Sugar-Based Polymers from d-Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release.

Enyne monomers derived from D-xylose underwent living cascade polymerizations to prepare new polymers with a ring-opened sugar and degradable linkage incorporated into every repeat unit of the backbone. Polymerizations were well-controlled and had living character, which enabled the preparation of high molecular weight polymers with narrow molecular weight dispersity values and a block copolymer. By tuning the type of acid-sensitive linkage (hemi-aminal ether, acetal, or ether functional groups), we could change the degradation profile of the polymer and the identity of the resulting degradation products. For instance, the large difference in degradation rates between hemi-aminal ether and ether-based polymers enabled the sequential degradation of a block copolymer. Furthermore, we exploited the generation of furan-based degradation products, from an acetal-based polymer, to achieve the release of covalently bound reporter molecules upon degradation.