Evolution of polyhydroxyalkanoate synthesizing systems toward a sustainable plastic industry

Designing sustainable biobased and/or biodegradable plastics opens up opportunities to achieve a low-carbon society and overcome plastic pollution. Bioplastics manufactured from renewable resources are being designed to feature a minimal carbon footprint and complete biodegradability/compostability. Among them, naturally occurring polyhydroxyalkanoates (PHAs) have currently received increasing attention from academia and industry. A symbolic state-of-the-art PHA industry is a rapidly growing market of PHBHTM Kaneka polymers that display excellent marine biodegradability. From an academic perspective, there have been several major breakthroughs in the PHA research field starting with the pioneering works of genetically engineered platforms for the production of artificial PHAs. The discovery of a lactate-polymerizing enzyme enabled us to produce lactate-based PHAs in one-pot microbial systems, whereas polylactide and other relevant copolymers are currently synthesized via biological and chemical processes. This proof-of-concept has been implemented in practical integrated bioprocesses for carbon-neutral polymer production starting from renewable raw bioresources. Challengingly, the photosynthetic machinery RuBisCO (ribulose-1,5-bisphosphate carboxylase/oxygenase), has also been applied to synthesize glycolate-based copolymers as a CO2 fixation model in the current project. Such game-changing technologies contribute to realizing a circular bioeconomy through the utilization of CO2. This review presents the current progress in evolving microbial polymerization systems, including the direct secretion of polymerized products and the creation of sequence-regulated polyesters, which have been considered nearly impossible biological events to date. Polyhydroxyalkanoates (PHAs) are biobased and biodegradable materials. The artificial PHAs, such as lactate-based polymers, synthesized by engineered platforms expand the range of physical properties. The artificial polymers with superior properties are produced mainly from CO2-derived biomass using microbial platform with engineered enzymes. The oligomers can be secreted from cells and derivatized into high-molecular-weight polymers through assembling with other segments. The review summaries recent advances in the biosynthesis and biodegradation of artificial PHAs and oligomers.