Enantiocomplementary Chiral Polyhydroxyenoate: Chemoenzymatic Synthesis and Helical Structure Control.

Here, we present the chemoenzymatic synthesis of two pairs of configuration-customized unsaturated chiral polyesters and discover that they are able to self-assemble into a helical superstructure. The chiral ( R )- or ( S )-polyesters with a polar unsaturated main-chain and an apolar side chain were designed to be stereoregular and amphiphilic-like. The solvent polarity, stereoregularity, unsaturated bond in the backbone and the structure of side chains were found to be the key factors to affect the self-assembly performance of the chiral polyesters. As the solvent polarity increased, the nanostructures of stereoregular unsaturated polyesters transformed from spheres to helical fibers, while there was no such transformation for the racemic or saturated polyesters.