Morphology and Enzymatic Degradation of Oriented Thin Film of Ultrahigh Molecular Weight Poly[(R)-3-hydroxybutyrate]

Thin films of ultrahigh molecular weight poly[(R)-3-hydroxybutyrate] (P(3HB)) were sheared and isothermally crystallized at 100 °C. Transmission electron microscopy and atomic force microscopy (AFM) observations revealed that thick fibrous textures, on which lamellae are overgrown normal to the long axis of the fibril, run parallel to the shearing direction. A selected area electron diffraction pattern taken from the fibrils exhibits a fiber pattern of P(3HB) α-modification, and the crystallographic c-axis (chain axis) of P(3HB) is set parallel to the long axis of the fibril. In situ AFM observations of enzymatic degradation for the thin film were performed with an extracellular P(3HB) depolymerase from Ralstonia pickettii T1 in a buffer solution. The film surface and thickness became rougher and thinner, respectively, with time after adding the enzyme. During the degradation, fine shish-kebab structures appeared gradually. This fact supports that the amorphous region in the film is preferentially degraded rather than the crystalline one by the depolymerase. The in situ AFM observations also revealed that one thick fibril in the original film is composed of three different states, namely, finer fibril (shish), stacked lamellae (kebab) in edge-on state, and the surrounding amorphous phase.