Polylactide (PLA) is a biobased synthetic polyester with
diverse
commercial applications. Nevertheless, PLA has been deemed unfavorable
owing to its constrained processability, impact resistance, and biodegradability.
Therefore, this study aimed at engineering novel biodegradable modifiers
based on a highly chiral enantiopure D-lactate (D-LA)-based polyester
called poly[D-LA-co-(R)-3-hydroxybutyrate
(3HB)] (LAHB) to improve the physical properties of PLA. High-molecular-weight
(hmw) LAHB was synthesized from the chemoautotrophic Cupriavidus necator in substantial quantities. The
tailor-made overproduction of LAHB was achieved by using a minimal
medium containing glucose and retaining the intrinsic synthetic pathway
for the 3HB homopolymer in C. necator, which produced the highest yields, reaching up to 27 g/L/48 h.
The molecular weight of LAHB substantially elevated up to 1.1 ×
106 g/mol and was termed ultrahigh-molecular-weight (uhmw)
LAHB. The LA faction in LAHB was modulated via a synergistic optimized
combination of the lactate dehydrogenase and propionyl-coenzyme A
transferase variants as well as by effective shut-off of the D-LA
escape route. Combination of PLA and the two selected biodegradable
uhmw-/hmw-LAHBs as demand-oriented biodegradable modifiers allowed
improved processability and impact resistance of PLA while retaining
transparency. These benefits of LAHB are distinguishable from those
of conventional biobased modifiers, including 3HB-based polymers.