Supramolecular polymeric materials via cyclodextrin-guest interactions.
TL;DR: This Account demonstrates some of the great advances in the development of supramolecular materials through host-guest interactions within the last 10 years, and uses the molecular recognition of CDs to achieve macroscopic self-assemblies, and this chemistry can direct these macroscopy objects into even larger aggregated structures.
Abstract: CONSPECTUS: Cyclodextrins (CDs) have many attractive functions, including molecular recognition, hydrolysis, catalysis, and polymerization. One of the most important uses of CDs is for the molecular recognition of hydrophobic organic guest molecules in aqueous solutions. CDs are desirable host molecules because they are environmentally benign and offer diverse functions. This Account demonstrates some of the great advances in the development of supramolecular materials through host-guest interactions within the last 10 years. In 1990, we developed topological supramolecular complexes with CDs, polyrotaxane, and CD tubes, and these preparation methods take advantage of self-organization between the CDs and the polymers. The combination of polyrotaxane with αCD forms a hydrogel through the interaction of αCDs with the OH groups on poly(ethylene glycol). We categorized these polyrotaxane chemistries within main chain type complexes. At the same time, we studied the interactions of side chain type supramolecular complexes with CDs. In these systems the guest molecules modified the polymers and selectively formed inclusion complexes with CDs. The systems that used low molecular weight compounds did not show such selectivity with CDs. The multivalency available within the complex cooperatively enhances the selective binding of CD with guest molecules via the polymer side chains, a phenomenon that is analogous to binding patterns observed in antigen-antibody complexes. To incorporate the molecular recognition properties of CDs within the polymer side chains, we first prepared stimuli-responsive sol-gel switching materials through host-guest interactions. We chose azobenzene derivatives for their response to light and ferrocene derivatives for their response to redox conditions. The supramolecular materials were both redox-responsive and self-healing, and these properties resulted from host-guest interactions. These sol-gels with built in switches gave us insight for creating materials that were self-healing or could serve as artificial muscle. Furthermore, we developed another self-healing material with CD inclusion complexes that showed selective self-healing properties after its surface was cut. These CD self-healing materials do not include chemical cross-linkers; instead the inclusion complex of CDs with guest molecules stabilized the material's strength. However, by introducing chemical cross-linkers into the hydrogels, we produced materials that could expand and contract. The chemical cross-linked hydrogels with responsive groups bent in response to external stimuli, and the cross-linkers controlled the ratio of inclusion complexes. Furthermore, we used the molecular recognition of CDs to achieve macroscopic self-assemblies, and this chemistry can direct these macroscopic objects into even larger aggregated structures. As we have demonstrated, reversible host-guest interactions have tremendous potential for the creation of a wide variety of functional materials.
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TL;DR: An overview of adaptable‐hydrogel design considerations and linkage selections is presented, with a focus on various cell‐compatible crosslinking mechanisms that can be exploited to form adaptable hydrogels for tissue engineering.
Abstract: Adaptable hydrogels have recently emerged as a promising platform for three-dimensional (3D) cell encapsulation and culture. In conventional, covalently crosslinked hydrogels, degradation is typically required to allow complex cellular functions to occur, leading to bulk material degradation. In contrast, adaptable hydrogels are formed by reversible crosslinks. Through breaking and re-formation of the reversible linkages, adaptable hydrogels can be locally modified to permit complex cellular functions while maintaining their long-term integrity. In addition, these adaptable materials can have biomimetic viscoelastic properties that make them well suited for several biotechnology and medical applications. In this review, an overview of adaptable-hydrogel design considerations and linkage selections is presented, with a focus on various cell-compatible crosslinking mechanisms that can be exploited to form adaptable hydrogels for tissue engineering.
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TL;DR: This critical review of the recent development of supramolecular polymeric systems involving metal-ligand interactions and host-guest molecular recognition is addressed and classified depending on the types of macrocyclic hosts are highlighted.
Abstract: Supramolecular polymers constructed by orthogonal self-assembly based on host–guest and metal–ligand interactions are attracting increasing attention currently because of their interesting properties and potential applications. Host–guest interactions impart these polymers with good selectivity and convenient enviro-responsiveness, and metal–ligand interactions endow them with various coordination geometries, strong yet tunable coordination binding abilities, as well as magnetic, redox, photophysical, and electrochromic properties. Therefore, supramolecular polymers constructed by orthogonal host–guest and metal–ligand interactions have wide applications in the fields of soft matter, fluorescence sensing, heterocatalysis, electronics, gas storage, etc. In this critical review, we will address the recent development of supramolecular polymeric systems involving metal–ligand interactions and host–guest molecular recognition. Specifically, we classify the related supramolecular polymers depending on the types of macrocyclic hosts, and highlight their intriguing properties originating from the elegant combination of host–guest complexation and metal centers.
461 citations
TL;DR: This work employed two different kinds of host-guest inclusion complexes of β-cyclodextrin with adamantane and ferrocene to bind polymers together to form a supramolecular hydrogel (βCD-Ad-Fc gel), which showed self-healing ability when damaged and responded to redox stimuli by expansion or contraction.
Abstract: Supramolecular materials cross-linked between polymer chains by noncovalent bonds have the potential to provide dynamic functions that are not produced by covalently cross-linked polymeric materials. We focused on the formation of supramolecular polymeric materials through host-guest interactions: a powerful method for the creation of nonconventional materials. We employed two different kinds of host-guest inclusion complexes of β-cyclodextrin (βCD) with adamantane (Ad) and ferrocene (Fc) to bind polymers together to form a supramolecular hydrogel (βCD-Ad-Fc gel). The βCD-Ad-Fc gel showed self-healing ability when damaged and responded to redox stimuli by expansion or contraction. Moreover, the βCD-Ad-Fc gel showed a redox-responsive shape-morphing effect. We thus succeeded in deriving three functions from the introduction of two kinds of functional units into a supramolecular material.
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TL;DR: Developments in molecular and supramolecular design and engineering open perspectives towards the realization of molecular photonic, electronic, and ionic devices that would perform highly selective recognition, reaction, and transfer operations for signal and information processing at the molecular level.
Abstract: Supramolecular chemistry is the chemistry of the intermolecular bond, covering the structures and functions of the entities formed by association of two or more chemical species. Molecular recognition in the supermolecules formed by receptor-substrate binding rests on the principles of molecular complementarity, as found in spherical and tetrahedral recognition, linear recognition by coreceptors, metalloreceptors, amphiphilic receptors, and anion coordination. Supramolecular catalysis by receptors bearing reactive groups effects bond cleavage reactions as well as synthetic bond formation via cocatalysis. Lipophilic receptor molecules act as selective carriers for various substrates and make it possible to set up coupled transport processes linked to electron and proton gradients or to light. Whereas endoreceptors bind substrates in molecular cavities by convergent interactions, exoreceptors rely on interactions between the surfaces of the receptor and the substrate; thus new types of receptors, such as the metallonucleates, may be designed. In combination with polymolecular assemblies, receptors, carriers, and catalysts may lead to molecular and supramolecular devices, defined as structurally organized and functionally integrated chemical systems built on supramolecular architectures. Their recognition, transfer, and transformation features are analyzed specifically from the point of view of molecular devices that would operate via photons, electrons, or ions, thus defining fields of molecular photonics, electronics, and ionics. Introduction of photosensitive groups yields photoactive receptors for the design of light-conversion and charge-separation centers. Redox-active polyolefinic chains represent molecular wires for electron transfer through membranes. Tubular mesophases formed by stacking of suitable macrocyclic receptors may lead to ion channels. Molecular self-assembling occurs with acyclic ligands that form complexes of double-helical structure. Such developments in molecular and supramolecular design and engineering open perspectives towards the realization of molecular photonic, electronic, and ionic devices that would perform highly selective recognition, reaction, and transfer operations for signal and information processing at the molecular level.
3,124 citations
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1,146 citations
TL;DR: The formation of supramolecular hydrogels and their redox-responsive and self-healing properties due to host–guest interactions are reported and cyclodextrin is employed as a host molecule because it is environmentally benign and has diverse applications.
Abstract: Stimulus-responsive hydrogels have previously been developed that display heat-, light-, pH- or redox-induced sol–gel transitions. Nakahata et al. develop a self-healing supramolecular hydrogel based on host–guest polymers in which redox potential can induce a reversible sol–gel phase transition.
1,140 citations