Biocatalytic synthesis of polylactate and its copolymers by engineered microorganisms

Poly(lactate), also called poly(lactic acid) or poly(lactide) [PLA], has been one of the most attractive bio-based polymers since it possesses desirable material properties for its use in general performance plastics in addition to biodegradability and biocompatibility. PLA has been produced by biological and chemical hybrid process comprising microbial fermentation for lactate (LA) production followed by purification and chemical polymerization process of LA. Recently, the direct one-step fermentative processes for production of PLA and several LA-containing polyesters have been developed by employing metabolically engineered microorganisms. Since natural microorganisms cannot produce the LA-containing polymers, several engineering strategies have been employed together based on the polyhydroxyalkanoate (PHA) biosynthesis system. In this chapter, we summarize strategies and procedures on developing the engineered microorganisms producing PLA and its copolymers, cultivating the cells, and extracting the polymers from the cells. Focuses were given on construction of enzymatic polymerization process of LA: design of metabolic pathway for PLA by mimicking PHA biosynthetic pathway, examination of possible enzymes, and engineering of the enzymes for better performances. This synthetic pathway has been established in a microorganism producing LA that enabled one-step fermentative production of LA-containing polyesters from carbohydrates derived from renewable biomass. Polymer production has been further enhanced by implementing strain engineering to concentrate the metabolic fluxes toward PLA formation. In addition, various monomers such as glycolate, 2-hydroxybutyrate, and phenyllactate have been copolymerized with LA by the microbial system. These fermentative production systems developed by using the engineered microorganisms can be versatile and sustainable platforms for the production of LA-containing polyesters and other non-natural polymers.