Computational Calorimetry of PNIPAM Cononsolvency in Water/Methanol Mixtures

被引：63

作者：

Dalgicdir, Cahit ^{[1
]}

Rodriguez-Ropero, Francisco ^{[1
,2
,3
]}

van der Vegt, Nico F. A. ^{[1
]}

机构：

[1] Tech Univ Darmstadt, Ctr Smart Interfaces, Eduard Zintl Inst Anorgan & Phys Chem, Darmstadt, Germany

[2] IIT, Dept Phys, Chicago, IL 60160 USA

[3] IIT, Ctr Mol Study Soft Condensed Matter, Chicago, IL 60160 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2017年 / 121卷 / 32期

关键词：

SIDE-CHAIN ORGANIZATION; MOLECULAR-DYNAMICS METHOD; LINEAR CONSTRAINT SOLVER; MISCIBLE GOOD SOLVENTS; AQUEOUS-METHANOL; POLYMER COLLAPSE; POLY(N-ISOPROPYLACRYLAMIDE) HYDROGELS; PREFERENTIAL ADSORPTION; CONFORMATION CHANGE; MIXED-SOLVENTS;

D O I：

10.1021/acs.jpcb.7b05960

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We revisit the mechanism for cononsolvency of PNIPAM in water/methanol mixtures. Using extensive molecular dynamics simulations, we calculate the calorimetric enthalpy. of the PNIPAM collapse transition and observe a unique fingerprint of PNIPAM cononsolvency which is analyzed in terms of microscopic interactions. We find that polymer hydration is the determining factor for PNIPAM collapse in the cononsolvency regime. In particular, it is shown that methanol frustrates the ability of water to form hydrogen bonds with the amide proton and therefore causes polymer collapse.

引用

页码：7741 / 7748

页数：8

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