A molecular insight into poly(methyl methacrylate) impregnation with mefenamic acid in supercritical carbon dioxide: A computational simulation

The process of poly(methyl methacrylate) (PMMA) matrix impregnation with mefenamic acid (MFA) in a supercritical carbon dioxide medium has been studied by the full atomistic classical molecular dynamics method. Simulations have been performed for two systems that differ in the polymer sample size (approximate to 270 kDa and approximate to 1080 kDa) at 333 K and 40 MPa. The characteristics of the systems, such as the radius of gyration, end-to-end distance, mean squared displacement, radial distribution functions, average number of hydrogen bonds, and number of close contacts, have been analyzed and discussed. It has been found that by the end of the simulation (15 ns), the MFA loadings reach about 1.43 w/w % and 1.14 w/w % for the small and big PMMA samples, respectively. It was shown that the solute was distributed in the molecular form inside the polymer matrix. At the same time, when the CO2 molecules were removed from the systems and the simulation was performed in a canonical ensemble with the same cell length as in the previous isobaric-isothermal ensemble, the MFA molecules began to self-associate and get adsorbed on the polymer surface as hydrogen-bonded aggregates. In order to estimate the strength of the intermolecular interaction between the system components, ab initio calculations were performed. The calculated energies of the electron donor-acceptor (EDA) and hydrogen-bonded (HB) complexes can be arranged in the following order (in absolute value): Delta E-EDA(PMMA-CO2)approximate to Delta E-HB(MFA-CO2) < Delta E-HB(PMMA-MFA) < Delta E-HB(MFA-MFA). (C) 2021 Elsevier B.V. All rights reserved.