Metal-organic Frameworks for Biomedical Applications

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Metal-Organic Frameworks for
Biomedical Applications
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Contributors
1
Nomenclature of MOFs
	Introduction
	What is coordination compound?
	What are polymer and coordination polymer?
	What is a CP?
	Metal-organic framework
	``Organic´´ in metal-organic
	Nomenclature of MOFs
	CP versus MOF
2
Secondary building units of MOFs
	Introduction
	Concept
	Single metal nodes-Pillared square grids, ZMOFs, and ZIFs
	Traditional carboxylate based (metal-oxide) SBUs
	Highly coordinated carboxylate-based (metal-oxide) SBUs
	Nitrogen-containing SBUs-Pyrazoles, triazoles, tetrazoles, and bio-MOFs
	Metal-organic polyhedra
	Infinite rod like SBUs
	Concluding remarks
	Acknowledgment
3
Mixed-metal systems for the synthesis of MOFs
	Introduction
	Mixed-metal MOFs
		Mixed-metal MOFs with alkali metals
		Mixed-metal MOFs with alkaline earth metals
		Mixed-metal MOFs with d10 metals
		Mixed-metal MOFs with transition metals
		Mixed-metal MOFs with rare earth metals
	Conclusions and perspectives
	Acknowledgments
4
Metal-organic frameworks for biomedical applications: The case of functional ligands
	Introduction
	Building blocks for MOFs
	Ligands as the core to access biomedical applications
		Amino acids and peptides
		Nucleobases
		Carboxylic acids
		Phosphonic acids
		Active pharmaceutical ingredients and dietary supplements
	Concluding remarks
	Acknowledgments
	References
5
The role of flexibility in MOFs
	Introduction
	General aspects of framework flexibility
		Breathing, swelling, linker rotation, and subnetwork displacement
		Photoinduction
		Thermal-induction
	Origins of flexibility in MOFs
		Secondary building units (SBUs)
		The impact of organic ligand
		Biomedical applications of flexible MOFs
	Conclusion
	References
6
Surface modification of metal-organic frameworks for biomedical applications
	Introduction
	Modified MOFs for Knoevenagel condensation
	Modified MOFs for Heck reaction
	Modified MOFs for Suzuki-Miyaura and Sonogashira reactions
	Conclusions
	References
7
Hydrothermal synthesis of MOFs
	Introduction to the hydrothermal method
	Basic mechanism and general protocols
	Synthesis of MOFs by the hydrothermal approach
		Synthesis of Fe-MOFs
		Synthesis of Zr-MOFs
		Synthesis of Cu-MOFs
		Synthesis of Zn-MOFs
		Synthesis of other MOFs
	Conclusions and prospects
	Acknowledgments
	References
8
Microwave synthesis of metal-organic frameworks
	Introduction
	Commercial microwave equipment
	Microwave synthesis of MOFs
		Influence of reaction conditions
		Postsynthetic modifications
		MOF film/membrane preparation
	Concluding remarks
	Acknowledgments
	References
	Further reading
9
Electrochemical synthesis of MOFs
	Introduction
	Electrochemical synthesis routes of thin films of MOFs
		Anodic dissolution
		Reductive electrosynthesis
		Bipolar electrosynthesis
		Electrophoretic deposition
		Galvanic displacement
		Miscellaneous methods
	Electrochemical synthesis of MOFs on various conductive substrates
		Deposition of MOFs on metallic substrates
		Deposition of MOFs on conductive glass substrates
		Deposition of MOF on carbonaceous substrates
	Conclusions and future perspectives
	References
10
Mechanochemical synthesis of MOFs
	Introduction
		Comparison between zeolites and MOFs
		Representative example of MOFs for bio-applications
		Engineering greener and more economical manufacturing process and control
	Production of MOFs
	Mechanochemical synthesis
		Three classifications of mechanochemical method
		Pioneering studies of MOFs mechanosynthesis
		Mechanochemical dry conversion of metal source to MOFs
		Porosification (volume expansion and density depletion) associated with crystal conversion
		Acceleration of mechanochemical reaction
		Continuous flow system of MOFs mechanosynthesis
	Conclusions and perspectives
		World\'s first commercial use of MOFs
		Commercial developments
		Challenges to the mainstream adoption of mechanochemical synthesis
	Acknowledgments
	References
11
Sonochemical synthesis of MOFs
	Introduction
	Use of ultrasounds in MOFs
		Comparison with conventional studies
		Alternative US methods
		Effects of synthesis parameters on final product
			Effect of solvents
			Effect of US power and temperature
			Effect of reaction time
			Effect of concentration
			Effect of modulators and additives
		MOF composites
		References
12
Postsynthetic modification of MOFs for biomedical applications
	Introduction
	Types of postsynthetic modification (PSM)
		Covalent postsynthetic modification
		Coordinative postsynthetic modification
		Noncovalent postsynthetic modification/encapsulation
		Hybridization with other materials
		Physical postsynthetic modification
	Typical functionalities added
		Polymers
		Biomolecules
		Photodynamic therapy and imaging units
	Conclusions
	References
	Further reading
13
Characterizations of MOFs for biomedical application
	Introduction
	Characterizations
		Structural characterization
			Phase purity and structure modeling
			Elemental and functionality analysis
		Surface characterization
			Surface morphology analysis
			Particle size and surface charge analysis
			Surface area analysis
		Thermal stability analysis
		Luminescent property analysis
		UV-visible spectroscopy
		Biocompatibility test
	Conclusion
	References
14
Adsorption, delivery, and controlled release of therapeutic molecules from MOFs
	Introduction
	Biological concerns for drug delivery development
		Toxicological study
		Stability and biodegradability
	MOFs: Structures and methods of synthesis
	Surface modification of MOFs for delivery purposes
	MOFs in pharmaceutical technology
		Stimuli-responsive MOFs for drug delivery
			pH-sensitive MOFs
			Ion-responsive MOFs
			Other stimuli-responsive MOFs
			Multiple-stimuli-responsive MOFs
		MOFs for the induction of antibacterial activities
		Targeted contrast agent delivery via NMOFs
			Magnetic resonance imaging
			PDT and PTT therapeutic methods
				PDT
				PTT
			X-ray computed tomography (CT) scan
			PET
			Optical imaging
	Future perspective
	References
	Further reading
15
BioMOFs
	Introduction of biomolecules
	Meaning of biomolecules
	Types of biomolecules
	Applications of biomolecules
	Incorporation of biomolecules with inorganic materials and metal-organic frameworks
	Definition of BioMOFs
	Design of BioMOFs with biomolecules
	Nucleobases
	Amino acids
	Peptides
	Proteins
	Porphyrins and metalloporphyrins
	Cyclodextrin and other biomolecules
	Conclusion and outlook
	References
16
Metal-organic frameworks and exemplified cytotoxicity evaluation
	Introduction
	Metal-organic frameworks
		Metal ions
		Organic ligands
		Solvent
		Secondary building units
	Synthetic method of metal-organic frameworks
		Nanodeposition method
		Solvothermal method
		Reverse microemulsion method
		Surfactant-template solvothermal method
	Characterization of metal-organic frameworks
		Transmission electron microscope and scanning electron microscope
	Application of metal-organic frameworks
		Gas storage
		Catalyst
		Biological application
	Materials and methods
	Results and discussions
	Formation and characterization of nanomaterials
	Magnetic properties of metal oxides
	In vitro toxicity evaluations
	Conclusions
	Acknowledgments
	References
17
Toxicity of nanoscale metal-organic frameworks in biological systems
	Introduction
	Factors affecting the toxicity of MOFs in biological systems
		Metal ions in the MOFs
		Organic linkers
		Solvent in the MOFs synthesis
		Particle size
		Solubility and degradation
		Stability
	Why nanoscale metal-organic frameworks in biological systems?
	In vitro and in vivo toxicity of nanoscale MOFs
		Human exposure to MOFs
	Conclusion
	References
18
Functional MOFs as theranostics
	Introduction
	MOFs NPs with multitherapy and MR/optical imaging properties
		Magnetic-based MOFs NPs
			Gd-based MOF NPs
			Fe-carboxylate MOFs NPs
			Composite nano-objects based on Fe-carboxylate MOFs
			Mn-based MOFs NPs
		MOFs NPs for photodynamic and photothermal therapy
		Nano-objects based on MOFs and inorganic NPs for optical imaging, photodynamic/photothermal therapy
			Core-shell Au NRsMOFs
			Nano-objects based on MOFs and Au nanospheres/nanoclusters
			Core-shell Au nanostar nanoMOF
			Nano-objects based on MOFs and upconversion NPs (UNCPs)
			Nano-objects based on CuS and MOF NPs
		Hybrid nanoparticles by combining MOFs with organic molecules and materials
			Photothermal MOFs-polymer nanocomposites
			C dots
			Graphitic carbon nitride (g-C3N4) nanosheets
			Fluorescent dyes
		MOF NPs for nuclear medical imaging
			Positron emission tomography (PET)
			Single photon emission computer tomography (SPECT)
			Computed tomography (CT)
		Other stimuli-responsive nanoMOF
	Challenges
	Conclusion/perspectives
	References
19
Functional MOFs as molecular imaging probes and theranostics
	Introduction
		Nanostructures as next-generation therapeutics
		Concept of metal-organic frameworks (MOFs)
		Advantages of MOFs
	Synthesis and characterization of MOFs
	Biomedical and pharmaceutical applications of MOFs
		Antimicrobial properties of MOFs
		Antiinfective properties of MOFs
		Phototherapy properties of MOFs
	MOFs as next-generation bioimaging tools
	MOFs as phototheranostics
	MOFs as magnetic theranostics
	Current trends and future perspectives
	Conclusion
	Acknowledgments
	References
20
Carbohydrates in metal organic frameworks: Supramolecular assembly and surface modification for biomedical applications
	Introduction
	MOFs synthesized from edible building blocks of CDs
		Synthesis methods for CD-MOFs
		Drug entrapment
	Carbohydrates as functional surface coatings for MOFs
	Conclusions and future outlook
	Acknowledgments
	References
	Further reading
21
Metal-organic frameworks for drug delivery: Degradation mechanism and in vivo fate
	Introduction
	Synthesis of biodegradable MOFs
	Drug loading and release
	Degradation
	Surface engineering
	Toxicity and in vivo fate
	Conclusions and future outlook
	References
	Further reading
22
Metal-organic frameworks (MOFs) for enzyme immobilization
	Introduction
	Design of MOF as a platform
	Enzyme-MOF composite
		Surface immobilization
		Pore encapsulation methods
		Covalent binding
		De novo encapsulation method
	Characteristics of MOF
		Catalytic activity
		Thermal stability
		Michealis-Menton kinetics
		Chemical stability
		Reusability
		Storage stability
	Multienzyme MOF composites
	Magnetic MOF-enzyme composite
	References
	Further reading
23
State-of-the-art and future perspectives of MOFs in medicine
	A brief story of MOFs, applications, and recent trends
	Toward the golden age of MOF technology in medicine
	Future trends and conclusions
	References
Index
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