Dynamic-Covalent Crosslinking of Benzenetricarboxamide-Phenylboronate Conjugates.

Abstract

In an effort to augment the function of supramolecular biomaterials, recent efforts have explored the creation of hybrid materials that couple supramolecular and covalent components. Here, the benzenetricarboxamide (BTA) supramolecular polymer motif is modified to present a phenylboronic acid (PBA) in order to promote the crosslinking of 1D BTA stacks by PBA-diol dynamic-covalent bonds through the addition of a multi-arm diol-bearing crosslinker. Interestingly, the combination of these two motifs serves to frustrate the resulting assembly process, yielding hydrogels with worse mechanical properties than those prepared without the multi-arm diol crosslinker. Both systems with and without the crosslinker do, however, respond to the presence of a physiological level of glucose with a reduction in their mechanical integrity; repulsive electrostatic interactions in the BTA stacks occur in both cases upon glucose binding, with added competition from glucose with PBA-diol bonds amplifying glucose response in the hybrid material. Accordingly, the present results point to an unexpected outcome of reduced hydrogel mechanics, yet increased glucose response, when two disparate dynamic motifs of BTA supramolecular polymerization and PBA-diol crosslinking are combined, offering a vision for future preparation of glucose-responsive supramolecular biomaterials.