Biocatalytic production of novel glycolipids with cellodextrin phosphorylase

► Cellodextrin phosphorylase from Clostridium stercorarium is able to synthesize new glycolipids. ► Glucolipid and sophorolipid acceptors are extended with one or two glucosyl moieties. ► Product precipitation drives the reactions to near completion and facilitates purification. ► The glycosyl donor α-galactose 1-phosphate allows the synthesis of lactolipid in highly pure form. Glycolipids have gained increasing attention as natural surfactants with a beneficial environmental profile. They are typically produced by fermentation, which only gives access to a limited number of structures. Here we describe the biocatalytic production of novel glycolipids with the cellodextrin phosphorylase from Clostridium stercorarium. This enzyme was found to display a broad donor and acceptor specificity, allowing the synthesis of five different products. Indeed, using either α-glucose 1-phosphate or α-galactose 1-phosphate as glycosyl donor, sophorolipid as well as glucolipid could be efficiently glycosylated. The transfer of a glucosyl moiety afforded a mixture of products that precipitated from the solution, resulting in near quantitative yields. The transfer of a galactosyl moiety, in contrast, generated a single product that remained in solution at thermodynamic equilibrium. These glycolipids not only serve as a new class of biosurfactants, but could also have applications in the pharmaceutical and nanomaterials industries.