The kinetics of the enzymatic degradation reactions of the naturally p
roduced polyesters poly(beta-hydroxybutyrate) (PHB) and poly(beta-hydr
oxybutyrate-co-beta-hydroxyvalerate (PHBV) by appropriate depolymerase
s were studied. Specially, the interaction between the extracellular P
HB depolymerase of Pseudomonas lemoignei and both PHB powder and solut
ion-cast films of PHBV was investigated. Kinetic analysis of titristat
ically and turbidimetrically determined rates of degradation has revea
led that the observed degradation behaviour was inconsistent with clas
sical Michaelis-Menten enzymatic kinetics. Depending upon the relative
concentrations of enzyme and substrate, each exhibited a range of kin
etic dependencies from zero order to first order. At high relative con
centrations of enzyme, the reaction rate became inversely proportional
to enzyme concentration. A new kinetic treatment was derived which pr
edicted the observed variations in kinetic dependence on both enzyme a
nd substrate, and it successfully described previously published kinet
ic data for this and other PHB depolymerases. The degradation of PHB b
y the PHB depolymerase of Aspergillus fumigatus M2A was investigated f
or comparison. While the specific rate constants of this enzyme differ
ed from that of P. lemoignei, the general kinetic model was still appl
icable. (C) 1997 Elsevier Science Ltd.