Comonomer Compositional Distribution, Physical Properties, and Enzymatic Degradability of Bacterial Poly(3-hydroxybutyrate-co-3-hydroxy-4-methylvalerate) Copolyesters

Abstract

Poly(3-hydroxybutyrate-co-3-hydroxy-4-methylvalerate) (P(3HB-co-3H4MV)) was synthesized by using Ralstonia eutropha strain PHB(-)4 (PHA-negative mutant) harboring with the N149S/D171G double mutation of PHA synthase gene from Aeromonas caviae (PhaC(Ac) NSDG mutant) with 4-methylvaleric acid and fructose as the carbon sources. Because the microbially synthesized P(3HB-co-3H4MV) samples were found to have broad comonomer compositional distribution, P(3HB-co-3H4MV) samples with 3H4MV content of 7, 11, and 35 mol % were fractionated into several fractions with different comonomer composition ranging from 2 to 47 mol % by using a chloroform/n-hexane mixture. It was confirmed that a series of well-fractionated P(3HB-co-3H4MV) samples had a statistically random distribution. Physical properties and structure of the fractionated P(3HB-co-3H4MV) random copolymers were investigated. Both the melting temperature and glass-transition temperature of P(3HB-co-3H4MV) copolymers decreased with an increase in the 3H4MV composition. The degree of X-ray crystallinity of fractionated P(3HB-co-3H4MV) films decreased from 60 to 13% as the 3H4MV fraction increased from 0 to 39 mol %. Enzymatic degradation test for fractionated P(3HB-co-3H4MV) films was carried out at 37 degrees C in the presence of PHB depolymerase from Ralstonia pickettii T1. The rates of enzymatic erosion markedly increased with an increase in the 3H4MV composition to reach the highest one at 7 mol % of 3H4MV, followed by a decrease in erosion rate.