No abstract

This study focuses on the estimation and validation of some interaction parameters of the Consistent Valence Force‐Field (CVFF), which are required for the calculation of thermodynamic and transport properties of oxaliplatin (a colorectal anticancer drug) in poly(lactic‐co‐glycolic) acids (PLGAs) matrices. Our methodology to validate the parameters for PLGAs consisted on calculation of glass transition temperature and correlations between structural properties as: fractional free volume, polymer density, and cohesive energy density using Molecular dynamic simulations. For the oxaliplatin, metal‐dependent and independent interaction parameters were included into CVFF and validated with an ab‐initio method (RHF/LanL2DZ). The results achieved in the present work showed that the CVFF has been wellparameterized.

No abstract

In light of the 60-year anniversary of the publishing of “Clathrate Solutions” by van der Waals and Platteeuw in 2019, we present a critical review of the famed solid solution model first disclosed in 1959. First, we lay out the groundwork in the 1950s aimed at the development of a phenomenological approach to clathrate modeling. Then we review the statistical thermodynamics fundamentals of the model, considering van der Waals and Platteeuw’s earlier works, to obtain a consistent interpretation of the model. We turn our focus to clathrate hydrates and discuss the major contributions that led to the current state-of-the-art of gas hydrate thermodynamic modeling. Finally, we present some of the areas in clathrate thermodynamics that we foresee as the new frontiers in this subject. We expect this review to help newcomers to clathrate science in elucidating some subtle aspects of the model and to intrigue clathrate experts with a fresh look on this well-established solid solution model.

For the engineering and process design of chemical and pharmaceutical plants, the knowledge of thermophysical properties is essential. Here, glass transition temperature (Tg), curves of heat capacity (Cp), isotropic thermal expansion (∝p), and isothermal compressibility (βT) are computed for amorphous/paracrystalline (Am‐Par) structures of cellulose over a wide range of temperature (380–680 K) using molecular dynamics with the CHARMM36 (C36) force field (FF). The fluctuation method under the NPT ensemble is used to calculate Cp, ∝p, and βT, whereas Tg is computed by monitoring specific volume versus temperature. Here, the fluctuation method is used with a quantum mechanical correction term for the calculation of Cp. Results of Cp, ∝p, and βT values at 298 K using extrapolation from these curves are also obtained. The thermophysical properties values from the simulations are compared with experimental data for cellulose with different degree of crystallinity and with those obtained by prominent FFs suggested for cellulose, such as GLYCAM06 and COMPASS. The findings reveal that ∝p, βT, and Tg are somewhat better reproduced than Cp with C36 over the studied temperature range. From this study, it is inferred that, for accurate modeling of heat capacity of pure Am‐Par celluloses with large fragments of glucose, the C36 FF needs re‐parameterization.