非添加离子效应驱动水中的热敏聚合物的崩和膨胀
Ellen E Bruce1, Pho T Bui2, Bradley A Rogers2
1Eduard-Zintl-Institut für Anorganische und Physikalische Chemie , Technische Universität Darmstadt , Alarich-Weiss-Straße 10 , D-64287 Darmstadt , Germany.
Journal of the American Chemical Society
|March 29, 2019
概括
强加和弱加水离子的混合物对聚合物溶液没有添加作用. 离子竞争通过改变水化和接口相互作用来影响聚烯酸胺的较低临界溶液温度 (LCST).
科学领域:
- 物理化学
- 聚合物科学
- 解决方案化学
背景情况:
- 聚合物溶液的行为对离子的存在敏感.
- 霍夫迈斯特系列描述了离子对蛋白质和聚合物可溶性的特异性影响.
- 了解离子混合物的作用对于控制聚合物溶液的特性至关重要.
研究的目的:
- 研究混合离子 (硫酸盐和) 对聚乙烯-异烯胺 (PNiPAM) 的较低临界溶液温度 (LCST) 的非添加作用.
- 使用计算和实验方法阐明这些非添加效应背后的分子机制.
主要方法:
- 使用分子动力学 (MD) 模拟来建模离子和聚合物相互作用.
- 使用振动总频谱 (VSFS) 来探测聚合物/水接口.
- 实验中使用固定的硫酸 (Na2SO4) 和不同的酸 (NaI) 度.
主要成果:
- 在较低的NaI度下,Na+离子优先与强度水的SO42-) 离子结合,使I-离子更加水.
- 在较高的NaI度下,SO42-) 离子有效地竞争,迫使I-离子向PNiPAM/水接口.
- 这些相互竞争的水分和界面相互作用导致对PNiPAM LCST的非添加效应.
结论:
- 混合盐溶液中的PNiPAM的LCST由离子水合和聚合物-离子相互作用之间的相互作用决定.
- 这些发现强调了在复杂的溶液系统中考虑竞争性离子效应的重要性.
- 这一概念适用于来自霍夫迈斯特系列的强和弱化离子的各种混合物.
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