Development Of Supramolecular Materials Research Articles

Ionic surfactants as assembly crosslinkers triggered supramolecular membrane with 2D↔3D conversion under multiple stimulus

HypothesisGeneral strategies leading to 2D assemblies promise a significant step forward in the development of supramolecular materials with diversity and superiority. Considering molecular packing parameter indicates a connection between molecular geometry and aggregate morphology, we predict the introduction of ionic surfactants as assembly crosslinker would be endowed to develop a methodology of 2D supramolecular assembles. ExperimentsIn this work, by introducing ionic surfactants such as sodium dodecylsulfate (SDS), the molecular packing parameter P in bolaamphiphile (A2G) system was increased, which successfully manipulated the transformation of the 3D vesicles into 2D membranes. This 2D membranes further showed excellent light and enzyme response, and thus 2D to 3D morphological conversion can be rationally controlled via UV/Vis light irradiation and alternate addition of β-CD and α-amylase. Significantly, the 2D feature revealed not only a remarkable fluorescence enhancement to luminescent molecules but also the ability to effectively remove pollutants from water through filtration. FindingsWe report a general and facile strategy for the construction of 2D supramolecular membranes, initiated by introducing ionic surfactants as assembly crosslinker to increase P. In the existence of stimulus response factors, 2D↔3D morphological conversion can be further controlled in a flexible manner, which opens up a new paradigm leading to interconvertible supramolecular materials.

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

Evolution of supramolecular chirality from self-assembly of achiral compounds and control over its handedness is closely related to the evolution of life and development of supramolecular materials with desired handedness. Here we report a system where the entire process of induction, control and locking of supramolecular chirality can be manipulated by light. Combination of triphenylamine and diacetylene moieties in the molecular structure allows photoinduced self-assembly of the molecule into helical aggregates in a chlorinated solvent by visible light and covalent fixation of the aggregate via photopolymerization by ultraviolet light, respectively. By using visible circularly polarized light, the supramolecular chirality of the resulting aggregates is selectively and reversibly controlled by its rotational direction, and the desired supramolecular chirality can be arrested by irradiation with ultraviolet circularly polarized light. This methodology opens a route to ward the formation of supramolecular chiral conducting nanostructures from the self-assembly of achiral molecules.

Supramolecular polymeric materials via cyclodextrin-guest interactions.

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.