Low-molecular-weight (LMW) molecules of biological origin like microbial glycolipid biosurfactants can selfassemble in water, with a tunable structure by a soft chemistry approach (pH, temperature, and ionic strength). The unique molecular structure of microbial glycolipids gives possible access to a wide variety of aqueous self-assembled structures, although highly unpredictable beforehand. The glycolipid presented here consists in a glucose group linked to a C18:1-cis fatty acid (G-C18:1) and produced by the fermentation of Starmerella bombicola ΔugtB1. Due to the carboxylic group of the fatty acid, the supramolecular self-assembly is pH dependent. In the pH range 5−7, G-C18:1 forms vesicles, while above pH 7, it forms a micellar phase. Adding a wide range of metal salts

Calcium or silver ions drive self-assembly of natural glycolipid low-molecular weight gelators (LMWGs) into a fibrillar network hydrogel with a unique “nano-fishnet” structure, characterized by entanglement and β-sheet-like rafts.

Amphiphiles obtained by microbial fermentation, known as biosurfactants or bioamphiphiles, are reviewed in terms of their solution experimental and theoretical self-assembly properties, interface properties and interactions with macromolecules.

Low-molecular weight gelators (LMWGs) are small molecules (Mw < ∼1 kDa), which form self-assembled fibrillar network (SAFiN) hydrogels in water.