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- Chemical vapor deposition (1)
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Organisationseinheit der BAM
Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(L‑lactide)
(2022)
The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(L-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75−80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance.
The synthesis of a disiloxane-functionalized [2.2]paracyclophane and its polymerization to the corresponding siloxane-substituted poly(p-xylylene) via chemical vapor deposition (CVD) has been described. Because of the enhanced solubility of the siloxane substituted poly(p-xylylene) analysis of the molecular structure by NMR, molecular weight, and polydispersity by gel permeation chromatography (GPC), and processing by film casting as well as nanofiber formation by electrospinning was possible. Structural isomers were found by NMR which was expected due to the isomeric mixture of the precursor. High molecular weights at moderate polydispersities were found by GPC which was unexpected for a vapor phase deposition polymerization. The amorphous morphology in combination with a low glass transition temperature led to high elongation at break for the siloxane substituted poly(p-xylylene). Significant difference for the wetting versus water was found for as-deposited films, solution cast films, and nanofibers obtained by electrospinning with contact angles up to 135° close to superhydrophobic behavior.
A novel route toward halogen-free fire retardancy of polymers through innovative surface coating is described. Nanofiber mats based on polyimide are deposited on PA66 through electrospinning. Scanning electron microscopy is used to characterize the nanofibers. Cone calorimeter tests were performed to evaluate the fire performance. Because of their low thermal conductivity, electrospun nanofiber mats act not only as sacrificial layers but also as a protective surface that delays ignition. The effect is influenced by the fiber diameters and the imidization.
In films of poly(para-phenylphenylenevinylene) a photoreaction has been observed. The significant feature is a decrease of the fluorescence emission intensity during irradiation. It is assumed that a cycloaddition between C=C- double-bonds leads to crosslinks in the material.
Under similar conditions of excitation a photoreaction has not been observed in poly(p-phenylenevinylene) prepared via the precursor-route.