Coil-to-globule transition of thermo-responsive γ-substituted poly (ɛ-caprolactone) in water: A molecular dynamics simulation study

Abstract The coil-to-globule behavior of poly{γ-2-[2-(2methoxyethoxy)ethoxy]ethoxy-3-caprolactone} (PMEEECL) as a γ-substituted poly (ɛ-caprolactone) was investigated via atomistic molecular dynamics (MD) simulation. For this purpose, radius of gyration, end-to-end distance and radial distribution function of the chain in the presence of water were calculated. Consequently, the lower critical solution temperature (LCST) of PMEEECL chain at which the coil-to-globule transition takes place, was determined in each calculated parameter curve. The simulation results indicated that the LCST of PMEEECL was occurred at close to 320 K, which is in a good agreement with previous experimental results. Additionally, the appearance of sudden change in both Flory-Huggins interaction parameter (χ) and interaction energy between the PMEEECL chain and water molecules at about 320 K confirmed the calculated LCST result. The radial distribution function (RDF) results showed that the affinity of the PMEEECL side chain to water molecules is lower than its backbone.