Atomistic insights into solvation dynamics and conformational transformation in thermo-sensitive and non-thermo-sensitive oligomers

Solvation dynamics and conformational transformation in oligomers with varying degree of temperature sensitivity is studied using molecular dynamics (MD) simulations. Conformational transformation in three model systems namely poly(N-isopropylacrylamide) (PNIPAM), poly(acrylamide) (PAA), and poly(ethylene glycol) (PEG) are compared and contrasted to understand the origin of a coil-to-globule transformations across the lower critical solution temperature (LCST) in thermo-sensitive oligomers. PNIPAM, PAA, and PEG are water-soluble oligomers. However, for the temperature range used in these simulations, PNIPAM shows an LCST whereas PM and PEG are non-thermo-sensitive. Oligomers of PNIPAM, PM, and PEG consisting of 30 monomer units (30-mer) each were simulated at 5 degrees C (278 K) and 37 degrees C (310 K). Conformational transformations in the oligomers are evaluated using structural and dynamical correlation functions such as radius of gyration, radial distribution function, residence time probabilities and hydrogen-bonding life-times. Our simulations suggest that the solubility, solvation dynamics, and conformation of the oligomers are dictated by two factors: (a) the local structure of proximal water and (b) the diffusion and exchange kinetics of proximal water with bulk water. In thermo-sensitive oligomer such as PNIPAM, we find that the coil-to-globule transition is closely related to the local ordering and solvation dynamics of PNIPAM. We have identified stable configurations of proximal water molecules for an oligomer undergoing conformational transition. The slow diffusional properties of proximal water molecules near PNIPAM oligomers suggests that water forms a stable network near hydrophilic groups of PNIPAM as compared to the hydrophilic groups of PM and PEG. Thermal perturbation of this solvated structure results in significant reduction in local ordering of water, which contributes to the globular collapse and the reduced solubility of PNIPAM above its LCST. On the other hand, non-thermo-sensitive oligomers such as PM and PEG are characterized by much faster diffusion and exchange kinetics of proximal water at the two simulated temperatures compared to PNIPAM. This faster exchange kinetics helps in maintaining higher hydration level of the oligomers and is responsible for the apparent hydrophilic character and thereby the observed solubility at the two simulated temperatures. (C) 2012 Elsevier Ltd. All rights reserved.