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Book Details
Abstract
The term ‘miktoarm polymers’ refers to asymmetric branched macromolecules, a relatively new entry to the macromolecular field. Recent advances in their synthesis and intriguing supramolecular chemistry in a desired medium has seen a fast expansion of their applications. The composition of miktoarm polymers can be tailored and even pre-defined to allow a desired combination of functions, meaning polymer chemists can have complete control of the overall architecture of these macromolecules. By carefully selecting the composition, they can create supramolecular structures with intriguing properties, particularly for applications in biology.
Miktoarm Star Polymers features chapters from experts actively working in this field, and provides the reader with a unique introduction to the fundamental principles of this exciting macromolecular system. Topics covered include the design, synthesis, characterization, self-assembly and applications of miktoarm polymers.
The book is an excellent overview and up to date guide to those working in research in polymer chemistry, materials science, and polymers for medical applications.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Miktoarm Star Polymers: From Basics of Branched Architecture to Synthesis, Self-assembly and Applications | i | ||
| Preface | vii | ||
| Contents | ix | ||
| Chapter 1 - Miktoarm Star (µ-Star) Polymers: A Successful Story | 1 | ||
| 1.1 The Genesis of Miktoarm (µ-Star) Star Polymers | 1 | ||
| 1.2 Synthesis of Miktoarm Star (µ-Star) Polymers | 6 | ||
| 1.2.1 Divinylbenzene (Homopolymerizable Linking Agent) | 6 | ||
| 1.2.2 Double Diphenylethylenes (Non-Homopolymerizable Linking Agents) | 7 | ||
| 1.2.3 Chlorosilanes | 8 | ||
| 1.2.3.1 Trichloromethylsilane and Tetrachlorosilane | 9 | ||
| 1.2.3.2 1,2-Bis(trichlorosilyl)ethane | 12 | ||
| 1.2.3.3 Hexadecachlorosilane (SiCl16) and Tetrahexicontachlorosilane (SiCl64) | 13 | ||
| 1.3 Miktoarm-Based Polymers with Complex Architectures | 13 | ||
| 1.4 Model Polyethylenes | 15 | ||
| 1.5 Individual Methods for the Synthesis of Miktoarm Stars | 15 | ||
| 1.5.1 3µ-Star Copolymers of the A2B Type | 15 | ||
| 1.5.2 µ-Stars of the AnB Type | 16 | ||
| 1.5.3 µ-Star Copolymers of the AnBm Type | 16 | ||
| 1.5.4 µ-Star Terpolymers of the ABC Type | 18 | ||
| 1.5.5 6µ-Star Copolymers of the A2B4 Type | 20 | ||
| 1.5.6 Miktoarm Macromolecular Chimeras | 21 | ||
| 1.6 Microphase Separation of Miktoarm Stars | 21 | ||
| 1.7 Concluding Remarks | 25 | ||
| Acknowledgements | 26 | ||
| References | 26 | ||
| Chapter 2 - Precise Synthesis of Multi-Component Miktoarm Star Polymers by a New Conceptual Iterative Methodology Using Living Anionic Polymerization | 31 | ||
| 2.1 Introduction | 32 | ||
| 2.2 Synthesis of Multi-Arm and Multi-Component Miktoarm Star Polymers by the Iterative Methodology Using a Difunctional Compound ... | 34 | ||
| 2.2.1 Iterative Methodology Using 1-(4-(3-Bromopropyl)phenyl)-1-phenylethylene | 34 | ||
| 2.2.2 Iterative Methodology Using 3 and Either 1,3-Bis (1-phenylethenyl)benzene or 1,1-Bis(3-(1-phenylethenyl)phenyl)ethylene | 35 | ||
| 2.2.3 Iterative Methodology Using 3,5-Bis(3-(4-(1-phenylethenyl)phenyl)propoxy)benzyl Bromide | 37 | ||
| 2.2.4 Synthesis of Miktoarm Star Polymers Using Intermediate Polymer Anions Prepared by the Iterative Methodology | 41 | ||
| 2.2.5 Iterative Methodology Using 6-Bromo-3-methylene-1-hexene | 43 | ||
| 2.3 Second-Generation Iterative Methodology | 45 | ||
| 2.3.1 Second-Generation Iterative Methodology Using a Difunctional DPE Anion Bearing Trimethylsilyl and Tert-Butyldimethylsilyl E... | 47 | ||
| 2.3.2 Second-Generation Iterative Methodology Using a Trifunctional DPE Anion Bearing Trimethylsilyl, Tert-Butyldimethylsilyl, an... | 49 | ||
| 2.3.3 Second-Generation Iterative Methodology Using a DPE Anion Bearing a 1,3-Dioxolane Group | 50 | ||
| 2.3.4 Second-Generation Iterative Methodology Using 9 and In-Chain Block Copolymer Anions | 51 | ||
| 2.4 Conclusions | 53 | ||
| References | 54 | ||
| Chapter 3 - Facile Synthesis of Multicomponent Star Copolymers via Controlled Polymerization and Click Chemistry | 56 | ||
| 3.1 Introduction | 56 | ||
| 3.2 Miktoarm Stars Synthesized by Living/Controlled Polymerization | 59 | ||
| 3.2.1 ‘Core First’ Approach | 59 | ||
| 3.2.2 ‘Arm First’ Approach | 62 | ||
| 3.2.3 ‘In–Out’ Method | 63 | ||
| 3.2.4 LAP-Based General and Iterative Methodologies | 64 | ||
| 3.3 Synthesis of Miktoarm Stars via Combinatorial Approaches Involving Click Chemistry | 67 | ||
| 3.3.1 Combinational Methods Involving CuAAC/SPAAC | 67 | ||
| 3.3.2 Combinatorial Approaches Involving DA/HDA Reactions | 73 | ||
| 3.3.3 Combinatorial Approaches with Thiol-Based Click Reactions | 75 | ||
| 3.3.4 Combinatorial Approaches Involving Other Click Reactions | 76 | ||
| 3.3.5 Combinatorial Methods Using Dual and Multiple Click Reactions | 76 | ||
| 3.3.5.1 Combination of Thiol–Ene and CuAAC Reactions | 77 | ||
| 3.3.5.2 Combination of CuAAC and DA/HDA Reactions | 77 | ||
| 3.3.5.3 Combination of CuAAC and Nitroxide Radical Coupling (NRC) Reactions | 77 | ||
| 3.3.5.4 Combination of CuAAC, DA, and NRC Reactions | 77 | ||
| 3.3.5.5 Combination of Thiol–Ene, CuAAC, and DA Reactions | 78 | ||
| 3.4 Conclusions and Outlook | 78 | ||
| Acknowledgements | 79 | ||
| References | 79 | ||
| Chapter 4 - Use of Click Chemistry as a Coupling Strategy for the Synthesis of Miktoarm Star Polymers | 90 | ||
| 4.1 Introduction | 90 | ||
| 4.2 Cu(i)-Catalyzed 1,3-Dipolar Azide–alkyne Cycloaddition Reaction (CuAAC) | 94 | ||
| 4.3 Diels–Alder Click Reactions | 102 | ||
| 4.4 Thiol-Based Click Reactions | 105 | ||
| 4.5 Atom Transfer Nitroxide Radical Coupling (ATNRC) Click Reactions | 108 | ||
| 4.6 Aldehyde–Aminooxy Click Reactions | 109 | ||
| References | 110 | ||
| Chapter 5 - Micellar and Emulsion-Assisted Drug Delivery: Comparison of Miktoarm Star Polymers and Block Copolymers | 116 | ||
| 5.1 Introduction | 116 | ||
| 5.2 Stimulus-Responsive Micellisation and Drug Delivery | 117 | ||
| 5.2.1 Synthesis of Block Copolymer and Miktoarm Star Polymer | 117 | ||
| 5.2.2 Micellisation and Drug Delivery | 120 | ||
| 5.2.2.1 pH-Responsive Delivery | 122 | ||
| 5.2.2.2 Temperature-Responsive Delivery | 128 | ||
| 5.2.2.3 Redox-Responsive Delivery | 129 | ||
| 5.2.2.4 Multi-Responsive Delivery | 130 | ||
| 5.3 Emulsions | 133 | ||
| 5.3.1 Emulsions Stabilised by Linear/Branched Di- and Triblock Copolymers | 133 | ||
| 5.3.2 Emulsions Stabilised by Star-Shaped Homo/Block Polymers and Bottle-Brush Copolymers | 136 | ||
| 5.3.3 Emulsions Stabilised by Miktoarm Polymers | 139 | ||
| 5.4 Conclusions and Perspective | 141 | ||
| List of Abbreviations | 142 | ||
| References | 144 | ||
| Chapter 6 - Synthetic Articulation of Miktoarm Polymers for Applications in Biology | 150 | ||
| 6.1 Introduction | 150 | ||
| 6.2 Miktoarm Polymers vs. Traditional Block Co-Polymers and Hyperbranched Structures for Biological Applications | 153 | ||
| 6.3 Challenges Toward the Synthesis of Miktoarm Polymers | 153 | ||
| 6.3.1 Methods Based on Living Anionic Polymerization | 154 | ||
| 6.3.1.1 Silyl Chloride Based Method66–69 | 154 | ||
| 6.3.1.2 Divinylbenzene (DVB) Based Method | 155 | ||
| 6.3.1.3 Diphenylethylene (DPE) Derivative Based Method | 155 | ||
| 6.3.1.4 Iterative Based Method | 156 | ||
| 6.3.1.5 Other Methodologies | 158 | ||
| 6.3.2 Methods Based on Living/Controlled Radical Polymerization | 162 | ||
| 6.3.2.1 Arm First Method97–99 | 162 | ||
| 6.3.2.2 Core First Method103,104 | 163 | ||
| 6.3.2.3 Click Chemistry36,106–110 | 164 | ||
| 6.4 Miktoarm Star Polymers for Drug Delivery Applications | 166 | ||
| 6.4.1 Physical Encapsulation of Drugs into Miktoarm Polymer-Based Self-Assembled Nanostructures | 166 | ||
| 6.4.2 Stimulus-Responsive Miktoarm Star Polymers | 170 | ||
| 6.4.3 Chemical Conjugation of Drugs to Multi-Arm Mixed Star Polymers | 172 | ||
| 6.5 Summary and Future Outlook | 173 | ||
| References | 174 | ||
| Chapter 7 - Supramolecular (Miktoarm) Star Polymers: Self-Assembly and Applications | 181 | ||
| 7.1 Introduction | 181 | ||
| 7.2 Supramolecular Chemistry | 184 | ||
| 7.2.1 Supramolecular Motifs | 184 | ||
| 7.2.2 Orthogonality of Supramolecular Motifs | 186 | ||
| 7.3 (Miktoarm) Star Polymers Based on Supramolecular Recognition | 187 | ||
| 7.3.1 Hydrogen Bonding | 189 | ||
| 7.3.2 Cyclodextrins | 193 | ||
| 7.3.3 Other Inclusion Complexes | 201 | ||
| 7.3.4 Metal Complexes | 204 | ||
| 7.3.5 Other Supramolecular Motifs | 207 | ||
| 7.4 Conclusions and Outlook | 207 | ||
| Acknowledgements | 208 | ||
| References | 208 | ||
| Subject Index | 217 |