Tailored Organic-Inorganic Materials (eBook, PDF)
Redaktion: Brunet, Ernesto; Clearfield, Abraham; Colón, Jorge L.
Tailored Organic-Inorganic Materials (eBook, PDF)
Redaktion: Brunet, Ernesto; Clearfield, Abraham; Colón, Jorge L.
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This book explores the limitless ability to design new materials by layering clay materials within organic compounds. Assembly, properties, characterization, and current and potential applications are offered to inspire the development of novel materials. * Coincides with the government's Materials Genome Initiative, to inspire the development of green, sustainable, robust materials that lead to efficient use of limited resources * Contains a thorough introductory and chemical foundation before delving into techniques, characterization, and properties of these materials * Applications in…mehr
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- Produktdetails
- Verlag: John Wiley & Sons
- Seitenzahl: 480
- Erscheinungstermin: 30. April 2015
- Englisch
- ISBN-13: 9781118773642
- Artikelnr.: 42830243
- Verlag: John Wiley & Sons
- Seitenzahl: 480
- Erscheinungstermin: 30. April 2015
- Englisch
- ISBN-13: 9781118773642
- Artikelnr.: 42830243
and Their Extraordinary Properties 1 1.1 Introduction 1 1.2 Synthesis and
Crystal Structure of alpha-Zirconium Phosphate 2 1.3 Zirconium
Phosphate-Based Dialysis Process 5 1.4 ZrP Titration Curves 7 1.5
Applications of Ion-Exchange Processes 11 1.6 Nuclear Ion Separations 11
1.7 Major Uses of alpha-ZrP 12 1.8 Polymer Nanocomposites 12 1.9 More
Details on alpha-ZrP: Surface Functionalization 17 1.10 Janus Particles 18
1.11 Catalysis 20 1.12 Catalysts Based on Sulphonated Zirconium
Phenylphosphonates 22 1.13 Proton Conductivity and Fuel Cells 27 1.14 Gel
Synthesis and Fuel Cell Membranes 30 1.15 Electron Transfer Reactions 32
1.16 Drug Delivery 34 1.17 Conclusions 39 References 40 2 Tales from the
Unexpected: Chemistry at the Surface and Interlayer Space of Layered
Organic-Inorganic Hybrid Materials Based on gamma-Zirconium Phosphate 45
2.1 Introduction 45 2.2 The Inorganic Scaffold: gamma-Zirconium Phosphate
(Microwave-Assisted Synthesis) 46 2.3 Microwave-Assisted Synthesis of
gamma-ZrP 48 2.4 Reactions 51 2.4.1 Intercalation 51 2.4.2
Microwave-Assisted Intercalation into gamma-ZrP 52 2.4.3
Phosphate/Phosphonate Topotactic Exchange 52 2.5 Labyrinth Materials:
Applications 57 2.5.1 Recognition Management 57 2.5.1.1 Chirality at Play
62 2.5.1.2 Gas and Vapour Storage 69 2.5.2 Dissymmetry and Luminescence
Signalling 71 2.5.3 Building DSSCs 75 2.5.4 Molecular Confinement 77 2.6
Conclusion and Prospects 78 References 79 3 Phosphonates in Matrices 83 3.1
Introduction: Phosphonic Acids as Versatile Molecules 83 3.2 Acid-Base
Chemistry of Phosphonic Acids 84 3.3 Interactions between Metal Ions and
Phosphonate Ligands 87 3.4 Phosphonates in 'All-Organic' Polymeric Salts 90
3.5 Phosphonates in Coordination Polymers 96 3.6 Phosphonate-Grafted
Polymers 97 3.7 Polymers as Hosts for Phosphonates and Metal Phosphonates
108 3.8 Applications 113 3.8.1 Proton Conductivity 113 3.8.2 Metal Ion
Absorption 117 3.8.3 Controlled Release of Phosphonate Pharmaceuticals 119
3.8.4 Corrosion Protection by Metal Phosphonate Coatings 125 3.8.5 Gas
Storage 125 3.8.6 Intercalation 126 3.9 Conclusions 127 References 128 4
Hybrid Materials Based on Multifunctional Phosphonic Acids 137 4.1
Introduction 137 4.2 Structural Trends and Properties of Functionalized
Metal Phosphonates 138 4.2.1 Monophosphonates 138 4.2.1.1 Metal Alkyl- and
Aryl-Carboxyphosphonates 138 4.2.1.2 Hydroxyl-Carboxyphosphonates 143
4.2.1.3 Nitrogen-funcionalized phosphonates 147 4.2.1.4 Metal
Phosphonatosulphonates 149 4.2.2 Diphosphonates 150 4.2.2.1
Aryldiphosphonates: 1,4-Phenylenebisphosphonates and Related Materials 151
4.2.2.2 1-Hydroxyethylidinediphosphonates 155 4.2.2.3
R-Amino-N,N-bis(methylphosphonates) and R-N,N'?]bis(methylphosphonates) 156
4.2.3 Polyphosphonates 163 4.2.3.1 Functionalized Metal Triphosphonates 163
4.2.3.2 Functionalized Metal Tetraphosphonates 167 4.3 Some Relevant
Applications of Multifunctional Metal Phosphonates 174 4.3.1 Gas Adsorption
175 4.3.2 Catalysis and Photocatalysis 175 4.3.3 Proton Conductivity 176
4.4 Concluding Remarks 181 References 181 5 Hybrid Multifunctional
Materials Based on Phosphonates, Phosphinates and Auxiliary Ligands 193 5.1
Introduction 193 5.1.1 Phosphonates and Phosphinates as Ligands for CPs:
Differences in Their Coordination Capabilities 195 5.1.2 The Role of the
Auxiliary Ligands 196 5.1.2.1 N-Donors 196 5.1.2.2 O-Donors 198 5.2 CPs
Based on Phosphonates and N-Donor Auxiliary Ligands 199 5.2.1
2,2'-Bipyridine and Related Molecules 199 5.2.2 Terpyridine and Related
Molecules 210 5.2.3 4,4'-Bipy and Related Molecules 210 5.2.4 Imidazole and
Related Molecules 222 5.2.5 Other Ligands 225 5.3 CPs Based on Phosphonates
and O-Donor Auxiliary Ligands 228 5.4 CPs Based on Phosphinates and
Auxiliary Ligands 233 5.5 Conclusions and Outlooks 240 References 241 6
Hybrid and Biohybrid Materials Based on Layered Clays 245 6.1 Introduction:
Clay Concepts and Intercalation Behaviour of Layered Silicates 245 6.2
Intercalation Processes in 1 : 1 Phyllosilicates 247 6.3 Intercalation in 2
: 1 Charged Phyllosilicates 252 6.3.1 Intercalation of Neutral Organic
Molecules in 2: 1 Charged Phyllosilicates 252 6.3.2 Intercalation of
Organic Cations in 2 : 1 Charged Phyllosilicates: Organoclays 256 6.4
Intercalation of Polymers in Layered Clays 263 6.4.1 Polymer-Clay
Nanocomposites 263 6.4.2 Biopolymer Intercalations: Bionanocomposites 269
6.5 Uses of Clay-Organic Intercalation Compounds: Perspectives towards New
Applications as Advanced Materials 275 6.5.1 Selective Adsorption and
Separation 276 6.5.2 Catalysis and Supports for Organic Reactions 280 6.5.3
Membranes, Ionic and Electronic Conductors and Sensors 281 6.5.4
Photoactive Materials 284 6.5.5 Biomedical Applications 284 References 286
7 Fine-Tuning the Functionality of Inorganic Surfaces Using Phosphonate
Chemistry 299 7.1 Phosphonate-Based Modified Surfaces: A Brief Overview 299
7.2 Biological Applications of Phosphonate-Derivatized Inorganic Surfaces
300 7.2.1 Phosphonate Coatings as Bioactive Surfaces 300 7.2.1.1 Supported
Lipid Bilayer 300 7.2.1.2 Surface-Modified Nanoparticles 303 7.2.2 Specific
Binding of Biological Species onto Phosphonate Surfaces for the Design of
Microarrays, 304 7.2.2.1 Single- and Double-Stranded Oligonucleotides 304
7.2.2.2 Proteins and Other Biomolecules 306 7.2.3 Calcium
Phosphate/Bisphosphonate Combination as a Route to Implantable Biomedical
Devices 308 7.3 Conclusion 314 References 315 8 Photofunctional
Polymer/Layered Silicate Hybrids by Intercalation and Polymerization
Chemistry 319 8.1 Introduction 319 8.2 Lighting Is Changing 320 8.3
Generalities 321 8.3.1 Layered Silicates 321 8.3.2 Polymer/Layered Silicate
Hybrid Structures 322 8.3.3 Methods of Preparation of PNs 323 8.4
Functional Intercalated Compounds 324 8.4.1 Dyes Intercalated Hybrids and
(Co)intercalated PNs 324 8.4.2 Light-Emitting Polymer Hybrids 331 8.4.2.1
Poly( p-Phenylene Vinylene)-Based Polymer Hybrids 331 8.4.2.2
Poly(fluorene)-Based Polymer Hybrids 333 8.5 Conclusions and Perspectives
337 References 338 9 Rigid Phosphonic Acids as Building Blocks for
Crystalline Hybrid Materials 341 9.1 Introduction 341 9.2 O verview of the
Synthesis of Rigid Functional Aromatic and Heteroaromatic Phosphonic Acids
343 9.3 Synthetic Methods to Produce Phosphonic-Based Hybrids 346 9.4
Hybrid Materials from Rigid Di- and Polyphosphonic Acids 347 9.5 Hybrid
Materials from Rigid Hetero-polyfunctional Precursors 357 9.5.1
Phosphonic-Carboxylic Acids 357 9.5.2 Phosphonic-Sulphonic Acids 366 9.5.3
O ther Functional Groups 368 9.6 Hybrid Materials from Phosphonic Acids
Linked to a Heterocyclic Compound 369 9.6.1 Aza-heterocyclic 369 9.6.2
Thio-heterocycles 373 9.7 Physical Properties and Applications 376 9.7.1
Magnetism 376 9.7.2 Fluorescence 378 9.7.3 Thermal Stability 382 9.7.4 Drug
Release 384 9.8 Conclusion and Perspectives 386 References 387 10 Drug
Carriers Based on Zirconium Phosphate Nanoparticles 395 10.1 Introduction
395 10.1.1 Zirconium Phosphates 396 10.1.2 Pre-intercalation and the
Exfoliation (Layer-by-Layer) Method 397 10.1.3 Direct Ion Exchange of ZrP
399 10.1.4 Direct Ion Exchange Using theta-ZrP 400 10.2 Drug Nanocarriers
Based on theta-ZrP 402 10.2.1 Insulin 402 10.2.2 Anticancer Agents 410
10.2.2.1 Nanoparticles and the Enhanced Permeability and Retention Effect
410 10.2.2.2 Cisplatin 410 10.2.2.3 Doxorubicin 418 10.2.2.4 Metallocenes
422 10.2.3 Neurological Agents 428 10.2.3.1 CBZ 429 10.2.3.2 DA 430 10.3
Conclusion 431 References 431
and Their Extraordinary Properties 1 1.1 Introduction 1 1.2 Synthesis and
Crystal Structure of alpha-Zirconium Phosphate 2 1.3 Zirconium
Phosphate-Based Dialysis Process 5 1.4 ZrP Titration Curves 7 1.5
Applications of Ion-Exchange Processes 11 1.6 Nuclear Ion Separations 11
1.7 Major Uses of alpha-ZrP 12 1.8 Polymer Nanocomposites 12 1.9 More
Details on alpha-ZrP: Surface Functionalization 17 1.10 Janus Particles 18
1.11 Catalysis 20 1.12 Catalysts Based on Sulphonated Zirconium
Phenylphosphonates 22 1.13 Proton Conductivity and Fuel Cells 27 1.14 Gel
Synthesis and Fuel Cell Membranes 30 1.15 Electron Transfer Reactions 32
1.16 Drug Delivery 34 1.17 Conclusions 39 References 40 2 Tales from the
Unexpected: Chemistry at the Surface and Interlayer Space of Layered
Organic-Inorganic Hybrid Materials Based on gamma-Zirconium Phosphate 45
2.1 Introduction 45 2.2 The Inorganic Scaffold: gamma-Zirconium Phosphate
(Microwave-Assisted Synthesis) 46 2.3 Microwave-Assisted Synthesis of
gamma-ZrP 48 2.4 Reactions 51 2.4.1 Intercalation 51 2.4.2
Microwave-Assisted Intercalation into gamma-ZrP 52 2.4.3
Phosphate/Phosphonate Topotactic Exchange 52 2.5 Labyrinth Materials:
Applications 57 2.5.1 Recognition Management 57 2.5.1.1 Chirality at Play
62 2.5.1.2 Gas and Vapour Storage 69 2.5.2 Dissymmetry and Luminescence
Signalling 71 2.5.3 Building DSSCs 75 2.5.4 Molecular Confinement 77 2.6
Conclusion and Prospects 78 References 79 3 Phosphonates in Matrices 83 3.1
Introduction: Phosphonic Acids as Versatile Molecules 83 3.2 Acid-Base
Chemistry of Phosphonic Acids 84 3.3 Interactions between Metal Ions and
Phosphonate Ligands 87 3.4 Phosphonates in 'All-Organic' Polymeric Salts 90
3.5 Phosphonates in Coordination Polymers 96 3.6 Phosphonate-Grafted
Polymers 97 3.7 Polymers as Hosts for Phosphonates and Metal Phosphonates
108 3.8 Applications 113 3.8.1 Proton Conductivity 113 3.8.2 Metal Ion
Absorption 117 3.8.3 Controlled Release of Phosphonate Pharmaceuticals 119
3.8.4 Corrosion Protection by Metal Phosphonate Coatings 125 3.8.5 Gas
Storage 125 3.8.6 Intercalation 126 3.9 Conclusions 127 References 128 4
Hybrid Materials Based on Multifunctional Phosphonic Acids 137 4.1
Introduction 137 4.2 Structural Trends and Properties of Functionalized
Metal Phosphonates 138 4.2.1 Monophosphonates 138 4.2.1.1 Metal Alkyl- and
Aryl-Carboxyphosphonates 138 4.2.1.2 Hydroxyl-Carboxyphosphonates 143
4.2.1.3 Nitrogen-funcionalized phosphonates 147 4.2.1.4 Metal
Phosphonatosulphonates 149 4.2.2 Diphosphonates 150 4.2.2.1
Aryldiphosphonates: 1,4-Phenylenebisphosphonates and Related Materials 151
4.2.2.2 1-Hydroxyethylidinediphosphonates 155 4.2.2.3
R-Amino-N,N-bis(methylphosphonates) and R-N,N'?]bis(methylphosphonates) 156
4.2.3 Polyphosphonates 163 4.2.3.1 Functionalized Metal Triphosphonates 163
4.2.3.2 Functionalized Metal Tetraphosphonates 167 4.3 Some Relevant
Applications of Multifunctional Metal Phosphonates 174 4.3.1 Gas Adsorption
175 4.3.2 Catalysis and Photocatalysis 175 4.3.3 Proton Conductivity 176
4.4 Concluding Remarks 181 References 181 5 Hybrid Multifunctional
Materials Based on Phosphonates, Phosphinates and Auxiliary Ligands 193 5.1
Introduction 193 5.1.1 Phosphonates and Phosphinates as Ligands for CPs:
Differences in Their Coordination Capabilities 195 5.1.2 The Role of the
Auxiliary Ligands 196 5.1.2.1 N-Donors 196 5.1.2.2 O-Donors 198 5.2 CPs
Based on Phosphonates and N-Donor Auxiliary Ligands 199 5.2.1
2,2'-Bipyridine and Related Molecules 199 5.2.2 Terpyridine and Related
Molecules 210 5.2.3 4,4'-Bipy and Related Molecules 210 5.2.4 Imidazole and
Related Molecules 222 5.2.5 Other Ligands 225 5.3 CPs Based on Phosphonates
and O-Donor Auxiliary Ligands 228 5.4 CPs Based on Phosphinates and
Auxiliary Ligands 233 5.5 Conclusions and Outlooks 240 References 241 6
Hybrid and Biohybrid Materials Based on Layered Clays 245 6.1 Introduction:
Clay Concepts and Intercalation Behaviour of Layered Silicates 245 6.2
Intercalation Processes in 1 : 1 Phyllosilicates 247 6.3 Intercalation in 2
: 1 Charged Phyllosilicates 252 6.3.1 Intercalation of Neutral Organic
Molecules in 2: 1 Charged Phyllosilicates 252 6.3.2 Intercalation of
Organic Cations in 2 : 1 Charged Phyllosilicates: Organoclays 256 6.4
Intercalation of Polymers in Layered Clays 263 6.4.1 Polymer-Clay
Nanocomposites 263 6.4.2 Biopolymer Intercalations: Bionanocomposites 269
6.5 Uses of Clay-Organic Intercalation Compounds: Perspectives towards New
Applications as Advanced Materials 275 6.5.1 Selective Adsorption and
Separation 276 6.5.2 Catalysis and Supports for Organic Reactions 280 6.5.3
Membranes, Ionic and Electronic Conductors and Sensors 281 6.5.4
Photoactive Materials 284 6.5.5 Biomedical Applications 284 References 286
7 Fine-Tuning the Functionality of Inorganic Surfaces Using Phosphonate
Chemistry 299 7.1 Phosphonate-Based Modified Surfaces: A Brief Overview 299
7.2 Biological Applications of Phosphonate-Derivatized Inorganic Surfaces
300 7.2.1 Phosphonate Coatings as Bioactive Surfaces 300 7.2.1.1 Supported
Lipid Bilayer 300 7.2.1.2 Surface-Modified Nanoparticles 303 7.2.2 Specific
Binding of Biological Species onto Phosphonate Surfaces for the Design of
Microarrays, 304 7.2.2.1 Single- and Double-Stranded Oligonucleotides 304
7.2.2.2 Proteins and Other Biomolecules 306 7.2.3 Calcium
Phosphate/Bisphosphonate Combination as a Route to Implantable Biomedical
Devices 308 7.3 Conclusion 314 References 315 8 Photofunctional
Polymer/Layered Silicate Hybrids by Intercalation and Polymerization
Chemistry 319 8.1 Introduction 319 8.2 Lighting Is Changing 320 8.3
Generalities 321 8.3.1 Layered Silicates 321 8.3.2 Polymer/Layered Silicate
Hybrid Structures 322 8.3.3 Methods of Preparation of PNs 323 8.4
Functional Intercalated Compounds 324 8.4.1 Dyes Intercalated Hybrids and
(Co)intercalated PNs 324 8.4.2 Light-Emitting Polymer Hybrids 331 8.4.2.1
Poly( p-Phenylene Vinylene)-Based Polymer Hybrids 331 8.4.2.2
Poly(fluorene)-Based Polymer Hybrids 333 8.5 Conclusions and Perspectives
337 References 338 9 Rigid Phosphonic Acids as Building Blocks for
Crystalline Hybrid Materials 341 9.1 Introduction 341 9.2 O verview of the
Synthesis of Rigid Functional Aromatic and Heteroaromatic Phosphonic Acids
343 9.3 Synthetic Methods to Produce Phosphonic-Based Hybrids 346 9.4
Hybrid Materials from Rigid Di- and Polyphosphonic Acids 347 9.5 Hybrid
Materials from Rigid Hetero-polyfunctional Precursors 357 9.5.1
Phosphonic-Carboxylic Acids 357 9.5.2 Phosphonic-Sulphonic Acids 366 9.5.3
O ther Functional Groups 368 9.6 Hybrid Materials from Phosphonic Acids
Linked to a Heterocyclic Compound 369 9.6.1 Aza-heterocyclic 369 9.6.2
Thio-heterocycles 373 9.7 Physical Properties and Applications 376 9.7.1
Magnetism 376 9.7.2 Fluorescence 378 9.7.3 Thermal Stability 382 9.7.4 Drug
Release 384 9.8 Conclusion and Perspectives 386 References 387 10 Drug
Carriers Based on Zirconium Phosphate Nanoparticles 395 10.1 Introduction
395 10.1.1 Zirconium Phosphates 396 10.1.2 Pre-intercalation and the
Exfoliation (Layer-by-Layer) Method 397 10.1.3 Direct Ion Exchange of ZrP
399 10.1.4 Direct Ion Exchange Using theta-ZrP 400 10.2 Drug Nanocarriers
Based on theta-ZrP 402 10.2.1 Insulin 402 10.2.2 Anticancer Agents 410
10.2.2.1 Nanoparticles and the Enhanced Permeability and Retention Effect
410 10.2.2.2 Cisplatin 410 10.2.2.3 Doxorubicin 418 10.2.2.4 Metallocenes
422 10.2.3 Neurological Agents 428 10.2.3.1 CBZ 429 10.2.3.2 DA 430 10.3
Conclusion 431 References 431