Quantitative analysis of factors determining the enzymatic degradation of poly(lactic acid)

Abstract

The enzymatic degradation of poly(lactic acid) was catalyzed with Proteinase K and the effect of various factors on the rate of degradation was analyzed quantitatively with the help of appropriate kinetic models. The Michaelis-Menten model was modified for the purpose by considering the heterogeneous nature of the reaction and the denaturation of the enzyme. The results proved that Proteinase K degrades the polymer very efficiently. The rate of degradation increases considerably up to 0.1 mg/ml enzyme concentration, but remains constant at larger values. Temperature has an optimum at around 50 °C that is somewhat higher than the 37 °C extensively used in the literature as the most advantageous temperature. If degradation occurs in the same medium throughout the process, the formation of lactic acid results in the rapid decrease of pH and finally in the denaturation of the enzyme. The dropping of pH below 5 slows down and finally stops degradation completely. The daily change of the medium results in degradation with a constant rate and the entire amount of the polymer can be decomposed mainly into monomer or smaller oligomer fragments. Degradation rate decreases slightly with increasing molecular weight and increasing d-lactide content. The use of appropriate kinetic models allows quantitative analysis and the prediction of the rate of enzymatic degradation of PLA.

Keywords: Kinetics; Modeling; Molecular weight; PLA; Proteinase K; d-lactide content.