In situ clicking methylglyoxal for hierarchical self-assembly of nanotubes in supramolecular hydrogel

Abstract

Methylglyoxal (MGO) is a toxic, dicarbonyl metabolite in all living cells and its detoxification is regulated by glyoxalase I (GLOI). Herein, we rationally designed a precursor o-phenylenediamine-Phe-Phe-OH (1) which “click” reacts with MGO to yield amphiphilic methylquinoxaline-Phe-Phe-OH (2) to self-assemble into supramolecular hydrogel II (Gel II). Cryo-TEM images of Gel II suggested that there existed two orders of self-assembly to form the 32.8 nm width-nanotubes in the hydrogel. The hypothesis was validated with the analyses of the fluorescence, transmittance, and circular dichroism data of the serial dilutions of Gel II. Interference tests indicated that hydrogelation of 1 with MGO would not be affected by nitric oxide (NO). Our results suggest that 1 could be applied for specific hydrogelation with MGO, and potentially the removal of MGO in vitro.