Shear recovery and temperature stability of Ca2+ and Ag+ glycolipid fibrillar metallogels with unusual $\beta$-sheet-like domains

TL;DR

This study investigates the shear recovery and temperature stability of biobased glycolipid fibrillar metallogels containing Ca2+ and Ag+ ions, revealing their unique structural features and exceptional thermal resistance, with potential for sustainable material applications.

Contribution

It introduces a novel SAFiN hydrogel with -sheet-like domains formed by glycolipid fibrillation triggered by metal ions, demonstrating unprecedented temperature stability and rapid mechanical recovery.

Findings

Ca2+ hydrogel stable up to 55b0C

Ag+ hydrogel stable up to 70b0C

Presence of -sheet-like domains in SAFiN gels

Abstract

Low-molecular weight gelators (LMWG) are small molecules (Mw < ~1 kDa), which form self-assembled fibrillar networks (SAFiN) hydrogels in water. The great majority of SAFiN gels is described by an entangled network of self-assembled fibers, in analogy to a polymer in a good solvent. Here, fibrillation of a biobased glycolipid bolaamphiphile is triggered by Ca2+ or Ag+ ions, added to its diluted micellar phase. The resulting SAFiN, which forms hydrogel above 0.5 wt%, has a ``nano-fishnet'' structure, characterized by a fibrous network of both entangled fibers and $\beta$-sheets-like rafts, generally observed for silk fibroin, actin hydrogels or mineral imogolite nanotubes, but generally not known for SAFiN. This work focuses on the strength of the SAFIN gels, their fast recovery after applying a mechanical stimulus (strain) and their unusual resistance to temperature, studied by coupling rheology to small angle X-ray scattering (rheo-SAXS) using synchrotron radiation. The Ca2+-based hydrogel keeps its properties up to 55{\textdegree}C, while the Ag+-based gel shows a constant elastic modulus up to 70{\textdegree}C, without appearance of any gel-to-sol transition temperature. Furthermore, the glycolipid is obtained by fermentation from natural resources (glucose, rapeseed oil), thus showing that naturally-engineered compounds can have unprecedented properties, when compared to the wide range of chemically derived amphiphiles.