Enzymatic transformation of bacterial polyhydroxyalkanoates into repolymerizable oligomers directed towards chemical recycling.
The enzymatic transformation into an oligomer was carried out with the objective of developing the chemical recycling of bacterial polyesters. Poly(R-3-hydroxyalkanoate)s (PHAs), such as poly[(R-3-hydroxybutyrate)-co-12%(R-3-hydroxyhexanoate)] and poly[(R-3-hydroxybutyrate)-co-12%(R-3-hydroxyvalerate)], were degraded by granulated Candida antarctica lipase B immobilized on hydrophilic silica (lipase GCA) in a diluted organic solvent at 70 degrees C. The degradation products were cyclic oligomers having a molecular weight of a few hundreds. The obtained cyclic oligomer was readily repolymerized by the same lipase (lipase GCA) to produce the corresponding polyester in a concentrated solution. The cyclic oligomer was copolymerized with epsilon-caprolactone using lipase to produce the corresponding terpolymers having an Mw of 21,000. This is the first example of the enzymatic chemical recycling of bacterial PHAs using lipase. Poly(R-3-hydroxybutyrate) [P(3HB)] was also degraded into the linear-type R-3HB monomer to trimer by P(3HB)-depolymerase (PHBDP) in phosphate buffer at 37 degrees C. The degradation using PHBDP required a longer reaction time compared with the lipase-catalyzed degradation in organic solvent. The monomer composition of the oligomer depended on the origin of the PHBDP. The R-3HB monomer was predominately produced by PHBDP from Pseudomonas stutzeri, while the R-3HB dimer was produced by PHBDP from Alcaligenes faecalis T1. Repolymerization of these oligomers by lipase in concentrated organic solvent produced a relatively low-molecular-weight P(3HB) (e.g., Mw=2,000). Degradation of P(3HB) by lipase in organic solvent into repolymerizable cyclic oligomer and degradation of P(3HB) by PHBDP in buffer into hydroxy acid type R-3HB dimer.
Kaihara
Sachiko
S
Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Osanai
Yasushi
Y
Nishikawa
Kimihito
K
Toshima
Kazunobu
K
Doi
Yoshiharu
Y
Matsumura
Shuichi
S
D042481:Alcaligenes faecalis / Q000201:enzymology; D001672:Biocompatible Materials / Q000138:chemical synthesis* / Q000378:metabolism; D001673:Biodegradation, Environmental; D002265:Carboxylic Ester Hydrolases / Q000737:chemistry; D004800:Enzymes, Immobilized / Q000737:chemistry; D005656:Fungal Proteins; D008049:Lipase / Q000737:chemistry*; D011091:Polyesters / Q000138:chemical synthesis* / Q000378:metabolism; D011108:Polymers / Q000138:chemical synthesis* / Q000378:metabolism; D044223:Pseudomonas stutzeri / Q000201:enzymology; D000094122:Polyhydroxybutyrates
D001672:Biocompatible Materials; D002265:Carboxylic Ester Hydrolases; D004800:Enzymes, Immobilized; D005656:Fungal Proteins; D008049:Lipase; D011091:Polyesters; D011108:Polymers; C052620:poly(3-hydroxybutyrate)-co-(3-hydroxyvalerate); D000094122:Polyhydroxybutyrates; C022417:poly-beta-hydroxybutyrate depolymerase; C431349:lipase B, Candida antarctica