Preface ..................................................... XIII
List of Contributors ......................................... XVII
1 Gold Nanoshells in Biomedical Applications ................... 1
Tim A. Erickson and James W. Tunnell
1.1 Introduction ............................................ 1
1.2 Physical Properties of Gold Nanoshells .................. 2
1.2.1 Overview of General Optical Properties ........... 2
1.2.2 The Physics of Gold Nanoshells ................... 5
1.2.2.1 The Dielectric Function of Gold ......... 6
1.2.2.2 The Quasi-Static Approximation and
Conditions for Surface Plasmon
Resonance ............................... 7
1.2.2.3 Mie Theory ............................. 13
1.2.2.4 Near-Field Enhancement ................. 13
1.2.2.5 Photoluminescence ...................... 14
1.2.3 Photo-Thermal Material Characteristics .......... 14
1.3 Synthesis and Bioconjugation ........................... 16
1.3.1 Synthesis ....................................... 16
1.3.2 Bioconjugation: Smarter Nanoshells .............. 18
1.4 Biodistribution, Toxicity Profile and Transport ........ 19
1.4.1 Biodistribution Studies ......................... 20
1.4.2 Transport Mechanisms ............................ 22
1.4.3 Toxicity ........................................ 25
1.5 Biomedical Applications ................................ 26
1.5.1 In Vitro Cancer Detection and Imaging ........... 26
1.5.2 In Vivo Detection and Imaging ................... 28
1.5.3 Integrated Cancer Imaging and Therapy Agents .... 29
1.5.4 In Vitro Studies ................................ 29
1.5.5 In Vivo Photothermal Therapy .................... 31
1.5.6 Drug Delivery ................................... 34
1.5.7 Tissue Welding .................................. 35
1.5.8 Biosensors ...................................... 35
1.5.8.1 Absorbance-Based Biosensing ............ 37
1.5.8.2 SERS Biosensing ........................ 37
1.6 Concluding Remarks ..................................... 38
References ............................................. 39
2 Anisotropic Bimetallic/Oxide Nanomaterials for The Life
Sciences
Jessica B. Graham, Megan E. Pearce and Aliasger K. Salem
2.1 Introduction ........................................... 45
2.2 Synthesis and Functionalization of Anisotropic
Bimetallic Nanoparticles ............................... 45
2.2.1 Nanorods ........................................ 45
2.2.2 Nano wires ...................................... 47
2.3 Applications in the Life Sciences ...................... 48
2.3.1 Biosensing ...................................... 48
2.3.2 Imaging ......................................... 49
2.3.3 Gene Delivery ................................... 49
2.3.4 Vaccine Applications ............................ 52
2.4 Conclusions ............................................ 54
References ............................................. 54
3 Au—Pt Nanomaterials and Enzymatic Catalysts for Biofuel
Cell Applications ........................................... 57
Aurélien Habrioux, Karine Servat, Boniface Kokoh and
Nicolas Alonso-Vante
3.1 Introduction ........................................... 57
3.2 Oxygen Reduction Reaction (ORR) ........................ 58
3.2.1 ORR Metal Catalysts ............................. 60
3.2.2 ORR Enzymatic Catalysts ......................... 61
3.2.2.1 Techniques Used for Enzyme
Immobilization ......................... 61
3.2.2.2 Enzymatic Reduction of Oxygen to
Water .................................. 63
3.3 Glucose Oxidation ...................................... 70
3.3.1 Process on Metal Electrodes ..................... 70
3.3.1.1 Synthesis and Structural Properties
of Gold-Platinum Nanoparticles ......... 71
3.3.1.2 Electrocatalytic Oxidation of
D-(+)-Glucose on Gold-Platinum
Catalysts .............................. 73
3.3.2 Glucose Oxidation via Enzymes ................... 77
3.3.2.1 Glucose Oxidation Catalyzed by GDH ..... 78
3.3.2.2 Glucose Oxidation Catalyzed by GOx ..... 79
3.4 Application to Fuel Cell Systems ....................... 85
3.4.1 Glucose/Oxygen Biofuel Cells .................... 85
3.4.2 Glucose/Oxygen Biofuel Cells with Au—Pt
Nanoparticles as Anode Catalysts ................ 90
3.5 Summary and Outlook .................................... 91
Acknowledgments ........................................ 92
Abbreviations .......................................... 93
References ............................................. 93
4 Spherical and Anisotropic Metallic Nanomaterials-Based
NSET Biosensors ............................................ 103
Paresh Chandra Ray, Jelani Griffin, Wentong Lu, Oleg
Tovmachenko, Anant K. Singh, Dulal Senapati and Gabriel
A. Kolawole
4.1 Introduction .......................................... 103
4.1.1 Nanotechnology Promises on Biological
Detection ...................................... 105
4.2 Size- and Shape-Dependent Super Quenching Properties
of Nanomaterials ...................................... 106
4.3 Nanomaterial Surface Energy Transfer (NSET) ........... 109
4.3.1 Portable NSET Probes ........................... 111
4.3.2 NSET Probe for DNA/RNA Hybridization
Detection ...................................... 112
4.3.2.1 Size-Dependence Sensitivity ........... 114
4.3.3 Distance-Dependent NSET ........................ 115
4.3.4 Multiplex DNA Detection ........................ 119
4.3.5 NSET for Monitoring Mg2+-Dependent RNA
Folding ........................................ 121
4.3.6 NSET for DNA Cleavage Detection ................ 125
4.3.7 NSET for Cancer Cell Detection ................. 128
4.4 Gold Nanoshell-Based Biosensors ....................... 129
4.5 Problems and Challenges ............................... 131
4.6 Summary ............................................... 131
Acknowledgments ....................................... 132
References ............................................ 132
5 Mixed-Metal Oxide Nanomaterials for Environmental
Remediation ................................................ 139
Dambar B. Hamal, Kennedy K. Kalebaila and Kenneth
J. Klabunde
5.1 Introduction .......................................... 139
5.2 TiO2 Heterogeneous Photocatalysis for Environmental
Remediation ........................................... 141
5.2.1 Metal-Doped TiO2 Mixed-Metal Oxides as
UV-Light-Sensitive Photocatalysts .............. 141
5.2.2 Metal-Doped TiO2 Mixed-metal Oxides as
Visible-Light-Sensitive Photocatalysts ......... 146
5.3 Other Mixed-metal Oxide Photocatalysts ................ 150
5.4 Conclusions ........................................... 156
References ................................................. 157
6 Building Nonmagnetic Metal@Oxide and Bimetallic
Nanostructures: Potential Applications in the Life
Sciences ................................................... 161
Мао-Song Mo and Xu-Sheng Du
6.1 Introduction .......................................... 161
6.2 Building Nonmagnetic Metal@Oxide and Bimetallic
Nanostructures ........................................ 162
6.2.1 Core-Shell Nanostructures and Building
Strategy ....................................... 162
6.2.2 Metal@Oxide Core-Shell Nanostructures .......... 163
6.2.3 Bimetallic Nanostructures ...................... 164
6.2.3.1 Bimetallic Core-Shell
Nanostructures ........................ 164
6.2.3.2 1-D Bimetallic Heteronanostructures ... 174
6.2.3.3 Bimetallic Alloy Nanostructures ....... 179
6.2.4 3-D Mesoscale Bimetallic Patterning ............ 185
6.3 Current and Future Applications in the Life
Sciences .............................................. 188
6.4 Summary and Outlook ................................... 191
Acknowledgments ....................................... 192
References ............................................ 192
7 Biofunctionalization of Spherical and Anisotropic
Bimetallic Nanomaterials ................................... 197
Davide Prosperi, Laura Polito, Carlo Morasso and Diego
Monti
7.1 Introduction .......................................... 197
7.2 Spherical Core-Shell Bimetallic Nanoparticles ......... 198
7.2.1 Agcore/Aushell Nanoparticles ..................... 198
7.2.2 Aucore/Agshell Nanoparticles ..................... 201
7.2.3 Silver Enhancement of Gold Nanoparticles ....... 204
7.2.4 DNA-Assisted Synthesis of Core-Shell
Nanoparticles .................................. 205
7.2.5 Biofunctionalization for the Construction of
Core-Shell Bimetallic Nanostructures ........... 206
7.3 Anisotropically Shaped Nanoparticles: Nanorods and
Nanowires ............................................. 209
7.3.1 Surface Modifications .......................... 210
7.3.2 NW/NR Functionalization with Protein
Molecules ...................................... 212
7.3.3 NW/NR Functionalization by DNA ................. 218
7.3.4 Detection and Sensing .......................... 220
7.4 Profunctional Bimetallic Alloys ....................... 224
7.4.1 Dendrimer-Encapsulated Bimetal Nanoparticles ... 225
7.4.2 Surface Stabilization by Ligand Exchange ....... 228
7.4.3 DNA Metallization .............................. 228
7.4.4 Miscellaneous .................................. 229
7.5 Outlook ............................................... 234
References ............................................ 234
8 Multielemental Nanorods (Nanowires): Synthesis,
Characterization and Analytical Applications ............... 241
Yang-Wei Lin, Zong-Hong Lin, Chih-Ching Huang and Huan-
Tsung Chang
8.1 Introduction .......................................... 241
8.2 Synthetic Strategies .................................. 243
8.2.1 Organic-Phase Synthesis ........................ 243
8.2.1.1 Bimetallic NRs ........................ 243
8.2.1.2 Semiconductor NRs ..................... 245
8.2.2 Aqueous-Phase Synthesis ........................ 248
8.2.2.1 Bimetallic NRs ........................ 248
8.2.2.2 Multisegmented NRs .................... 250
8.2.2.3 Bimetallic/Trimetallic Oxide NRs ...... 252
8.2.2.4 Semiconductor NRs ..................... 254
8.3 Properties ............................................ 255
8.3.1 Absorption ..................................... 256
8.3.2 Emission ....................................... 258
8.3.3 Surface-Enhanced Raman Scattering .............. 260
8.3.4 Catalytic Properties ........................... 262
8.3.5 Magnetism ...................................... 263
8.4 Analytical Applications ............................... 264
8.4.1 Detection of Gaseous Molecules ................. 265
8.4.2 Detection of Metal Ions ........................ 265
8.4.3 Separation and Sensing of Proteins ............. 267
8.4.4 DNA Detection .................................. 269
8.4.5 Detection of Pathogens and Bacteria ............ 271
8.5 Conclusions ........................................... 271
Abbreviations ......................................... 272
References ............................................ 273
9 Spherical and Anisotropic Nonmagnetic Core-Shell
Nanomaterials: Synthesis and Characterization .............. 281
Tewodros Asefa, Abhishek Anan, Cole Duncan and Youwei Xie
9.1 Introduction: Core-Shell Nanomaterials and Their
Biological/Medical Applications ....................... 281
9.2 Nonmagnetic Core-Shell Nanomaterials .................. 287
9.3 Synthesis of Cores in Core-Shell Nanostructures ....... 288
9.3.1 Metal Cores .................................... 288
9.3.2 Metal Oxide Cores .............................. 289
9.3.3 Polymeric Cores ................................ 290
9.3.4 Semiconductor Cores ............................ 290
9.4 Deposition of Shells over the Core Nanomaterials ...... 290
9.5 Types of Core-Shell Nanomaterial ...................... 291
9.5.1 Metal-Insulator Core-Shell Nanomaterials ....... 291
9.5.1.1 Metal-Dense Metal Oxide Core-Shell
Nanomaterials ......................... 292
9.5.1.2 Metal-Functionalized Metal Oxide
Core-Shell Nanoparticles .............. 294
9.5.1.3 Metal-Porous Metal Oxide Core-Shell ... 294
9.5.1.4 Metal-Polymer Core-Shell
Nanoparticles ......................... 295
9.5.1.5 Hollow Metal-Metal Oxide Shells by
Controlled Core-Dissolution ........... 298
9.5.1.6 Metal Core-Dendrimer Core-Shell
Nanoparticles ......................... 300
9.5.1.7 Metal Core-Semiconducting Metal
Oxide Shell Nanoparticles ............. 300
9.5.2 Insulator-Metal Core-Shell Nanomaterials ....... 301
9.5.2.1 Metal Oxide-Metal Core-Shell
Nanostructures ........................ 301
9.5.2.2 Polymer-Metal Core-Shell
Nanostructures ........................ 301
9.5.3 Insulator-Insulator Core-Shell Nanoparticles ... 302
9.5.3.1 Polymer-Metal Oxide Core-Shell
Nanomaterials ......................... 302
9.5.3.2 Polymer-Polymer Core-Shell
Nanomaterials ......................... 303
9.5.3.3 Biomolecule (Protein) Core-Polymer
Shell Core-Shell Nanoparticles ........ 304
9.5.3.4 Metal Oxide-Metal Oxide Core-Shell
Nanomaterials ......................... 305
9.5.3.5 Metal Oxide-Dye-Doped Silica and
Dye-Doped Silica-Metal Oxide Core-
Shell Nanostructures .................. 305
9.5.3.6 Metal Oxide-Polymer Core-Shell
Nanoparticles ......................... 305
9.5.3.7 Other Inorganic Materials Cores:
Metal Oxide Shells .................... 306
9.5.4 Semiconductor-Insulator Core-Shell
Nanomaterials .................................. 307
9.5.5 Semiconductor-Semiconductor Core-Shell
Nanomaterials .................................. 308
9.5.6 Semiconductor-Semiconductor-Dendrimer Core-
Shell-Shell Nanoparticles ...................... 308
9.5.7 Insulator-Semiconductor Core-Shell
Nanomaterials .................................. 309
9.5.8 Metal-Metal Core-Shell ......................... 310
9.5.9 Insulator-Metal Core-Shell Nanoparticles ....... 313
9.5.10 Carbon-Containing Core-Shell Nanomaterials ..... 313
9.5.10.1 Metal Oxide-Carbon Core-Shell
Nanoparticles ......................... 313
9.5.11 Other Carbon-Containing Core-Shell
Nanomaterials .................................. 313
9.5.12 Synthetic Methods to Create Core-Shell
Nanomaterials, and their Characterizations ..... 316
9.6 Applications .......................................... 317
9.6.1 Applications in Biology and Medicine ........... 317
9.6.1.1 Bioimaging and Immunoassay ............ 318
9.6.1.2 Drug or Biomolecular Delivery
Vehicles .............................. 319
9.6.2 Core-Shell Nanomaterials for Catalysis ......... 319
9.7 Conclusions and Future Prospects ...................... 320
Acknowledgments ....................................... 321
References ............................................ 321
10 Spherical and Anisotropic Silica Shell Nanomaterials ....... 331
Chih-Wei Lai, Jong-Kai Hsiao, Yu-Chun Chen and Pi-Tai
Chou
10.1 Introduction .......................................... 331
10.2 Silica-Coated Metal Nanoparticles ..................... 332
10.2.1 Noble Metal Nanoparticles: An Overview ......... 332
10.2.1.1 Sol-Gel method for Silica Coating ..... 334
10.2.2 Silica Shell for Biofunctionalization .......... 338
10.2.3 Application of Silica-Coated Metal
Nanoparticles .................................. 338
10.2.3.1 Silica Shell Modified with
Oligonucleotides ...................... 338
10.2.3.2 Surface-Enhanced Raman Scattering
Effect ................................ 339
10.2.3.3 Enhanced Luminescence Intensity ....... 342
10.2.4 Coating Silica Gold Nanorods ................... 344
10.2.5 Silica-Encapsulated Platinum ................... 345
10.3 Silica-Coated Quantum Dots ............................ 345
10.3.1 The Advantages of Coating QDs with Silica ...... 346
10.3.2 Different Types of Silica-Coated QDs ........... 347
10.3.2.1 Hydrophobic QDs ....................... 347
10.3.2.2 Hydrophilic QDs ....................... 349
10.4 Silica-Encapsulated Magnetic Nanoparticles ............ 351
10.4.1 Silica-Coated Alloy Metal Nanoparticles ........ 354
10.4.2 Silica-Coated Magnetic Metal Oxide
Nanoparticles .................................. 356
10.4.3 Applications of Silica-Coated Magnetic
Nanoparticles .................................. 359
10.4.3.1 Forming Hybrid Materials with Optic
Materials Dopant ...................... 359
10.5 Hollow Silica Spherical Structures .................... 363
10.5.1 Au and Pt Nanoparticles in Hollow Spheres ...... 363
10.6 Conclusions ........................................... 367
References ............................................ 368
11 Spherical and Anisotropic Core-Shell and Alloy
Nanomaterials: Characterization Using X-Ray Absorption
Spectroscopy ............................................... 377
Loka Subramanyam Sarma, Hung-Lung Chou, Ming-Yao Cheng,
Fadlilatul Taufany, Feng-Ju Lai, Meng-Che Tsai, Shih-Hong
Chang and Bing-Joe Hwang
11.1 I ntroduction ......................................... 377
11.2 Nanoparticle Systems for Biomedical Applications ...... 381
11.2.1 Bioimaging (Magnetic Resonance Imaging) ........ 381
11.2.2 Drug Delivery .................................. 382
11.3 Characterization of Spherical and Anisotropic
Core-Shell and Alloy Nanomaterials using X-Ray
Absorption Spectroscopy (XAS) ......................... 383
11.3.1 XAS Fundamentals ............................... 384
11.3.2 XAS Data Collection and Analysis ............... 386
11.3.3 Structural Characterization: XAS
Methodologies .................................. 387
11.3.3.1 Particle Size, Shape and Aspect
Ratio of Nanoparticles ................ 387
11.3.3.2 Alloy Versus Core-Shell Structure,
Atomic Distribution and Degree of
Alloying of Nanomaterials: An XAS
Methodology ........................... 389
11.3.3.3 Surface and Core Composition in
Bimetallic Nanoparticles: An XAS
Methodology ........................... 391
11.3.4 Review of XAS Characterization Methodologies
for Nanomaterials .............................. 392
11.3.5 XAS Characterization of Surface Interactions ... 399
11.4 Conclusions ........................................... 400
Acknowledgments ....................................... 401
References .................................................. 401
12 Anisotropic Hexagonal Boron Nitride Nanomaterials:
Synthesis and Applications ................................. 411
Wei-Qiang Han
12.1 Introduction .......................................... 411
12.2 Synthesis of В N Nanotubes ............................ 412
12.2.1 Introduction ................................... 412
12.2.2 Arc Discharge .................................. 413
12.2.3 Laser Ablation ................................. 416
12.2.4 Carbon Nanotubes-Substitution Reaction ......... 420
12.2.5 Chemical Vapor Deposition ...................... 426
12.2.6 Solid-Gas Reaction ............................. 429
12.2.7 Low-Temperature Autoclaving .................... 430
12.2.8 Pore-Template .................................. 430
12.2.9 Arc-Jet Plasma ................................. 432
12.3 BNNT-Based Nano-Objects ............................... 433
12.3.1 Filled BNNTs ................................... 433
12.3.2 Functionalized BNNTs ........................... 436
12.4 Porous BN and BN Mesh ................................. 439
12.4.1 Direct Pyrolyzing Borazinic Precursors ......... 439
12.4.2 Use of Mesoporous Molds ........................ 440
12.4.3 Carbon Template-Substitution Reaction .......... 442
12.5 BN Mono- or Few-Layer Sheets .......................... 443
12.6 Physical Properties of h-BN ........................... 446
12.7 Applications .......................................... 447
12.7.1 Pharmaceutical Table Lubricant ................. 447
12.7.2 Cosmetic Materials ............................. 448
12.7.3 10BNNTs for Cancer Therapy and Diagnostics ..... 449
12.7.4 BNNT Composites ................................ 449
12.7.5 Gas Adsorption ................................. 450
12.7.6 Electrical Nanoinsulators ...................... 452
12.7.7 Ultraviolet Lasers and LEDs .................... 452
12.7.8 BN as Support for Catalysts .................... 452
12.8 Concluding Remarks .................................... 453
Acknowledgments ....................................... 453
References ............................................ 453
13 Spherical and Anisotropic Boron Nitride Nanomaterials:
Synthesis and Characterization ............................. 463
Chengchun Tang and Yangxian Li
13.1 Introduction .......................................... 463
13.2 BN Nanomaterials Synthesis ............................ 464
13.2.1 Spherical BN Particles ......................... 464
13.2.2 Anisotropic BN Nanostructures .................. 470
13.2.2.1 Multiwalled Nanorubes ................. 470
13.2.2.2 Single-Walled Nanorubes ............... 476
13.2.2.3 Collapsed BN Nanorubes ................ 478
13.2.2.4 Nanowires ............................. 480
13.3 Remarks on Properties and Applications ................ 483
13.3.1 High-Temperature Chemical Inertness ............ 484
13.3.2 Electrical Properties .......................... 484
13.3.3 High Thermal Conductivity ...................... 485
13.3.4 Mechanical Properties .......................... 486
13.3.5 Hydrogen Storage ............................... 487
13.3.6 Life Sciences .................................. 487
13.4 Concluding Remarks .................................... 489
Acknowledgments ....................................... 491
References ............................................ 491
Index ......................................................... 499
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