Rd. Ashby et al., USE OF POLY(ETHYLENE GLYCOL) TO CONTROL THE END GROUP-STRUCTURE AND MOLECULAR-WEIGHT OF POLY(3-HYDROXYBUTYRATE) FORMED BY ALCALIGENES LATUSDSM-1122, Tetrahedron, 53(45), 1997, pp. 15209-15223
Poly(ethylene glycol), PEG, which is known to associate with lipid mem
branes and proteins, was used to control the molecular weight and end-
group structure of poly(3-hydroxybutyrate), P3HB, produced by Alcalige
nes latus DSM 1122. A series of PEGs with varying molecular weights (P
EG-106 to PEG-10,000) was added to the A. latus incubation medium. In
general, PEGs of relatively lower molecular weight and high concentrat
ions of PEG in the medium had deleterious effects on cell growth, poly
mer yield and P3HB productivity. PEGs with molecular weights at or bel
ow 1000 g/mol resulted in the formation of P3HB with reduced molecular
weights. The extent of molecular weight reduction was dependent on th
e concentration and molecular weight of the PEG added to the incubatio
n medium. Larger molecular weight reductions at identical medium conce
ntrations were achieved by using PEG of relatively fewer molecular wei
ght. PEG-106 was most effective in regulating P3HB molecular weight in
that only a 1% (w/v) medium concentration was required to reduce the
number average molecular weight (M-n) by 89% (from 267,000 to -30,000
g/mol). Study of the purified polymers showed that for PEG molecular w
eights up to 1,000 g/mol, P3HB chains were esterified at their carboxy
l terminus with PEG chain segments. Thus, products having ''tailored''
molecular weights and end-group structure were formed. This was expla
ined by that for P3HB formation by A. latus, PEG of sufficiently low m
olecular weight served as a chain terminating agent. In other words, t
he in-vivo esterification of P3HB chain ends with PEG increases the ra
te of chain termination relative to propagation and, thereby, results
in reduced P3HB molecular weight. (C) 1997 Elsevier Science Ltd.