysts since 2000

She has authored around 140 publications She co-authored Catalysis by

Gold (Imperial College Press, 2006) with Geoffrey C Bond and David T.

Thompson She is also the author of seven book chapters on synthesis of

sup-ported metal catalysts and CO oxidation of gold nanoparticles From 2006

to 2013, she was the Director of Or-Nano (www.or-nano.com), a CNRS

network gathering around 500 French researchers (physics, chemists and

biologists) working with gold nanoparticles

Chapter 2

Pekka Pyykkö was an Associate Professor

of Quantum Chemistry at Åbo Akademi versity (1974–1984) and Professor of Chem-istry at the University of Helsinki (1984–2009) Since November 2009, he is enjoy-ing research there as Professor Emeritus Hecurrently has published about 320 papers Heidentified the chemical difference between sil-ver and gold as a relativistic effect (1976, withJean-Paul Desclaux), pointed out the impor-tance of electron correlation, or dispersion,effects in aurophilicity 1991 (with Zhao Yongfang and later co-workers)

Uni-and wrote the reviews Theoretical Chemistry of Gold I–III (2003–2008) He

chaired the European Science Foundation programme Relativistic Effects

in Heavy-Element Chemistry and Physics (REHE) during which the Hanau

conference on the Science and Technology of Gold was held in 1996

Geoffrey C Bond held academic positions

at the Universities of Leeds and Hull beforebeing appointed Head of the Johnson MattheyResearch Group on Catalysis (1962–1970)

He then became Professor of Applied istry at Brunel University, Uxbridge, where

he held various posts (Head of the Chem-istry Department, Dean of the Faculty of Sci-ence, Vice-Principal) until his retirement in

Chem-1992 His research has mainly concerned ported metal catalysts for hydrogenation andhydrogenolysis and supported oxides for selective oxidation He has pub-

sup-lished more than 250 scientific papers and review articles Since retirement,

he has worked on gold catalysts, and has co-authored several review articles

as well as the book Catalysis by Gold published by Imperial College Press.

Earlier books include Catalysis by Metals (1962), Heterogeneous Catalysis,

Principles and Applications (2nd edn., 1987) and Metal-Catalysed

Reac-tions of Hydrocarbons (2005).

Chapter 3

Olivier Pluchery graduated from the Ecole

Normale Supérieure de Cachan (Paris, France)

in 1997 with a specialisation in laser physics

He obtained his PhD in chemical physics fromUniversity Paris-Sud in 2000 and was inter-ested in the investigation of the electrochem-ical reactions on a gold interface, monitoredwith sum frequency generation, a nonlinearoptical spectroscopy In 2001, he joined YvesChabal’s team at Bell Labs (USA) to work onsemiconductor interfaces In 2002, he obtained

a position as Associate Professor at University Pierre et Marie Curie (Paris)

where he developed several research programmes dealing with the control

of the adsorption of organic molecules on silicon for molecular electronics

and the use of gold nanoparticles for nanoelectronics He is the founder with

Catherine Louis of the research network Or-Nano (www.or-nano.com)

Chapter 4

Bruno Palpant is a Professor at

Centrale-Supélec in Paris region He leads researchactivities in the Quantum and MolecularPhotonics Laboratory (LPQM, belonging toCNRS, CentraleSupélec and Ecole NormaleSupérieure de Cachan) He is in charge of agroup devoted to the study and application

of the ultrafast transient optical and thermalresponses of plasmonic nanoparticles He gothis PhD in 1998 from University of Lyon(France) about quantum size effects in the opti-cal properties of noble metal nanoparticles, before joining Keio University

(Japan) for one year Assistant professor in the Institut des NanoSciences de

Paris (CNRS-UPMC) for 10 years, he has been interested in the linear and

non-linear optical responses of noble metal nanoparticles as well as their

link with thermal transport at small space and time scales More recently,

his activities have focused on the applications in biology, chemistry and

photonics of nanoscale energy conversion processes

Chapter 5

Changhyoup Lee is a Postdoctoral Fellow in

Karlsruhe Institute of Technology (Germany)

He received his PhD for quantum ics in 2011 from Hanyang University (Korea).Then he has worked as a post-doctoral fellow

plasmon-at Hanyang University (Korea), and Centrefor Quantum Technologies, National Univer-sity of Singapore (Singapore) until he joinedKarlsruhe Institute of Technology in 2016.His recent research focuses on the use ofquantum metrology techniques in plasmonic

or nanophotonic sensing platforms

Mark Tame is an Associate Professor at the

University of KwaZulu-Natal in South Africa

He leads research activities in quantum tonics at the Centre for Quantum Technol-ogy He is in charge of a group focused

pho-on experimental and theoretical researchinto nanophotonic systems operating in thequantum regime He received his PhD in

2007 from Queen’s University, Belfast (UK)

on the topic of optical quantum tion processing He has held research fel-lowship positions at Imperial College London (EPSRC) and Osaka

informa-University in Japan (JSPS) He is currently a visiting professor at

Osaka University His main research interests are in the application

of quantum optics to nanoscale systems such as plasmonic

nanopar-ticles and metamaterials, with the main goal of developing new

devices that can be used in quantum information processing This includes

single-photon sources and switches, quantum sensing and entanglement

generation

Chapter 6

Woong Choi received his BSc in Chemistry at

the Korea Advanced Institute of Science andTechnology (KAIST) in 2013 He is currently

a candidate of combined master’s and ate programme in chemistry under the direc-tion of Professor Hyunjoon Song at KAIST

doctor-His research has focused on the fabrication ofcomplex nanostructures with multiple compo-nents based on noble metal nanoparticles andtheir applications for photocatalysts and SPRsensors

Chapters 6 and 7

Hyunjoon Song received his B.S., M.S and

PhD degrees from the Department of istry at KAIST in 1994, 1996 and 2000, underthe direction of Prof Joon T Park After post-doctoral works at KAIST and the University

Chem-of California at Berkeley (with PrChem-of PeidongYang), he was appointed as an Assistant Pro-fessor in 2005, and was promoted to an Asso-ciate and to a Full Professor in 2008 and 2014

in the Department of Chemistry at KAIST Hewas appointed as a KAIST-endowed chair pro-fessor in 2015 His research interests are morphology control of metal hybrid

nanostructures and their applications for surface plasmon monitoring and

catalysis in organic and photochemical reactions

Chapter 7

Souhir Boujday is an Associate Professor at

University Pierre and Marie Curie (UPMC),Sorbonne Universities, Laboratory of SurfaceReactivity She is currently a Visiting Profes-sor at Nanyang Technological University inSingapore She graduated from UPMC with

a PhD in Chemistry in 2002 on the cial molecular recognition between transitionmetal complexes and silica surface during cat-alyst preparation After post-doctoral studies

interfa-on photocatalysis (cinterfa-onsortium CNRS, Rhodia,Lapeyre, Arch-Coating and Hahn Meitner Institute (Berlin, Germany)), she

joined UPMC as an Assistant Professor in 2004 She was involved in the

creation of a new research group on biointerfaces where she was responsible

for the biosensors theme of research Her research activity is focused on the

optimisation of the molecular approach of material surface modification to

ensure the highest efficiency of the functional material She defended her

habilitation to research supervision thesis on ‘Surface nanostructuration and

molecular recognition at the solid/liquid interface’ in 2012

Atul N Parikh is a Professor and member

of the faculty in the Departments of ical Engineering and Materials Science andEngineering at the University of California,Davis Since 2012, he is also serving as aVisiting Professor in the school of MaterialsScience and Engineering at Nanyang Techno-logical University in Singapore He studiedChemical Engineering at the Department ofChemical Technology (UDCT) University ofBombay (B Chem Eng., 1987) and Materials

Biomed-Science (Specialisation: Polymer Biomed-Science) at the Pennsylvania State

University (PhD 1993) Between 1996 and 2001, as post-doctoral scholar

and then technical staff member in the Chemical Science and Bioscience

divisions at Los Alamos National Laboratory (LANL), he explored design

of biologically inspired materials and biosensors His research interests

include surface chemistry, soft matter and membrane biophysics

Bo Liedberg is a Full Professor of Materials

Science at the School of Materials Science andEngineering, Nanyang Technological Univer-sity (NTU), Singapore where he is leading auniversity-wide initiative on biomimetic sen-sor science Liedberg is also serving as theDean of the Interdisciplinary Graduate School,NTU He received his PhD in applied physicsfrom Linköping University (LiU), Sweden, in

1986 After an industrial post-doc and severalyears abroad, he obtained a full professorship

in sensor science (2000) and later in molecular physics (2004) also at LiU

He has a long experience in surface vibrational spectroscopy, in particular

for the analysis of thin molecular films and self-assembled architectures on

solid supports He has also been the principal investigator for a

success-ful activity in biochemical and chemical sensing at LiU This work started

in early 1980s when he and his colleagues developed the surface

plas-mon resonance-based detection principle, which today is one of the

corner-stones in the Biospecific Interaction Analysis (BIAcore) system advertised

by GE Healthcare He has published more than 270 papers/reviews in

peer-reviewed international journals and magazines Liedberg was in 2005 the

recipient of the Distinguished Scientist Award for his contributions in the

field of molecular physics and sensor science awarded by the Research

Council of Italy (CNR)

Chapter 9

Evgeny (Eugene) Beletskiy received his PhD

from the University of Minnesota under thesupervision of Prof Steven Kass investigat-ing novel hydrogen bond catalysts, phosphateion receptors and an organometallic catalysismethodology He then studied gold nanopar-ticle and tin Lewis acid catalysts as a post-doctoral fellow with Prof Harold Kung atthe Northwestern University He is now work-ing on next generation oxidation catalysts as

a Research Chemist at the Scientific DesignCompany in Little Ferry, New Jersey

Mayfair C Kung is a Research Associate

Professor in the Chemical and BiologicalEngineering Department at the Northwest-ern University She received her B.Sc inbiochemistry from the University of Wis-consin, Madison, PhD in chemistry fromNorthwestern University and her post-doctoraltraining at University of Pennsylvania Herresearch interests include selective alkaneoxidation, water purification and synthe-sis of organosilicon compounds as catalyticstructures

Harold H Kung is a Walter P Murphy

Professor of Chemical and Biological neering at the Northwestern University Hereceived his B.S from the University of Wis-consin and PhD from Northwestern Univer-sity, and has been on the editorial team of

Engi-Applied Catalysis A: General since 1996.

His research interest focuses on neous catalysis, but includes energy materials,synthesis of nanostructured materials, globalenergy supply and consumption, and sustain-

heteroge-ability He is the author of Transition Metal Oxides: Surface Chemistry and

Catalysis (1989, Elsevier Science, holds six patents (one pending), has

pub-lished over 270 journal articles in catalysis and energy storage and an editor

of five monographs Recently, his work was given the R.H Wilhelm Award

of the American Institute of Chemical Engineers and the Gabor A Somorjai

Award of the American Chemical Society

Chapter 10

Ewa Kowalska is an Associate Professor and a

leader of Research Cluster for Plasmonic catalysis in Institute for Catalysis, Hokkaido Uni-versity She received her PhD in chemical tech-nology from Gdansk University of Technology,Poland, in 2004 After completing JSPS fellowship(2005–2007), GCOE post-doctoral fellowships(2007–2009) in Japan and Marie Sklodowska-Curie fellowships in France (2002–2003) and inGermany (2009–2012), she joined Institute forCatalysis as an Associate Professor in 2012 Her current work focuses on

Photo-heterogeneous photocatalysis, environmental protection, plasmonic

nano-materials and anti-microbial properties on nanonano-materials

Chapter 11

Eric Le Moal is a CNRS junior researcher

at the Institute of Molecular Sciences ofOrsay (ISMO), France He received his PhD

in Physics in 2007 from Pierre and MarieCurie Paris VI University, France, on thefluorescence enhancement of dye molecules

on plasmonic nanostructures He is a mer post-doctoral fellow of the Alexander-von-Humboldt Foundation (2007–2009) in theOrganic Films group of M Sokolowski inBonn, Germany Before joining CNRS in

for-2011, he spent two post-doctoral years at the Fresnel Institute in

Mar-seille, France, where he co-invented new optical microscopy techniques

His research interests include plasmonics, organic semiconductors, surface

science and instrumentation in optics He currently conducts experimental

work on electrical nanosources of light and surface plasmons, based on

tech-niques combining scanning tunnelling microscopy with optical microscopy

Gérald Dujardin is a Directeur de Recherche

Emérite at CNRS He started working on pulation of single molecules with the STM’ at IBM(Yorktown, USA) in 1991 with Phaedon Avouris

‘Mani-He studied molecular nano-machines and their tronic and optical control His current research inter-ests are focused on the electrical excitation of hybridplasmon-exciton optical devices

elec-Elizabeth Boer-Duchemin is a Junior

Pro-fessor at the University of South Paris andthe Orsay Institute of Molecular Sciences(ISMO) She received her PhD in appliedphysics from the California Institute of Tech-nology in 2001, under the supervision ofHarry Atwater From 2001 to 2003, she was

a Research Engineer at Alcatel Opto+, coussis, France, working on high-power semi-conductor pump lasers for optical amplifiers,before spending a year at Thales Research andTechnology on quantum cascade lasers Her more recent interests are the

Mar-development and exploitation of electrical plasmon nanosources and their

integration, as well as novel uses of scanning probe microscopies

Chapter 12

Shamil Shaikhutdinov has received his PhD

(1986) in physics at the Moscow Institute ofPhysics and Technology Then he joined theBoreskov Institute of Catalysis at Novosibirsk

to carry out surface science studies of catalyticsystems In addition, he has been working as

a post-doctoral fellow in several research tres in Germany and France Since 2004, he

cen-is leading the group ‘Structure and Reactivity’

in the Department of Chemical Physics of theFritz-Haber Institute at Berlin His researchinterest is focused on an understanding of the atomic structure and surface

chemistry of functional materials

Chapter 13

Hannu Häkkinen has PhD in physics in 1991

at the University of Jyväskylä, Finland AfterPhD, he worked for several years as post-doctoral researcher, senior research scientistand Academy of Finland Research Fellow atGeorgia Institute of Technology, Atlanta and

in University of Jyväskylä Since 2007, he is

a professor in computational nanoscience inUniversity of Jyväskylä in a joint position atPhysics and Chemistry Departments and at theNanoscience Center He is currently the Sci-entific Director of the Jyväskylä University Nanoscience Center and has

been nominated as the Academy Professor for 2016–2020 by the Academy

of Finland He leads a group of about 10 researchers focusing on

computa-tional studies of electronic, optical, magnetic and catalytic properties of

vari-ous metal nanoclusters, nanostructures and cluster–bionanoparticle hybrids

His teaching curriculum includes solid state physics, physical chemistry and

computer simulation methods He has co-authored about 200 peer-reviewed

articles (http://users.jyu.fi/∼hahakkin/)

Chapter 14

Romain Quidant received his PhD in Physics

in 2002 from the University of Dijon (France)

Since then, he has worked in Barcelona atICFO in the field of nanoplasmonics In 2006,

he was appointed Junior Professor and groupleader of the Plasmon NanoOptics group atICFO In 2009, he became ICREA Professorand tenure group leader at ICFO Quidant carries out his research at Institut

de Ciencies Fotoniques in Barcelona (ICFO) — where he leads the plasmon

nanooptics group His research focuses on the study of the optical

proper-ties of metal nanostructures, known as nanoplasmonics The activiproper-ties of his

group cover both fundamental and applied research The fundamental part

of his work is mainly directed towards enhanced light–matter interaction for

quantum optics From a more applied viewpoint, his group investigates new

strategies to control light and heat at the nanometre scale for biomedical

applications, including early detection and hyperthermia

Chapter 15

Fred Currell is a Professor of Physics at the

School of Mathematics and Physics and is theDirector of the Centre for Advanced and Inter-disciplinary Radiation Research (CAIRR),both part of Queen’s University, Belfast Hereceived his PhD from Manchester University

in 1987 His research involves joint mental and modelling approaches to under-stand interactions of radiation and matter

experi-These studies range from fundamental physicsand chemistry studies to health care applica-

tions (predominantly cancer care) He is the editor of Cancer

Nanotechnol-ogy, and open access Springer journal.

Balder Villagomez-Bernabe is a Research

Fellow at the School of Mathematics andPhysics at Queen’s University, Belfast, since

2014 He received his PhD from the NationalOptics Institute in Puebla City, Mexico in

2013 His PhD involved a stay at the StanfordLinear Accelerator in USA in order to imple-ment Monte Carlo simulations of the Ramanscattering process for optical photons His cur-rent research comprises the performance ofMonte Carlo simulations to calculate the doseenhancement in tumour cells by the use of high-density nanoparticles as

radiosensitisers during radiotherapy cancer treatments

Chapter 16

Christian Villiers is a Member of the Research

Institute INSERM (National Institute for Health andMedical Research) and Vice Director of the Insti-tute for Advanced Biosciences located in Greno-ble (France) He graduated in biochemistry from

a high-tech Education Establishment (INSA —Lyon, France) and received his PhD in biology andimmunology from the University of Grenoble in

1984 He worked as a post-doctoral fellow at theMRC Centre of Cambridge (UK) in 1985 His cur-rent interest relates to the modification of the immune response resulting

from inflammation with a special focus on the assessment of potential

inter-ferences of nanoparticles with the cellular behaviour and the immune

sys-tem He is the author of more than 90 original articles

Chapter 17

Marie Carrière is a Senior Research Scientist

at the Atomic Energy Commission (CEA) inGrenoble, France She joined the Nucleic AcidLesions Laboratory in the CEA Nanoscienceand Cryogeny Institute (INAC) in 2011 afterstudying metal and nanoparticle toxicity inLaboratoire Pierre Süe, CEA Saclay, for sevenyears She received her PhD from the NationalInstitute of Agronomics at Paris in February

2002 for studying the efficiency, cell bution and metabolisation of lipidic vectorsdeveloped for gene therapy applications She then did post-doctoral work

distri-at CEA Saclay centred on the study of toxicological impact of heavy

met-als on cultured animal and human cell lines Her current research

inter-ests are toxicology, ecotoxicology and bioavailabillity of metal and metal

oxide nanoparticles as well as carbon nanotubes She also participated in

the development of innovative therapeutic and diagnostic approaches using

nanoparticles

Chapter 18

Michael Cortie is a Professor of

Nanotechnol-ogy and Director of the Institute for NanoscaleTechnology at the University of Technology,Sydney, in Australia He has a BSc (Engineer-ing) degree in physical metallurgy from theUniversity of the Witwatersrand, South Africa(1978), a Masters in Engineering degree onfrom the University of Pretoria, South Africa(1983), and a PhD on metal fatigue at high tem-peratures from the University of the Witwa-tersrand (1987) He joined Mintek, the SouthAfrican National Minerals and Metals Research Organisation in 1987 Hewas a Senior Engineer there before becoming head of its Physical Met-

allurgy Division between 1997 and 2002 While at Mintek, he consulted

widely to the international precious metals industry in the areas of

nan-otechnology, catalysis and physical metallurgy He relocated to the

Univer-sity of Technology Sydney in July 2002 Michael’s main research interests

are the nanoparticles and intermetallic compounds of the precious metals,

especially as these relate to optical properties

Chapter 1

Gold Nanoparticles in the Past:

Before the Nanotechnology Era

Catherine Louis

Laboratoire de Réactivité de Surface, UPMC-CNRS, Paris, France

1.1 The First Usage of Gold

The role played by gold in history relies on its outstanding qualities among

metals, making it exceptionally valuable from the earliest civilisations until

the present day As quoted by Auric Goldfinger in a James Bond movie,

gold is attractive due to ‘its brilliance, its colour, its divine heaviness’, and

also due to its incorruptibility and scarcity Its great malleability makes gold

one of the easiest metal to work with Moreover, it often occurs naturally in

a fairly pure state

The first uses of gold were linked to deities and royalty in early

civili-sations The word ‘gold’ exists in all old languages, often connected with

the image of the Sun, with light and life-giving warmth, growth and hence

power In cultures like ancient Egypt, which deified the Sun, gold

repre-sented its earthly form In fact, nothing has changed throughout history,

and the same thinking about gold exists (golden crown of the kings, gold

medals, wedding rings, cult objects, gold ingots)

1.1.1 Quest for Gold and Gold Production

The earliest signs of crude metallurgy occurred sometime from 9000 to

7000 BCE (before the Common Era) For instance, in Ali Kosh in Iran and

Cayönü Tepesi, which is close to Ergani in Anatoly, humans first began

using native copper and gold, meteoric iron, silver and tin to create tools

and possibly jewellery ornamentation Gold was most probably discovered

as shining, yellow nuggets Although it can be easily worked with because

of its ductility, it is not clear whether it was worked with before copper.a

It is known that the Egyptians mined gold before 3500 BCE in the

eastern desert of Egypt and in Nubia.1The Turin Papyrus drawn during the

reign of Ramesses IV (1151–1145 BCE) is the earliest known topographic

and geological map.2Along with specifics of the geology and topography,

it shows an ancient gold-working settlement, gold-bearing quartz veins in

Wadi Hammamat, a dry river bed in Egypt’s eastern desert Large mines

were also present across the Red Sea in present Saudi Arabia By 325 BCE,

the Greeks had mined in areas from Gibraltar to Asia Minor and Egypt

The Romans mined gold extensively throughout the empire, developing the

technology of mining to new levels of sophistication For example, they

would divert streams of water in order to mine hydraulically, and even

pioneered ‘roasting’, the technique of separating gold from rock

Occasional passages on mining and metallurgy of metals can be found

in the works of Theophrastus (Greek, 372–288 BCE), Vitruvius (Roman

90–20 BCE), Strabo (63/64 BCE–c 24 CE), Pliny the Elder (Roman,

23–79 CE) and Discorides (Greek, 40–90 CE) One important surviving

document is the Leyden Papyrus X of the Museum of Antiquities in the

Netherlands: it is the working notebook of a goldsmith and jeweller,

proba-bly written in the early years of the fourth century It gathers 111 recipes of

refining, alloying and working of gold; some of them are reported in Hunt’s

paper.3Details on the first techniques of gold metallurgy and gold thin film

technology can be found in Greene’s paper.4

Another important date for the history of gold is 1492, with the discovery

of America and the beginning of massive expeditions and exploration with

the quest for the El Dorado, and the encounter with Native American people

of Central America and South America and their extensive displays of gold

ornaments The Aztecs regarded gold as literally the product of the gods,

calling it ‘the sweat of the sun’.

Two hundred years later, in 1700, gold was discovered in Minas Gerais

in Brazil, which became the largest producer by 1720, responsible for nearly

a One can read in some websites that the earliest traces of gold dated back to the Paleolithic period

40,000–10,000 BC and were found in Spanish caves of Maltravieso; this is wrong according to Dr Antoni

Canals y Salomó (Universidad de Tarragona), a paleontolongist, and specialist of this cave.