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Preface xi Acknowledgments xv PART 1. CONCEPTS, DISCOVERIES AND THE RAPID DEVELOPMENT OF NANOTECHNOLOGIES1 Chapter 1. Nanotechnologies in Context: Social and Scientific Awareness of their Impact 3 1.1. Feynman, the visionary 3 1.2. Nanotechnologies and their definition 5 1.3. The consideration of nanotechnologies by scientific organizations 8 1.4. Bibliography 11 Chapter 2. The Rapid Expansion of Nanotechnology: New Ways of Observing the Infinitesimal and the Discovery of Carbonaceous Nanomaterials with Unusual Properties 13 2.1. Improving tools for observing the infinitesimal 15 2.1.1. Transmission electron microscopes 15 2.1.2. Scanning electron microscopes 18 2.1.3. Near-field microscopes 21 The tunnel-effect microscope (STM or scanning tunneling microscopy) 22 Atomic force microscopy 26 2.2. The discovery of new carbonaceous nanomaterials 28 2.2.1. Some basic concepts relative to the electronic structure of carbon and to the bonding rules between carbon atoms 29 The enigma of carbon atoms 29 Diamond or the perfect and unique tetrahedral chain of carbon atoms 31 Graphite or the intrusion of electrons in the assembly of carbon atoms 32 2.2.2. The fullerenes or graphite sheets rolled into a ball 34 2.2.3. Carbon nanotubes: tubes of graphite sheets 36 2.2.4. Graphene or graphite sheets 39 The identification of graphene 39 Some remarkable electrical properties 41 Remarkable progress: solid, flexible and easily manipulated graphene paper 43 2.2.5. Link between conjugated carbonaceous nanomaterials 45 2.3. Conclusions 46 2.4. Bibliography 46 Chapter 3. Nanomaterials in All Their Forms: New Properties Due to the Confinement of Matter 49 3.1. The different types of nano-objects: main methods of preparation 50 3.1.1. Colloidal solutions of gold NPs 50 3.1.2. Hybrid and magnetic NPs (ferromagnetic fluids) 52 3.1.3. Semiconducting NPs (quantum dots) 54 3.1.4. Phospholipid vesicles and encapsulation by liposomes 58 3.1.5. Nanowires 60 3.2. Organizing nanoparticles into arrays 63 3.2.1. Self-assembly 64 Molecular self-assembly and the formation of nanometric networks 65 Self-assembly of NPs on solid surfaces 70 3.2.2. Assembling by ultrathin alumina membranes 74 3.2.3. Assembling by colloidal lithography 75 3.3. Conclusions 78 3.4. Bibliography 78 Chapter 4. Some Amazing Properties of Nanomaterials and of Their Assembly into Networks 81 4.1. The first effect of the confinement of matter: unusual catalytic and physicochemical properties 81 4.2. The optoelectronic properties of NPs due to confinement 82 4.2.1. Some concepts of physics that can be applied to solid materials 83 4.2.2. The plasmon resonance effect and the optical properties of gold NPs 85 4.2.3. Surface enhanced Raman scattering 87 4.2.4. The photothermic effect or how to heat up gold NPs 89 4.2.5. The optoelectronic properties of Quantum Dots 89 4.3. The amazing properties of NP networks or nanostructured surfaces 91 4.3.1. Wettability of structured surfaces 91 4.3.2. Optical properties 94 Photonic crystals 97 Waveguides 98 Qdot LASER diodes 100 Antireflective surfaces 105 Plasmonic crystals and the SERS effect 106 4.3.3. Nanoelectronics applied to the detection of trace elements: nanowire transistors 109 The operating principle of the FET sensor 110 An example of how it could be applied: detecting explosives 110 Electronic noses 113 4.4. Conclusions and perspectives 113 4.5. Bibliography 114 PART 2. APPLICATIONS AND SOCIETAL IMPLICATIONS OF NANOTECHNOLOGY 117 Chapter 5. Nanoelectronics of the 21st Century 119 5.1. Some history 119 5.2. Molecular electronics 123 5.2.1. Single Electronics. Dream or reality? 124 Electron box and electron transfer by quantum tunneling 124 The single-electron transistor (SET) 127 5.2.2. The ultimate step: the molecule 130 Technical issues in the assembly of a metal/single molecule/metal junction 130 Molecular diodes made from self-assembled organic molecules 132 Electrical properties of self-assembled organic layers 133 The organic field-effect transistor 135 5.2.3. Conclusion 137 5.3. Spintronics 137 5.3.1. Electron spin and ferromagnetic materials 138 5.3.2. Magnetoresistance 139 5.3.3. Giant magnetoresistance 140 5.4. Conclusions 143 5.5. Bibliography 144 Chapter 6. Energy and Nanomaterials 147 6.1. Electrochemical storage of electricity 148 6.1.1. Electrical properties of an accumulator 150 6.1.2. Lithium batteries 151 The functional originality of a Li-ion electrochemical cell 154 Nanotechnology to the rescue: the grapheme solution? 156 6.1.3. Electrochemical capacitors and supercapacitors 157 Peculiarities of the electrochemical capacitor 158 The developments and the state of the art 161 6.1.4. Conclusions 164 6.2. The conversion of solar energy into electrical energy 165 6.2.1. The principle of the conversion 166 The photoelectric effect and its history 166 Photoionization of a semiconductor and collection of the charges at the electrodes 168 6.2.2. The inorganic route based on mineral semiconductors 170 6.2.3. The organic route 172 Organic photovoltaic cells 172 Gratzel dye-sensitized solar cells (DSSC) 176 6.3. Fuel cells 179 6.3.1. Functional principles of PEMFCs 181 6.3.2. Can the cost of dihydrogen fuel cells be reduced? 183 6.4. General conclusions 188 6.5. Bibliography 189 Chapter 7. Nanobiology and Nanomedicine 193 7.1. Introduction 193 7.2. Bionanoelectronics 194 7.2.1. The multiplexed detection of PSA using transistorized nanowires 195 Immunological assay of proteins by labeling 195 Use of nanowire networks 197 The simplified and ultrasensitive detection of PSA 197 Conclusions 201 7.2.2. Connecting the organic and the artificial 201 The construction of a nanosensor and its function 202 Proton exchanges and their inhibition by calcium ions 204 Conclusions 205 7.3. Nanomedicine 205 7.3.1. Biological barriers and the alteration of the cellular tissue surrounding a tumor 206 The extravasation of nanoparticles toward cancerous tissue 208 7.3.2. Nanoprobes for in vivo real-time imaging 210 Imagery resulting from plasmon resonance of gold NPs and from their interaction with enzymes characteristic of a pathological process 210 Luminescence imaging triggered by enzymes or reactive oxygen species characteristic of a pathology 213 Magnetic resonance imaging coupled with nanophototherapy 215 An innovative strategy for an improved penetration of the NPs in the cancerous cell tissue 218 7.3.3. Challenges of nanomedicine and some significant clinical results 221 The first commercial nanomedication 221 New paths in development 223 7.3.4. Problems related to the toxicity of nanomaterials 228 A few general considerations 228 The multiple causes of nanomaterial-induced toxicity 231 Recommendations for a better evaluation of NP toxicity 232 7.4. Conclusions and perspectives 234 7.5. Bibliography 235 Chapter 8. Nanorobotics and Nanomachines of the Future 239 8.1. Natural molecular machines 240 8.1.1. ATP-synthase 240 8.1.2. Myosin: a linear protein nanomotor 242 8.2. Artificial molecular machines 243 8.2.1. Artificial molecular machines in solution 244 Rotaxanes (translational molecular shuttles) 245 Catenanes 249 Promising applications for diagnosis and therapy 251 8.2.2. Nanomachines with mechanical properties 253 Rotors and gyroscopes 254 Motorized molecular vehicles 256 8.3. Conclusions 258 8.4. Bibliography 259 Conclusions and Outlook 263 Index of Names 267 Index 269

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