In this edge article we report the preparation of a supramolecular carbohydrate hydrogel containing cyclodextrin vesicles as 3D junctions. A cellulose polymer is randomly modified with hydrophobic side groups that act as guests for the cyclodextrin hosts on the surface of the vesicles. Hence, the vesicles interconnect the polymer chains into a three-dimensional network and act as multivalent linkages. The resulting gel shows significant shear-thinning and self-healing properties, which make it highly suitable for applications that require injectability. Furthermore, SAXS and cryo-TEM measurements indicate that intact vesicles are present in the gel matrix.
The ligation of gold(I) metalloamphiphiles with biomolecules is reported, using water-soluble Au -N-alkynyl substituted maleimide complexes. For this purpose, two different polar ligands were applied: 1) a neutral, dendritic tetraethylene glycol-functionalized phosphane and 2) a charged, sulfonated N-heterocyclic carbene (NHC). The retro Diels-Alder reaction of a furan-protected maleimide gold(I) complex, followed by cycloaddition with a diene-functionalized biotin under mild conditions leads to a novel gold(I) metalloamphiphile. The strong streptavidin-biotin binding affinity in buffered aqueous solution of the resulting biotin alkynyl gold(I) phosphane conjugate remains intact. The cytotoxicity of the biotinylated gold(I) complex against a T47D human breast cancer cell line is higher than for cisplatin.
We report the synthesis of an alkyne functionalised NHC-Au(i)-complex which is conjugated with amphiphilic oligopeptides using a copper(i) catalysed cycloaddition. The resulting Au(i)-metalloamphiphiles are shown to self-assemble into charge-regulated stimulus-responsive supramolecular polymers in water via a weakly cooperative polymerisation mechanism.
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