物理化学学报 >> 2019, Vol. 35 >> Issue (1): 49-57.doi: 10.3866/PKU.WHXB201802071

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Hofmeister离子对水溶液中热响应聚合物的局域环境的影响

薛智敏1,*(),严传玉2,赵新辉2,于东琨2,牟天成2,*()   

  1. 1 北京林业大学材料科学与技术学院, 北京 100083
    2 中国人民大学化学系,北京 100872
  • 收稿日期:2018-01-19 发布日期:2018-06-13
  • 通讯作者: 薛智敏,牟天成 E-mail:zmxue@bjfu.edu.cn;tcmu@ruc.edu.cn
  • 基金资助:
    中央高校基本科研业务费(2017ZY40);国家自然科学基金(21773307);国家自然科学基金(21503016)

How Hofmeister Ions Change the Local Environment around Thermoresponsive Polymers in Aqueous Solutions: an NMR Study

Zhimin XUE1,*(),Chuanyu YAN2,Xinhui ZHAO2,Dongkun YU2,Tiancheng MU2,*()   

  1. 1 Beijing Key Laboratory of Lignocellulosic Chemistry, College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, P. R. China
    2 Department of Chemistry, Renmin University of China, Beijing 100872, P. R. China
  • Received:2018-01-19 Published:2018-06-13
  • Contact: Zhimin XUE,Tiancheng MU E-mail:zmxue@bjfu.edu.cn;tcmu@ruc.edu.cn
  • Supported by:
    the Fundamental Research Funds for The Central Universities, China(2017ZY40);National Natural Science Foundation of China(21773307);National Natural Science Foundation of China(21503016)

摘要:

Hofmeister离子效应的机制仍然未知。为了进一步探索,我们应用质子核磁共振(1H-NMR)波谱研究了特定离子对聚(2-乙基-2-恶唑啉)和聚(N-异丙基丙烯酰胺)的模型化合物N, N-二甲基丙酰胺(NDA)和N-异丙基异丁酰胺(NPA)水溶液的局域环境的影响。这些聚合物具有热响应性质,是重要的生物工程材料,也受到特异离子效应影响。通过将酰胺键两侧的两个甲基的化学位移的变化相关联,发现对于所有NDA的甲基,特异离子的作用几乎相同。然而,NPA是一个较大的分子,我们发现并不是所有的甲基具有相同程度的特异离子效应。这项研究的结果表明,霍夫梅斯特离子效应可能主要是一种全局效应,而离子与溶质的局部相互作用也起了关键作用。

关键词: 热响应聚合物, 酰胺, 霍夫梅斯特效应, 离子, 核磁共振波谱

Abstract:

The Hofmeister ion effect is a very interesting but elusive phenomenon, the importance of which is revealed in self-assembly, ion recognition, and protein folding regulation. With an increasing number of studies suggesting that interactions between ions and solutes play a role in the Hofmeister ion effect, the nature of the Hofmeister phenomenon becomes more debatable. Yet, it is not clear whether the Hofmeister ion effect is a local effect or bulk effect that can reach beyond many hydration shells, where specific interactions between ions and solutes play key roles. In order to further explore this, we applied proton nuclear magnetic resonance (1H-NMR) spectroscopy to study the effects of specific ions on the local environment around N, N-dimethylpropionamide (NDA) and N-isopropylisobutyramide (NPA), which are the model compounds for poly(2-ethyl-2-oxazoline) and poly(N-isopropylacrylamide), respectively. These polymers are important bio-engineering materials that possess thermoresponsive properties and are also subject to specific ion effects. By correlating the changes in chemical shifts of the two methyl groups on either side of the amide bond, it was found that the Hofmeister ion effects on NPA were more anisotropic than on NDA, and that the cationic effects were more anisotropic than the anionic effects on NPA. These results indicated that the effects of specific ions were almost identical for all methyl groups of NDA. On the other hand, NPA is a larger molecule; thus, not all of its methyl groups were subjected to the specific ion effects to the same extent. The calculation of the electrostatic potential surfaces of NDA and NPA suggested that these observations on the Hofmeister ion effects might be due to steric hindrance, and that the observations on the cationic effects might be due to the interactions between cations and NPA being stronger than the interactions between anions and NPA. This would explain why the highly charged cations caused a significant anisotropicity. Additionally, we found that the chemical shift of the water protons (ΔδH2O) of conventional kosmotropic anions was larger than zero, which suggested a stronger HB and more charge transfer between water and these anions. The ΔδH2O of conventional chaotropic anions was less than zero. Despite the different solutes, the results were indifferent in both NDA and NPA solutions. Surprisingly, the ΔδH2O of Cl- at concentrations lower than 1 mol∙L-1 was zero, thus becoming the benchmark between chaotropes and kosmotropes. These results suggested a quantitative measurement of kosmotropicity/chaotropicity, where the anion would be kosmotropic if its ΔδH2O were higher than that of Cl- and chaotropic for the opposing condition. Moreover, the results showed that the effects of the cations on the water structure were minimal, which was consistent with minimal charge transfer between the cations and water. The overall results of this study suggest that the Hofmeister ion effect is a global effect, while local interactions of ions with solutes also play a key role.

Key words: Thermoresponsive polymer, Amide, Hofmeister effects, Ions, NMR

MSC2000: 

  • O642