Recent advances in the synthesis of biodegradable polyesters by sustainable polymerization: lipase-catalyzed polymerization.

Over the past three decades, enzymatic polymerization has dramatically developed and gradually broadened as a creative methodology in the construction of polymeric materials with tailor-made structures and properties. Compared with transition metal catalyst polymerizations, enzymatic polymerization is more attractive in the biomedicine field due to the metal-free residue, good biocompatibility, and few by-products. Meanwhile, enzymatic polymerization has far more activity towards macrolides. In this review, the synthesis of lipase-catalyzed polymer materials is systematically summarized, focusing on the synthesis of the complex and well-defined polymers. The enzymatic polyester synthesis was then discussed concerning the different reaction types, including ring-opening polymerization, polycondensation, a combination of ring-opening polymerization with polycondensation, and chemoenzymatic polymerization. Besides, exploration of novel biocatalysts and reaction media was also described, with particular emphasis on the enzymes obtained immobilization or protein engineering strategies, green solvents, and reactors. Finally, recent developments in catalytic kinetics and mechanistic studies through the use of spectroscopy, mathematics, and computer techniques have been introduced. Besides, we addressed the remaining central issues in enzymatic polymerization and discussed current studies aimed at providing answers.