A Comparison between the Lower Critical Solution Temperature Behavior of Polymers and Biomacromolecules

• Published in: Physchem 2022-03, Vol.2 (1), p.52-71
• Main Authors: Xie, Yuxin, Li, Nan K., Singh, Abhishek, Deshmukh, Sanket A., Yingling, Yaroslava G.
• Format: Article
• Language: English
• Subjects: all-atom molecular dynamics simulations; Boundary conditions; Hydrogen; lower critical solution temperature; Molecular weight; Peptides; Polymerization; Polymers; polymers and biopolymers; Simulation; Solvents
• ISSN: 2673-7167; 2673-7167
• DOI: 10.3390/physchem2010005

All-atom molecular dynamics (MD) simulations are employed to compare the lower critical solution temperature (LCST) behaviors of poly(N-isopropylacrylamide) (PNIPAM) and elastin-like polypeptides (ELPs) with the canonical Val-Pro-Gly-Val-Gly ((VPGVG)n) sequence over a range of temperatures from 280 K to 380 K. Our simulations suggest that the structure of proximal water dictates the conformation of both the (VPGVG)n ELPs and PNIPAM chains. Specifically, the LCST transition in ELPs can be attributed to a combination of thermal disruption of the network of the proximal water near both hydrophilic and hydrophobic groups in the backbone and side-chain of (VPGVG)n, resulting in a reduction in solvent accessible surface area (SASA). This is accompanied with an increase in the secondary structure above its LCST. In the case of PNIPAM, the LCST transition is a result of a combination of a reduction in the hydrophobic SASA primarily due to the contributions of isopropyl side-chain and less to the backbone and the formation of intra-chain hydrogen bonds between the amide groups on the side-chain above its LCST.