Photofunctional Nanomaterials for Biomedical Applications

Summary of the controlled synthesis of photofunctional nanoparticles and their hybrid nanocomposites, as well as their potential in biomedical applications Photofunctional Nanomaterials for Biomedical Applications presents the latest research and developments surrounding photofunctional nanomaterials, including rare earth luminescence nanomaterials and photothermal agents, for biomedical applications related to imaging, biosensing, controlled drug delivery and release, and tumor diagnosis and therapy, as well as other applications such as bacteria engineering, optical information storage, acoustic sensing, and temperature detection. The book elucidates the underlying functioning mechanisms of these nanomaterials in depth and extensively discusses their current challenges and future development prospects. Written by two highly qualified professors with significant research experience in the field, Photofunctional Nanomaterials for Biomedical Applications discusses sample topics including: Fabrication of composites based on lanthanide-doped up conversion nanomaterials and metal-organic frameworks Photosensitizers for photodynamic therapy (PDT), covering basic principles of PDT, classifications of various photosensitizers, mechanisms during treatment, and x-ray-activated PDT Nanomaterials-induced pyroptosis and immunotherapy including pyroptosis pathways and their potential in immunotherapy, especially in activating effector T cells and promoting dendritic cell maturation Design of ternary quantum dots, antibacterial mechanisms in photofunctional antibacterial nanomaterials, and inorganic nanomaterials in photothermal therapy Establishing a robust groundwork for the future clinical translation, Photofunctional Nanomaterials for Biomedical Applications is an essential up-to-date reference on the subject for materials scientists, photochemists, biochemists, and electronic engineers.

Table of Contents:
Foreword xv Preface xvii Acknowledgments xix 1 General Introduction and Background of Photofunctional Nanomaterials in Biomedical Applications 1 Chunxia Li and Jun Lin 1.1 Introduction to Nanomaterials 1 1.1.1 Surface and Interfacial Effects 1 1.1.2 Small Size Effect 2 1.1.3 Quantum Size Effect 2 1.1.4 Macroscopic Quantum Tunneling Effects 2 1.2 Introduction and Classification of Photofunctional Nanomaterials 3 1.2.1 Capture of Photons 3 1.2.2 Absorption and Conversion of Photons 4 1.2.3 Physical-chemical Processes at the Surface Interface 5 1.3 Introduction to Nanobiomedicine 6 1.3.1 Nano-drug Delivery Systems 6 1.3.2 Nano-imaging Technology 6 1.3.3 Nano-diagnostic Technologies 6 1.3.4 Nanotherapeutic Technology 8 1.3.5 Nano-biosensors 8 1.3.6 Tissue Engineering 8 1.4 Classification of Photofunctional Nanomaterials 9 1.4.1 Fluorescent Nanomaterials 9 1.4.1.1 Quantum Dots 10 1.4.1.2 Silicon-Based Fluorescent Nanomaterials 12 1.4.1.3 Rare Earth Luminescent Nanomaterials 13 1.4.1.4 Organic Fluorescent Nanomaterials 18 1.4.2 Photothermal Nanomaterials 20 1.4.2.1 Metallic Photothermal Nanomaterials 20 1.4.2.2 Semiconductor Photothermal Nanomaterials 22 1.4.2.3 Organic Photothermal Nanomaterials 22 1.4.2.4 Carbon-Based Photothermal Nanomaterials 24 1.4.2.5 Certain Two-Dimensional (2D) Nanomaterials 26 1.4.2.6 Biomass Photothermal Nanomaterials 27 1.4.3 Photodynamic Nanomaterials 29 1.4.3.1 Photosensitizer-Loaded Nanomaterials 29 1.4.3.2 Nanomaterials with Intrinsic Photodynamic Effects 32 1.4.3.3 Energy Conversion Nanomaterials for Photosensitizers 33 1.4.4 Photoelectrochemical Nanomaterials 38 1.4.4.1 Photocurrent Signal Generation Mechanism 39 1.4.4.2 Core Elements of Photoelectrochemical Biosensors 40 1.4.4.3 Types of Photoelectrochemical Biosensors 41 1.4.5 Photoacoustic Nanomaterials 45 1.4.5.1 Introduction to Photoacoustic Imaging 46 1.4.5.2 Selection of Photoacoustic Contrast Agents 46 1.5 Conclusion 55 References 55 2 Mechanism in Rare-Earth-Doped Luminescence Nanomaterials 77 Yulei Chang 2.1 Introduction 77 2.2 Composition of RE-Doped Luminescence Nanomaterials: Substrate (Host), Activator, and Sensitizer 77 2.3 Mechanism of RE-Doped Luminescence Nanomaterials 79 2.3.1 Luminescence: Downshifting, Upconversion, and Downconversion 79 2.3.1.1 Downshifting Luminescence 79 2.3.1.2 Upconversion Luminescence (UCL) 81 2.3.1.3 Downconversion/Quantum Cutting (QC) 83 2.3.2 Nonradiative Transition: Energy Transfer and Migration 83 2.3.2.1 Energy Transfer (ET) 83 2.3.2.2 Energy Migration (EM) 84 2.4 Luminescence Modulation 85 2.4.1 Crystal Field (CF) Regulation 85 2.4.2 Surface Defects Passivation 87 2.4.3 ET Regulation 89 2.4.3.1 Multicolor Tuning (MCT) of UCL 89 2.4.3.2 Energy Transfer–Triggered Novel Upconversion Excitation 90 2.4.4 Cross-Relaxation (CR) Regulation 90 2.4.4.1 Alleviating Concentration Quenching (CQ) for Highly Doped UCNPs 91 2.4.4.2 NIR Downshifting Modulation by CR 92 2.4.5 Phonon-Assisted Energy Transfer (PAET) 93 2.4.6 Dye Sensitization 95 2.4.6.1 Dye-Sensitized Core Nanoparticles 95 2.4.6.2 Dye-Sensitized Core–Shell Nanoparticles 96 2.4.7 Combined Excitation Regulation 97 2.4.7.1 Esa 97 2.4.7.2 Sted 98 2.4.8 External Field Modulation 98 2.4.8.1 Magnetic Field Modulation 98 2.4.8.2 Electric Field Modulation 100 2.4.8.3 Plasma Resonance Enhancement 104 References 105 3 Upconversion and NIR-II Luminescence Modulation of Rare-Earth Composites Using Material Informatics 117 Wenjing li and Ruichan lv 3.1 Introduction 117 3.2 Typical Processes of Upconversion Luminescence 118 3.2.1 Excited State Absorption 118 3.2.2 Photon Avalanche 119 3.2.3 Energy Transfer 119 3.2.4 Cross-Relaxation 120 3.2.5 Cooperative Upconversion 120 3.2.6 Second Harmonic Generation 121 3.3 Synthesis Methods of Upconversion Nanoparticles 121 3.3.1 Thermal Decomposition Methods 121 3.3.2 Hydrothermal/Solvothermal Method 122 3.3.3 Co-precipitation Method 123 3.3.4 Sol–Gel Method 123 3.3.5 Other Methods 124 3.4 Material Informatics in UCL 126 3.4.1 Genetic Algorithm 126 3.4.2 Particle Swarm Optimization 127 3.4.3 Simulated Annealing 127 3.4.4 Other Methods 128 3.5 Cancer Therapy Based on UCNPs 130 3.5.1 Photodynamic Therapy 131 3.5.2 Photothermal Therapy 131 3.5.3 Photo-Immunotherapy 133 3.5.4 Photo-Gene Therapy 135 3.6 Conclusion and Perspective 136 References 137 4 Composites Based on Lanthanide-Doped Upconversion Nanomaterials and Metal-Organic Frameworks: Fabrication and Bioapplications 147 Ze Yuan and Xiaoji Xie 4.1 Introduction 147 4.2 Fabrications of Composites 148 4.2.1 In Situ Encapsulation 148 4.2.2 Partial Embedment 155 4.2.3 Interfacial Attachment 157 4.3 Bioapplications 159 4.3.1 Therapy 159 4.3.2 Bioimaging 169 4.3.3 Biosensing 170 4.4 Conclusion and Perspectives 172 References 173 5 Lanthanide-Doped Nanomaterials for Luminescence Biosensing and Biodetection 181 Zhijie Ju, Peng Zhao, and Renren Deng 5.1 Introduction 181 5.2 Basics of Optical Bioprobe and Lanthanide-Doped Nanoparticles 181 5.2.1 Design Considerations for Bioprobe Development 181 5.2.2 Characteristics of Lanthanide-Doped Nanoparticles 182 5.2.3 NIR Biological Windows 186 5.2.4 Energy Transfer: A Key Factor in Biodetection 187 5.3 Synthesis and Functionalization of Lanthanide-Dope Nanocrystals 189 5.3.1 Design and Synthesis of Core–Shell Structured Nanocrystals 189 5.3.1.1 Design of Upconversion Nanoparticles (UCNPs) 190 5.3.1.2 Design of Downshifting Nanoparticles (DSNPs) 191 5.3.2 Functionalization of Lanthanide-Doped Nanoparticles (LnNPs) 192 5.3.2.1 Amphiphilic Polymer Absorption 192 5.3.2.2 Ligand Removal 192 5.3.2.3 Ligand Exchange 192 5.3.2.4 Surface Silanization 193 5.4 Applications of Luminescence Biosensing and Biodetection 193 5.4.1 Temperature Sensing 193 5.4.2 pH Sensing 196 5.4.3 Detection of Biomolecules 198 5.4.4 Detection of Small Molecules and Ions 202 5.5 Integrated Devices for Point-of-Care Testing 208 5.6 Summary 211 References 212 6 Rare Earth Luminescent Nanomaterials for Gene Delivery 219 Jiajun Li and Tao Zhang 6.1 Introduction 219 6.2 UCNPs Nanovectors 221 6.3 Surface Modification 221 6.3.1 Silica 221 6.3.2 Cationic Polymers 223 6.4 Increasing Endosomal Escape 224 6.5 Controlling Delivery Strategy 225 6.5.1 Photodegradable Polymers 226 6.5.2 Changes in Carrier Surface Charge 226 6.5.3 Photoisomerization 228 6.5.4 Microenvironments Stimulation 228 6.5.4.1 Reactive Oxygen Species (ROS) 228 6.5.4.2 Matrixmetallo Proteinases (MMPs) 229 6.5.5 Light Cage 230 6.5.6 Orthogonal Control 231 6.5.7 Release Monitoring 233 6.6 Gene Therapy and Syndication 234 6.6.1 Phototherapy 234 6.6.2 Chemotherapy 235 6.7 Other Lanthanide-Based Nanovectors 236 6.8 Perspective 238 References 239 7 Biosafety of Rare-Earth-Doped Nanomaterials 247 Yang Li and Guanying Chen 7.1 Internalization of UCNPs into Cells 247 7.2 Distribution of UCNPs 249 7.3 Excretion Behavior of UCNPs 252 7.4 The Toxic Effect of Cell Incubated with UCNPs 253 7.5 Toxic Effect of UCNPs In Vivo 256 7.6 Conclusions and Prospects 258 References 259 8 Design and Construction of Photosensitizers for Photodynamic Therapy of Tumor 269 Ruohao Zhang, Jing Feng, Yifei Zhou, Jitong Gong, and Hongjie Zhang 8.1 Introduction 269 8.2 Small Molecule Photosensitizers 273 8.2.1 Porphyrins 273 8.2.2 Phthalocyanines 275 8.2.3 BODIPYs 277 8.2.4 Indocyanine Dyes 278 8.2.5 AIEgens 278 8.3 Metal Complexes 279 8.3.1 Ru(II) Complexes 279 8.3.2 Ir(III) Complexes 280 8.3.3 MOFs 282 8.3.4 COFs 282 8.3.5 HOFs 284 8.4 Inorganic Photosensitizers 284 8.4.1 Carbon-Based Photosensitizers 284 8.4.2 Silicon-Based Photosensitizers 285 8.4.3 Simple Substance Photosensitizers 286 8.4.4 Metal Oxides-Based Photosensitizers 288 8.4.5 Lanthanide Upconversion Nanoparticles-Based PSs 290 8.5 Conclusions and Perspectives 292 References 293 9 Persistent Luminescent Materials for Optical Information Storage Applications 305 Cunjian Lin, Yixi Zhuang, and Rong-Jun Xie 9.1 Introduction 305 9.2 Luminescent Mechanism of Persistent Luminescent Materials with Deep Traps 307 9.3 Persistent Luminescent Materials with Deep Traps 308 9.3.1 Halides or Oxyhalides 309 9.3.2 Sulfides 318 9.3.3 Oxides 320 9.3.3.1 Monobasic Cation Oxide 320 9.3.3.2 Silicate/Germanate/Stannate 321 9.3.3.3 Aluminate/Gallate 323 9.3.3.4 Titanate/Zirconate 326 9.3.3.5 Oxide Glass 327 9.3.4 Nitride or Oxynitrides 327 9.4 Outlooks 331 References 332 10 The Application of Ternary Quantum Dots in Tumor-Related Marker Detection, Imaging, and Therapy 343 Ling Yang, Xiaojiao Kang, Jun Lin, and Ziyong Cheng 10.1 Introduction 343 10.1.1 Fundamental Properties of QDs 344 10.1.2 Synthesis Methods of QDs 346 10.1.2.1 Metal-Organic Synthesis Method 346 10.1.2.2 Hydrophilic Synthesis Method 347 10.1.2.3 Biosynthesis Method 348 10.1.3 Synthesis Methods of Ternary QDs 349 10.1.3.1 Hot-Injection Method 349 10.1.3.2 Ion Exchange Method 350 10.1.3.3 Hydrothermal Method 350 10.1.4 Performance Control of QDs 351 10.1.4.1 Core–Shell Structure 351 10.1.4.2 Alloying 352 10.1.4.3 Ioning 352 10.1.5 Modification of QDs 352 10.1.5.1 Surfacing Ligand Molecular Exchange 352 10.1.5.2 Amphiphilic Organic Macromolecular Coating 353 10.1.6 Characterization of QDs 353 10.1.7 Biomedical Applications of QDs 353 10.1.7.1 Biological Detection 354 10.1.7.2 Cell Imaging 355 10.1.7.3 Live Imaging 356 10.1.7.4 Tumor Therapy 357 10.2 Conclusion 362 References 363 11 Nanomaterials-Induced Pyroptosis and Immunotherapy 373 Hao Chen, Binbin Ding, Jun Lin, and Ping’an Ma 11.1 Discovery and Definition of Pyroptosis 373 11.2 Mechanisms of Pyroptosis 373 11.2.1 Inflammasome and Pyroptosis 374 11.2.2 Caspases, Gasdermins, and Pyroptosis 374 11.3 Pyroptosis and Tumor Immunotherapy 376 11.3.1 Ions Interference Therapy 379 11.3.2 TME-Responsive Pyroptosis Therapy 386 11.3.3 Demethylation-Activated Pyroptosis 386 11.3.4 The Other Pyroptosis Therapies 389 11.4 Summary and Outlook 392 References 393 12 NIR Light-Activated Conversion Nanomaterials for Photothermal/Immunotherapy 399 Yaru Zhang and Zhiyao Hou 12.1 Introduction 399 12.2 The Photothermal Conversion Mechanism 400 12.3 Classification of Inorganic Photothermal Materials 402 12.3.1 Noble Metal Nanomaterials 402 12.3.2 Semiconductor Nanomaterials 406 12.3.2.1 Transition Metal Oxides 406 12.3.2.2 Transition Metal Chalcogenides 408 12.3.3 Carbon-Based Materials 410 12.3.4 Other Types of PTAs 413 12.4 Mechanisms of PTT and Immunotherapy 413 12.4.1 Mechanism of PTT 413 12.4.2 Response of Tumor Cells to Heat Stress 414 12.4.3 PTT-Induced Necrosis and Apoptosis 414 12.4.4 PTT-Induced Immunogenic Cell Death 415 12.4.5 The Impact of PTT on Tumor Microenvironment 416 12.5 Nanomaterial-Based Photothermal/Immunotherapy 417 12.5.1 PTT-Synergized ICB Therapy 417 12.5.1.1 CTLA-4 Checkpoint 418 12.5.1.2 PD-1/PD-L1 Checkpoint 420 12.5.1.3 Other Immune Checkpoints 423 12.5.2 PTT-Synergized Immunoadjuvant Therapy 425 12.5.3 PTT-Synergized Adoptive Cellular Immunotherapy 427 12.5.4 PTT-Synergized Therapeutic Cancer Vaccine 429 12.6 Summary and Outlook 431 References 433 13 Near-Infrared Region-Responsive Antimicrobial Nanomaterials for the Treatment of Multidrug-Resistant Bacteria 449 Manlin Qi, Shangyan Shan, Biao Dong, and Lin Wang 13.1 Introduction 449 13.2 The Antibacterial Mechanisms of Photofunctional Antibacterial Nanomaterials 451 13.3 Photofunctional Nanomaterials and Antibacterial Activity Against MDR Bacteria 452 13.3.1 Representative NIR PDT Photosensitizers 453 13.3.1.1 NIR-Responsive Porphyrins 453 13.3.1.2 NIR-Responsive Phthalocyanines 455 13.3.2 NIR-Responsive PTT Agents 455 13.3.2.1 Gold Nanoparticles and Derived Nanostructures 455 13.3.2.2 Carbon Nanotubes 457 13.3.2.3 Graphene Oxide 458 13.3.2.4 Semiconductor Nanoparticles 458 13.3.3 NIR-Responsive PDT/PTT Agents 459 13.3.3.1 NIR Cyanine Dyes 459 13.3.3.2 NIR QDs 461 13.3.3.3 Aggregation-Induced Emission Luminogens 464 13.4 Limitations and Challenges 465 13.4.1 Common PDT or PTT Resistance Mechanism 465 13.4.1.1 Oxidative Stress Defense 465 13.4.1.2 Thermal Stress Defense 467 13.4.2 MDR Bacteria Drug Resistance Mechanism 467 13.5 Conclusions 468 References 469 14 Photoelectrochemical Nanomaterials for Biosensing Applications 477 Qianqian Sun and Piaoping Yang 14.1 Introduction 477 14.2 Classification of Photoelectrochemical Materials 477 14.2.1 Inorganic Photoelectrochemical Materials 479 14.2.2 Organic Photoelectrochemical Materials 480 14.2.3 Composite Photoelectrochemical Materials 480 14.3 Introduction to Biorecognition Elements 481 14.4 Factors Affecting the Photocurrent Signal 482 14.5 Signal Amplification and Bursting Strategies 484 14.5.1 Photocurrent Signal Amplification Strategies 484 14.5.2 Photocurrent Signal Bursting Strategies 489 14.6 Applications of Photoelectrochemical Biosensors 493 14.6.1 Direct Photoelectrochemical Detection 493 14.6.2 Photoelectrochemical Enzyme Detection 494 14.6.3 Photoelectrochemical Nucleic Acid Detection 495 14.6.4 Photoelectrochemical Immunoassay 497 14.7 Challenges and Potential Clinical Applications 498 References 500 15 X-Ray-Induced Photodynamic Therapy for Deep-Seated Tumors 507 Jinliang Liu 15.1 Introduction 507 15.2 Mechanisms of Interaction Between X-Rays and Scintillation Materials 509 15.3 X-Ray-Sensitive Materials 511 15.3.1 Metallic Materials 511 15.3.1.1 Lanthanide-based Nanophosphors 511 15.3.1.2 Metal Cluster Nanomaterials 514 15.3.1.3 Long-Afterglow Luminescent Nanomaterials 516 15.3.1.4 Quantum Dots 518 15.3.1.5 Metal–Organic Complexes 521 15.3.1.6 Metal-Organic Frameworks (MOFs) 523 15.3.2 Nonmetallic Materials 525 15.3.2.1 Organic Materials 525 15.3.2.2 Nonmetallic Inorganic Materials 526 15.4 X-Ray-Activated Therapy 527 15.4.1 Type I X-Ray-Excited PDT 527 15.4.2 Type II X-Ray-Excited PDT 529 15.4.3 Combined Type I and Type II X-Ray-Excited PDT 531 15.4.4 X-Ray-Induced Generation of RNS for Dynamic Therapy 532 15.4.5 Synergistic Therapy 536 15.5 Conclusions and Perspectives 539 References 540 16 Conclusions and Perspectives 549 Chunxia Li and Jun Lin Index 551