Polyoxometalates: Advances, Properties, and Applications

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Polyoxometalates are anionic metal-oxo nanoclusters, which constitute a unique class of compounds owing to their rich solution equilibria and their unique compositional, electronic, reactive, and structural diversity. This book reviews metal-oxide cluster chemistry by covering topics ranging from fundamental aspects (i.e., structure, properties, self-assembly processes, derivatization) to functional materials that incorporate these molecular units, as well as their applications in the fields of current socioeconomic interest, such as energy storage systems, catalysis, molecular electronics, and biomedicine. Edited by prominent researchers in the field of polymer and polyoxometalate chemistries, the book compiles contributions from some of the most distinguished and promising scientists worldwide in such a way that it will appeal to a general readership involved in research areas related to chemistry and materials science.

Author(s): Leire Ruiz Rubio, José Luis Vilas Vilela, Beñat Artetxe, Juan Manuel Gutiérrez-Zorrilla
Publisher: Jenny Stanford Publishing
Year: 2022

Language: English
Pages: 381
City: Singapore

Cover
Half Title
Title Page
Copyright Page
Table of Contents
Preface
Chapter 1: General Principles and Structural Chemistry of Polyoxometalates
1.1: Introduction
1.2: Structural Principles
1.3: General Properties
1.4: Classification
1.4.1: Isopolyoxometalates
1.4.2: Heteropolyoxometalates
1.4.3: Unconventional POMs
1.4.3.1: Giant molybdenum clusters
1.4.3.2: Uranium clusters
1.4.3.3: Noble metal containing POMs
1.5: Functionalization of POMs
1.5.1: 3d Metal Containing POMs
1.5.2: 4f Metal Containing POMs
1.5.3: Organic Functionalizaion
1.5.3.1: p-block organoderivatives
1.5.3.2: Substitution of surface oxygen atoms
1.5.3.3: Organic functionalization of 3d or 4f metal substituted POMs
1.6: Conclusion
Chapter 2: Polyoxometalate Macroions in Solution
2.1: Introduction
2.2: The Self-Assembly of POM Macroions into Blackberry Structures
2.2.1: Experimental Methods to Characterize the Self-Assembly of POM Macroions into Blackberry Structures
2.2.2: The Major Driving Forces of Blackberry Formation: Counterion-Mediated Attraction
2.2.3: Counterion-Specific Effects in the Self-Assembly of POMs
2.2.4: Other Non-Covalent Interactions Contribute to Blackberry Structure Formation
2.2.4.1: Hydrogen bond
2.2.4.2: Hydrophobic interaction
2.2.5: The Connection Between the Self-Assembly of POM Macroions and Complex Biomacromolecule Assemblies
2.2.5.1: The self-assembly kinetics of POM macroions and connection to viral capsid formation
2.2.5.2: Cations transport across POM macroion and blackberry “membrane”
2.2.5.3: Self-recognition and chiral selection in the self-assembly of POM macroions, connecting to the origin of biological homochirality
2.3: Conclusion
Chapter 3: Rational Design and Self-Assembly of Polyoxometalate-Peptide Hybrid Materials
3.1: Introduction
3.2: Covalent POM-Peptide Hybrids
3.2.1: Synthesis and Characterization of Covalent Hybrids
3.2.1.1: Synthesis via TRIS functionalization
3.2.1.2: Synthesis via organotin functionalizaion
3.2.1.3: Characterization of POM-peptide hybrids
3.2.2: Self-Assembly, Folding, and Supramolecular Chemistry
3.2.2.1: Charge and morphology of the POM
3.2.2.2: Peptide properties
3.2.3: Stereochemistry in POM-Peptide Hybrids: Study and Application
3.2.4: Future Perspectives
3.3: Ionic POM-Peptide Hybrids
3.3.1: Building Blocks: POMs & Peptide
3.3.1.1: POM clusters
3.3.1.2: Peptides
3.3.2: Mechanisms of Assembly: A Case Study
3.3.3: Applications
3.3.3.1: Biomedical applications
3.3.3.2: Adhesives
3.3.3.3: Catalysis
3.3.4: Future Perspectives
Chapter 4: Polyoxometalate–Polymer Hybrid Materials
4.1: Introduction
4.2: Development of Hybrid POM/Polymer Materials
4.2.1: Physical Blends of POM/Polymers
4.2.2: Hybrid Composites Formed by Non-Covalent Interactions
4.2.3: Covalently Linked POM/Polymer Hybrids
4.2.3.1: Hybrid materials formed by monomer modification
4.2.3.2: Covalently linked hybrid POM/polymers formed afterpolymerization
4.3: Applications
4.3.1: Drug Delivery System for Breast Cancer Therapies
4.3.2: Self-Healing Hybrid Hydrogels
4.3.3: Moisture Responsive Sensors
4.3.4: Solar UV Sensor
4.3.5: Intumescent Flame Retardant
4.3.6: Electrochemical Capacitors
4.3.7: Solid-State Proton Conductors
4.3.8: Near-Infrared and Visible Light Modulated Electrochromic Devices
4.4: Conclusion
Chapter 5: Polyoxometalates in Catalysis
5.1: Introduction
5.2: Stability of POMs
5.3: Porosity-Accessibility in POMs
5.3.1: HPAs Supported on Porous Solids: Impregnation and Sol–Gel Methods
5.3.2: Development of Tailored Porosity in Nanostructured Heteropolysalts
5.4: POMs as Catalysts
5.4.1: HPAs as Acid Catalysts
5.4.2: HPAs as Redox Catalysts
5.4.3: Heteropolysalts as Bifunctional Catalysts
Chapter 6: Transition Metal Oxide–Based Storage Materials
6.1: Molecular Metal Oxides in Magnetism and Semiconductors
6.2: Abundance of Raw Materials
6.3: Introduction: Building the Nanoworld
6.4: Molecular Metal Oxides: POMs, Synthesis, and Structural Features
6.5: Magnetic Materials
6.6: Metal Oxides in Memory Devices
6.7: Future Challenges and Research
6.8: Conclusion
Chapter 7: Polyoxometalate-Based Redox Flow Batteries
7.1: Introduction
7.2: RFBs
7.2.1: All-VRFBs
7.2.2: Alternatives to all-VRFBs
7.3: POM-Based RFBs
7.3.1: Fundamental Redox Mechanisms of POMs at Electrodes and ESS
7.3.2: State of the Art in POM–RFBs
7.4: Conclusion
Chapter 8: Polyoxometalates with Anticancer, Antibacterial and Antiviral Activities
8.1: Introduction
8.2: Antitumor Activity of POMs
8.2.1: Decavanadate and POVs
8.2.2: POMos and POTs
8.3: Mechanisms of Action of POMs as Anticancer Agents
8.3.1: Effects in Mitochondria, Oxidative Stress, and Mechanisms of Cell Death
8.3.2: Autophagy and POMs
8.3.3: Inhibition of Ecto-Nucleosidases and Histone Deacetylases
8.3.4: Inhibition of ALPs, Kinases, P-type ATPases and Aquaporins
8.4: Antibacterial Activity of POMs
8.4.1: Decavanadate and POVs
8.4.2: POTs and POMos
8.5: Mechanisms of Action of POMs as Antibacterial Agents
8.5.1: Modulation of Gene Expression
8.5.2: POMs Interactions with Proteases, Phosphatases, P-Type ATPases and Actin
8.5.3: Effects on Sialyl- and Sulfotransferase
8.5.4: Bioenergetic and Redox Disturbance
8.6: Antiviral Activity of POMs
8.6.1: Decavanadate and POVs
8.6.2: POTs and POMos
8.7: POMs Mechanisms of Antiviral Activity
8.8: Conclusion and Perspective
8.8.1: Anticancer Activities
8.8.2: Antibacterial Activities
8.8.3: Antiviral Activities
Index