Probing Enzymatic PET Degradation: Molecular Dynamics Analysis of Cutinase Adsorption and Stability.

Understanding the mechanisms influencing poly(ethylene terephthalate) (PET) biodegradation is crucial for developing innovative strategies to accelerate the breakdown of this persistent plastic. In this study, we employed all-atom molecular dynamics simulation to investigate the adsorption process of the LCC-ICCG cutinase enzyme onto the PET surface. Our results revealed that hydrophobic, π-π, and H bond interactions, specifically involving aliphatic, aromatic, and polar uncharged amino acids, were the primary driving forces for the adsorption of the cutinase enzyme onto PET. Additionally, we observed a negligible change in the enzyme's tertiary structure during the interaction with PET (RMSD = 1.35 Å), while its secondary structures remained remarkably stable. Quantitative analysis further demonstrated that there is about a 24% decrease in the number of enzyme-water hydrogen bonds upon adsorption onto the PET surface. The significance of this study lies in unraveling the molecular intricacies of the adsorption process, providing valuable insights into the initial steps of enzymatic PET degradation.

Toward a Better Understanding of the Poly(glycerol sebacate)-Water Interface.

Molecular simulations were conducted to provide a better description of the poly(glycerol sebacate) (PGS)-water interface. The density and the glass-transition temperature as well as their dependencies on the degree of esterification were examined in close connection with the available experimental data. The work of adhesion and water contact angle were calculated as a function of the degree of esterification. A direct correlation was established between the strength of the hydrogen bond network in the interfacial region and the change in the water contact angle with respect to the degree of esterification. The interfacial region was described by local density profiles and orientations of the water molecules.

Development of anisotropic force fields for homopolymer melts at the mesoscale.

With the aim of producing realistic coarse-grained models of homopolymers, we introduce a tabulated backbone-oriented anisotropic potential. The parameters of the model are optimized using statistical trajectory matching. The impact of grain anisotropy is evaluated at different coarse-graining levels using cis-polybutadiene as a test case. We show that, at the same time, tuning the aspect ratio of the grains can lead to a better density and structure and may reduce the unphysical bond crossings by up to 90%, without increasing the computation time too much and thereby jeopardizing the main advantage of coarse-grained models.

Energetic and Structural Characterizations of the PET-Water Interface as a Key Step in Understanding Its Depolymerization.

We report molecular simulations of the interaction between poly(ethylene terephthalate) (PET) surfaces and water molecules with a short-term goal to better evaluate the different energy contributions governing the enzymatic degradation of amorphous PET. After checking that the glass transition temperature, density, entanglement mass, and mechanical properties of an amorphous PET are well reproduced by our molecular model, we extend the study to the extraction of a monomer from the bulk surface in different environments, i.e., water, vacuum, dodecane, and ethylene glycol. We complete this energetic characterization by the calculation of the work of adhesion of PET surfaces with water and dodecane molecules and by the determination of the contact angle of water droplets. These calculations are compared with experiments and should help us to better understand the enzymatic degradation of PET from both the thermodynamic and molecular viewpoints.