ADMET polymerization of $\alpha$,$\omega$-unsaturated glycolipids: synthesis and physico-chemical properties of the resulting polymers

TL;DR

This study explores the synthesis of unsaturated glycolipid polymers via ADMET polymerization, analyzing their physical properties, phase behavior, and self-assembly characteristics.

Contribution

It introduces a new method for synthesizing trehalose-based unsaturated glycolipid polymers using enzymatic esterification and ADMET polymerization.

Findings

Successful synthesis of trehalose diundecenoate and copolymers confirmed by NMR and SEC.

Phase separation behavior characterized by DSC and X-ray scattering.

Self-assembly properties studied by DLS in aqueous solutions.

Abstract

Trehalose diesters exhibiting $\alpha$,$\omega$-unsaturation are glycolipids which can be easily polymerized by ADMET (acyclic diene metathesis) polymerization. In this paper, enzymatic esterification was performed to selectively esterify primary hydroxyl groups of trehalose (6 and 6'-positions) with vinyl undecenoate. The vinyl ester was beforehand obtained by palladium-catalyzed transesterification of undecenoic acid with vinyl acetate. The resulting trehalose diundecenoate was homopolymerized and copolymerized with undecenyl undecenoate in order to obtain random copolymers with different compositions. The synthesis of such copolymers was confirmed by 1 H NMR spectroscopy and size exclusion chromatography (SEC). Their solid-state phase separation were investigated by DSC and X-ray scattering as function of temperature and their solution self-assembly was investigated by dynamic light scattering (DLS) in water.