Enantiocomplementary Chiral Polyhydroxyenoate: Chemoenzymatic Synthesis and Helical Structure Control

Abstract

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.

100th Anniversary of Macromolecular Science Viewpoint: Block Copolymer Particles: Tuning Shape, Interfaces, and Morphology

“…One promising direction is to investigate the 3D confined assembly of alternative macromolecular architectures, as the majority of studies in BCP particles were based on simple linear coil–coil diBCPs (Scheme ). The assembly behavior and the resulting particle shape of triBCPs, miktoarm, supramolecular combs, − branched copolymers, bottlebrushes, rigid rods, and stereocontrolled polymers − within evaporative emulsion conditions are still unknown. The importance of these novel structures lies in their potential for further tunability of interfacial curvature, chain stretching and bending penalties, and conformation asymmetries of the repeat units.…”

Organic chiral nano- and microfilaments: types, formation, and template applications

“…6e). 75 Remarkably, however, both (S)-poly-3 as well as (R)-poly-3 (independent of whether the R group was heptyl or phenyl) formed exclusively left-handed helical filaments after precipitation in CH 2 Cl 2 /n-hexane. Moreover, the acryloyl group (explicitly the CQC bond) turned out to be a prerequisite for the formation of helical filaments.…”

Enzymatic Synthesis of Polyesters and Their Bioapplications: Recent Advances and Perspectives

“…Subsequently, chemical polycondensation gave rise to chiral polyester with either aromatic or aliphatic side chains. [ 86 ] More recently, Xiang et al. [ 87 ] combined enzymatic ROP with ring‐opening metathesis polymerization (ROMP), a non‐radical polymerization using Grubbs catalyst (ruthenium alkylidene).…”