Presenting the work of pioneering experts in this exciting field of supramolecular polymer chemistry, this monograph covers an extensive range of applications, including drug delivery and catalysis. It focuses on new structures and phenomena of cyclodextrin-based supramolecular polymers and many other compound classes. While providing a deeper insight in macromolecular recognition and the mechanisms of living systems, this book also introduces fascinating novel phenomena beyond natural systems.
Akira Harada is a professor of Graduate School of Science at Osaka University. Having obtained his Ph.D. from Osaka University in 1977, he spent most of his career working for the same university. During that time, he worked for IBM research as a visiting scientist and as a Post Doc at Colorado State University. After he was working at the Institute of Scientific and Industrial Research (ISIR) in Osaka University, he became professor at Graduate School of Science, Osaka University in 1988. He was also a visiting scientist at the Scripps Institute. He has received several awards including IBM Science Award, Osaka Science Award, Japan Polymer Society Award, Cyclodextrin Society Award, Izatt-Christensen International Award and the Medal with Purple Ribbon from the Japanese Government. His research interests cover supramolecular chemistry, polymer synthesis and assembly of bio-related polymers.
Preface PART I: Formation of Supramolecular Polymers MULTIPLE HYDROGEN-BONDED SUPRAMOLECULAR POLYMERS Introduction General Concepts of Hydrogen-Bonding Motifs Hydrogen-Bonded Main-Chain Supramolecular Polymers From Supramolecular Polymers to Supramolecular Materials Future Perspectives CYCLODEXTRIN-BASED SUPRAMOLECULAR POLYMERS Introduction Supramolecular Polymers in the Solid State Formation of Homo-Intramolecular and Intermolecular Complexes by CDs-Guest Conjugates Formation of Intermolecular Complexes by CD and Guest Dimers Artificial Molecular Muscle Based on c2-Daisy Chain Conclusion and Outlook SUPRA-MACROMOLECULAR CHEMISTRY: TOWARD DESIGN OF NEW ORGANIC MATERIALS FROM SUPRAMOLECULAR STANDPOINTS Introduction Small Molecules, Macromolecules, and Supramolecules: Design of their Composite Materials Conclusion and Outlook POLYMERIZATION WITH DITOPIC CAVITAND MONOMERS Introduction Cavitands Self-Assembly of Ditopic Cavitand Monomers Conclusions and Outlook PART II: Supramolecular Polymers with Unique Structures POLYMERS CONTAINING COVALENTLY BONDED AND SUPRAMOLECULARLY ATTACHED CYCLODEXTRINS AS SIDE GROUPS Polymers with Covalently Bonded Cyclodextrins as Side Groups Side Chain Polyrotaxanes and Polypseudorotaxanes ANTIBODY DENDRIMERS AND DNA CATENANES Molecular Recognition in Biological Systems Antibody Supramolecules DNA Supramolecules Conclusions CROWN ETHER-BASED POLYMERIC ROTAXANES Introduction Daisy Chains Supramolecular Polymers Dendritic Rotaxanes Dendronized Polymers Main Chain Rotaxanes Based on Polymeric Crowns (Including Crosslinked Systems) Side Chain Rotaxanes Based on Pendent Crowns Polyrotaxanes Polyrotaxanes Polymeric End Group Pseudorotaxanes Chain Extension and Block Copolymers from End Groups Star Polymers from Crown Functionalized Polymers PART III: Properties and Functions PROCESSIVE ROTAXANE CATALYSTS Introduction Results and Discussion Conclusion EMERGING BIOMEDICAL FUNCTIONS THROUGH 'MOBILE' POLYROTAXANES Introduction Multivalent Interaction using Ligand-Conjugated Polyrotaxanes The Formation of Polyrotaxane Loops as a Dynamic Interface Cytocleavable Polyrotaxanes for Gene Delivery Conclusion Appendix SLIDE-RING MATERIALS USING POLYROTAXANE Introduction Pulley Effect of Slide-Ring Materials Synthesis of Slide-Ring Materials Scattering Studies of Slide-Ring Gels Mechanical Properties of Slide-Ring Gels Sliding Graft Copolymers Recent Trends of Slide-Ring Materials Concluding Remarks STIMULI-RESPONSIVE SYSTEMS Introduction Stimuli and Responses Examples of Stimuli-Responsive Supramolecular Polymer Systems Concluding Remarks PHYSICAL ORGANIC CHEMISTRY OF SUPRAMOLECULAR POLYMERS Introduction and Background Linear Supramolecular Polymers Cross-Linked SPs Networks Hybrid Polymer Gels Conclusion TOPOLOGICAL POLYMER CHEMISTRY: A QUEST FOR STRANGE POLYMER RINGS Introduction Systematic Classification of Nonlinear Polymer Topologies Topological Isomerism Designing Unusual Polymer Rings by Electrostatic Self-Assembly and Covalent Fixation Conclusion and Future Perspectives STRUCTURE AND DYNAMIC BEHAVIOR OF ORGANOMETALLIC ROTAXANES Introduction Conclusion Appendix: Experimental Section POLYROTAXANE NETWORKS AS A TOPOLOGICALLY CROSS-LINKED POLYMER: SYNTHESIS AND PROPERTIES Introduction Linking of Wheels of Main-Chain-Type Polyrotaxane - Structurally Defined Polyrotaxane Network Linking of Macrocyclic Units of Polymacrocycle with Axle Unit to Directly Yield a Polyrotaxane Network Linking of Wheels of Polyrotaxane Cross-Linker to Afford Polyrotaxane Network: Design of the Cross-Linker Conclusion FROM CHEMICAL TOPOLOGY TO MOLECULAR MACHINES Introduction Copper(I)-Templated Synthesis of Catenanes: The 'Entwining' Approach and the 'Gathering and Threading' Strategy Molecular Knots Molecular Machines Based on Catenanes and Rotaxanes Two-Dimensional Interlocking Arrays A rotaxane Acting as an Adjustable Receptor: Toward a Molecular 'Press' Conclusion