Enzymatic Degradation of PLA: Preferential Degradation of the Amorphous Fraction

Polylactic acid (PLA), a widely used biobased biopolymer, is highly resistant to biodegradation under ambient conditions, contributing to persistent plastic pollution and posing potential environmental and health risks. This study investigates the enzymatic degradation of PLA by Proteinase K, a proteolytic hydrolase enzyme with the ability to degrade PLA, and explores the underlying mechanisms for degradation. Both amorphous and semi-crystalline PLA were treated with Proteinase K (2 mg/mL) at 37 °C over varying time periods. PLA degradation was evaluated using multiple techniques, including weight loss measurement, pH reduction, quantification of lactic acid monomer release by High-Performance Liquid Chromatography (HPLC), surface morphology analysis through Scanning Electron Microscopy (SEM), changes in thermal properties by Differential Scanning Calorimetry (DSC), and structural changes by X-Ray Diffraction (XRD). The data revealed that the degradation of amorphous regions of the PLA polymer was faster and more extensive than the crystalline regions of the polymer. Repeated enzymatic treatments significantly enhanced the degradation rate. Furthermore, Proteinase K showed a clear preference for degrading amorphous regions of the PLA, as evidenced by higher weight loss, sharper pH decline, higher lactic acid production, and more pronounced surface disruptions, such as visible gaps between degraded oligomer structures.