Front Cover......Page 1
Metal-Organic Frameworks for Biomedical Applications......Page 4
Copyright......Page 5
Contents......Page 6
Contributors......Page 16
Chapter 1: Nomenclature of MOFs......Page 20
1.1. Introduction......Page 21
1.3. What are polymer and coordination polymer?......Page 22
1.5. Metal-organic framework......Page 23
1.7. Nomenclature of MOFs......Page 24
1.8. CP versus MOF......Page 26
References......Page 27
2.2. Concept......Page 30
2.3. Single metal nodes-Pillared square grids, ZMOFs, and ZIFs......Page 35
2.4. Traditional carboxylate based (metal-oxide) SBUs......Page 38
2.5. Highly coordinated carboxylate-based (metal-oxide) SBUs......Page 44
2.6. Nitrogen-containing SBUs-Pyrazoles, triazoles, tetrazoles, and bio-MOFs......Page 51
2.7. Metal-organic polyhedra......Page 55
2.8. Infinite rod like SBUs......Page 57
References......Page 59
3.1. Introduction......Page 64
3.2.1. Mixed-metal MOFs with alkali metals......Page 66
3.2.2. Mixed-metal MOFs with alkaline earth metals......Page 68
3.2.3. Mixed-metal MOFs with d10 metals......Page 70
3.2.4. Mixed-metal MOFs with transition metals......Page 75
3.2.5. Mixed-metal MOFs with rare earth metals......Page 80
3.3. Conclusions and perspectives......Page 82
References......Page 83
Chapter 4: Metal-organic frameworks for biomedical applications: The case of functional ligands......Page 88
4.1. Introduction......Page 89
4.2. Building blocks for MOFs......Page 90
4.3. Ligands as the core to access biomedical applications......Page 91
4.3.1. Amino acids and peptides......Page 92
4.3.2. Nucleobases......Page 95
4.3.3. Carboxylic acids......Page 97
4.3.4. Phosphonic acids......Page 100
4.3.5. Active pharmaceutical ingredients and dietary supplements......Page 102
4.4. Concluding remarks......Page 106
References......Page 107
5.1. Introduction......Page 112
5.2.1. Breathing, swelling, linker rotation, and subnetwork displacement......Page 115
5.2.2. Photoinduction......Page 116
5.2.3. Thermal-induction......Page 117
5.3.1. Secondary building units (SBUs)......Page 118
5.3.2. The impact of organic ligand......Page 119
5.3.3. Biomedical applications of flexible MOFs......Page 121
References......Page 125
6.1. Introduction......Page 130
6.2. Modified MOFs for Knoevenagel condensation......Page 132
6.3. Modified MOFs for Heck reaction......Page 140
6.4. Modified MOFs for Suzuki-Miyaura and Sonogashira reactions......Page 144
References......Page 152
7.1. Introduction to the hydrothermal method......Page 160
7.2. Basic mechanism and general protocols......Page 162
7.3.1. Synthesis of Fe-MOFs......Page 164
7.3.2. Synthesis of Zr-MOFs......Page 166
7.3.3. Synthesis of Cu-MOFs......Page 169
7.3.4. Synthesis of Zn-MOFs......Page 171
7.4. Conclusions and prospects......Page 172
References......Page 174
Chapter 8: Microwave synthesis of metal-organic frameworks......Page 178
8.1. Introduction......Page 179
8.2. Commercial microwave equipment......Page 180
8.3. Microwave synthesis of MOFs......Page 183
8.3.1. Influence of reaction conditions......Page 184
8.3.2. Postsynthetic modifications......Page 188
8.3.3. MOF film/membrane preparation......Page 190
References......Page 192
9.1. Introduction......Page 196
9.2.1. Anodic dissolution......Page 198
9.2.2. Reductive electrosynthesis......Page 202
9.2.4. Electrophoretic deposition......Page 203
9.2.5. Galvanic displacement......Page 204
9.3.1. Deposition of MOFs on metallic substrates......Page 205
9.3.2. Deposition of MOFs on conductive glass substrates......Page 207
9.4. Conclusions and future perspectives......Page 208
References......Page 209
10.1.1. Comparison between zeolites and MOFs......Page 216
10.1.2. Representative example of MOFs for bio-applications......Page 218
10.2. Production of MOFs......Page 220
10.3. Mechanochemical synthesis......Page 222
10.3.2. Pioneering studies of MOFs mechanosynthesis......Page 223
10.3.3. Mechanochemical dry conversion of metal source to MOFs......Page 224
10.3.4. Porosification (volume expansion and density depletion) associated with crystal conversion......Page 225
10.3.5. Acceleration of mechanochemical reaction......Page 226
10.4. Conclusions and perspectives......Page 230
10.4.2. Commercial developments......Page 232
10.4.3. Challenges to the mainstream adoption of mechanochemical synthesis......Page 234
Acknowledgments......Page 235
References......Page 236
11.1. Introduction......Page 242
11.2.1. Comparison with conventional studies......Page 244
11.2.2. Alternative US methods......Page 249
11.2.3.1. Effect of solvents......Page 250
11.2.3.3. Effect of reaction time......Page 252
11.2.3.4. Effect of concentration......Page 253
11.2.3.5. Effect of modulators and additives......Page 254
11.2.4. MOF composites......Page 256
References......Page 258
12.1. Introduction......Page 264
12.2.1. Covalent postsynthetic modification......Page 265
12.2.2. Coordinative postsynthetic modification......Page 267
12.2.3. Noncovalent postsynthetic modification/encapsulation......Page 269
12.2.4. Hybridization with other materials......Page 270
12.2.5. Physical postsynthetic modification......Page 275
12.3.1. Polymers......Page 277
12.3.2. Biomolecules......Page 284
12.3.3. Photodynamic therapy and imaging units......Page 287
References......Page 292
13.1. Introduction......Page 296
13.2.1. Structural characterization......Page 297
13.2.1.1. Phase purity and structure modeling......Page 298
13.2.1.2. Elemental and functionality analysis......Page 300
13.2.2.1. Surface morphology analysis......Page 303
13.2.2.2. Particle size and surface charge analysis......Page 305
13.2.2.3. Surface area analysis......Page 307
13.2.3. Thermal stability analysis......Page 308
13.2.4. Luminescent property analysis......Page 309
13.2.5. UV-visible spectroscopy......Page 310
References......Page 311
14.1. Introduction......Page 316
14.2.1. Toxicological study......Page 317
14.2.2. Stability and biodegradability......Page 318
14.3. MOFs: Structures and methods of synthesis......Page 319
14.4. Surface modification of MOFs for delivery purposes......Page 320
14.5. MOFs in pharmaceutical technology......Page 321
14.5.1.1. pH-sensitive MOFs......Page 322
14.5.1.3. Other stimuli-responsive MOFs......Page 324
14.5.1.4. Multiple-stimuli-responsive MOFs......Page 325
14.5.2. MOFs for the induction of antibacterial activities......Page 327
14.5.3.1. Magnetic resonance imaging......Page 328
PDT......Page 329
PTT......Page 331
14.5.3.4. PET......Page 332
14.5.3.5. Optical imaging......Page 333
14.6. Future perspective......Page 334
References......Page 335
15.2. Meaning of biomolecules......Page 340
15.4. Applications of biomolecules......Page 341
15.5. Incorporation of biomolecules with inorganic materials and metal-organic frameworks......Page 342
15.6. Definition of BioMOFs......Page 343
15.8. Nucleobases......Page 344
15.9. Amino acids......Page 346
15.10. Peptides......Page 348
15.11. Proteins......Page 352
15.12. Porphyrins and metalloporphyrins......Page 356
15.13. Cyclodextrin and other biomolecules......Page 357
15.14. Conclusion and outlook......Page 358
References......Page 359
16.1. Introduction......Page 366
16.2.1. Metal ions......Page 369
16.2.2. Organic ligands......Page 371
16.2.3. Solvent......Page 373
16.3.1. Nanodeposition method......Page 374
16.3.2. Solvothermal method......Page 376
16.3.3. Reverse microemulsion method......Page 378
16.4. Characterization of metal-organic frameworks......Page 379
16.4.1. Transmission electron microscope and scanning electron microscope......Page 380
16.5.2. Catalyst......Page 383
16.6. Materials and methods......Page 384
16.7. Results and discussions......Page 385
16.8. Formation and characterization of nanomaterials......Page 386
16.9. Magnetic properties of metal oxides......Page 389
16.10. In vitro toxicity evaluations......Page 390
16.11. Conclusions......Page 392
Acknowledgments......Page 393
References......Page 394
17.1. Introduction......Page 402
17.2.1. Metal ions in the MOFs......Page 403
17.2.4. Particle size......Page 404
17.2.6. Stability......Page 405
17.3. Why nanoscale metal-organic frameworks in biological systems?......Page 406
17.4. In vitro and in vivo toxicity of nanoscale MOFs......Page 407
17.4.1. Human exposure to MOFs......Page 410
References......Page 412
Chapter 18: Functional MOFs as theranostics......Page 416
18.1. Introduction......Page 417
18.2.1.1. Gd-based MOF NPs......Page 418
18.2.1.2. Fe-carboxylate MOFs NPs......Page 419
18.2.1.3. Composite nano-objects based on Fe-carboxylate MOFs......Page 421
18.2.2. MOFs NPs for photodynamic and photothermal therapy......Page 422
18.2.3. Nano-objects based on MOFs and inorganic NPs for optical imaging, photodynamic/photothermal therapy......Page 423
18.2.3.1. Core-shell Au NRsMOFs......Page 424
18.2.3.2. Nano-objects based on MOFs and Au nanospheres/nanoclusters......Page 425
18.2.3.4. Nano-objects based on MOFs and upconversion NPs (UNCPs)......Page 427
18.2.4.1. Photothermal MOFs-polymer nanocomposites......Page 428
18.2.4.4. Fluorescent dyes......Page 431
18.2.5.2. Single photon emission computer tomography (SPECT)......Page 432
18.2.5.3. Computed tomography (CT)......Page 433
18.2.6. Other stimuli-responsive nanoMOF......Page 434
18.3. Challenges......Page 436
References......Page 437
19.1. Introduction......Page 444
19.1.2. Concept of metal-organic frameworks (MOFs)......Page 445
19.1.3. Advantages of MOFs......Page 446
19.2. Synthesis and characterization of MOFs......Page 447
19.3. Biomedical and pharmaceutical applications of MOFs......Page 449
19.3.1. Antimicrobial properties of MOFs......Page 450
19.3.2. Antiinfective properties of MOFs......Page 452
19.4. MOFs as next-generation bioimaging tools......Page 453
19.5. MOFs as phototheranostics......Page 454
19.6. MOFs as magnetic theranostics......Page 455
19.7. Current trends and future perspectives......Page 457
References......Page 458
20.1. Introduction......Page 464
20.2. MOFs synthesized from edible building blocks of CDs......Page 466
20.2.1. Synthesis methods for CD-MOFs......Page 468
20.2.2. Drug entrapment......Page 470
20.3. Carbohydrates as functional surface coatings for MOFs......Page 475
20.4. Conclusions and future outlook......Page 480
References......Page 481
21.1. Introduction......Page 486
21.2. Synthesis of biodegradable MOFs......Page 488
21.3. Drug loading and release......Page 490
21.4. Degradation......Page 496
21.5. Surface engineering......Page 499
21.6. Toxicity and in vivo fate......Page 503
21.7. Conclusions and future outlook......Page 504
References......Page 505
22.1. Introduction......Page 510
22.2. Design of MOF as a platform......Page 511
22.3. Enzyme-MOF composite......Page 512
22.3.1. Surface immobilization......Page 513
22.3.2. Pore encapsulation methods......Page 515
22.3.3. Covalent binding......Page 517
22.3.4. De novo encapsulation method......Page 518
22.4.3. Michealis-Menton kinetics......Page 527
22.4.5. Reusability......Page 528
22.4.6. Storage stability......Page 529
22.5. Multienzyme MOF composites......Page 530
22.6. Magnetic MOF-enzyme composite......Page 532
References......Page 536
Chapter 23: State-of-the-art and future perspectives of MOFs in medicine......Page 544
23.1. A brief story of MOFs, applications, and recent trends......Page 545
23.2. Toward the golden age of MOF technology in medicine......Page 556
23.3. Future trends and conclusions......Page 559
References......Page 565
Index......Page 572
Back Cover......Page 586