Ordered Microdomain Structures in Saccharide–Polystyrene–Saccharide Hybrid Conjugates

Hybrid conjugates consist of synthetic polymers and naturally occurring saccharides, and are capable of microphase separation at small molecular weights to form ordered domain structures. In this study, we synthesize ABA triblock-like conjugates with polystyrene as the synthetic mid-segment and either trisaccharide maltotriose (MT) or disaccharide maltose (Mal) as the end unit. Hybrid conjugates of varying compositions are prepared by a combination of atom transfer radical polymerization and a click reaction, and their morphologies are examined by small-angle X-ray scattering and transmission electron microscopy. The MT-containing conjugates are found to form well-ordered domain structures with a sub-10 nm periodicity, and morphology transition from cylinders to spheres to disordered spheres is observed with decreasing saccharide weight fraction. The Mal-containing conjugates also show microphase separation. However, the observed domain morphologies lack regular packing due to the close proximity of polymer glass transition temperature and order-disorder transition temperature. The saccharide-containing conjugates are also found to undergo an irreversible morphology change at high temperatures, attributed to saccharide dehydration-induced pentablock-like structure formation.