大环疏水效应: 冠醚在DMF+H2O混合物中的焓对作用

doi:10.3866/PKU.WHXB201305103

物理化学学报 >> 2013, Vol. 29 >> Issue (10): 2114-2122.doi: 10.3866/PKU.WHXB201305103

大环疏水效应: 冠醚在DMF+H₂O混合物中的焓对作用

程维娜¹, 胡新根¹, 邵爽²

1 温州大学化学与材料工程学院, 浙江温州 325035;
2 浙江外国语学院化学系, 杭州 310012

收稿日期:2013-03-26 修回日期:2013-05-09 发布日期:2013-09-26
通讯作者: 胡新根 E-mail:hxgwzu@126.com
基金资助:
国家自然科学基金(21073132)资助项目

Macrocyclic Hydrophobic Effect：Enthalpic Pairwise Interactions of Crown Ethers in Mixtures of DMF and Water

CHENG Wei-Na¹, HU Xin-Gen¹, SHAO Shuang²

1 College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang Province, P. R. China;
2 Department of Chemistry, Zhejiang International Studies University, Hangzhou 310012, P. R. China

Received:2013-03-26 Revised:2013-05-09 Published:2013-09-26
Contact: HU Xin-Gen E-mail:hxgwzu@126.com
Supported by:
The project was supported by the National Natural Science Foundation of China (21073132).

摘要/Abstract

摘要：

利用等温滴定微量热法测定了298.15 K时12-冠-4、15-冠-5、18-冠-6和4,13-二氮杂-18-冠-6四种冠醚在纯水及不同质量分数(w=0-0.3)的N,N-二甲基甲酰胺(DMF)+H₂O混合物中的稀释焓, 根据McMillan-Mayer理论计算得到相应的焓对作用系数(h_xx). 实验发现, h_xx均为较大的正值, 表明在冠醚-冠醚自相互作用中疏水性成分占绝对优势, 主要表现为两种机制: (1) 当疏水-疏水作用发生时, 共球交盖使得水结构形成减少, 对h_xx有正的贡献; (2) 当疏水-亲水作用发生时, 共球交盖使得水结构破坏增加, 对h_xx有正的贡献. 此外, 四种冠醚h_xx的大小关系为: h_xx(18-冠-6)>h_xx(4,13-二氮杂-18-冠-6)≈h_xx(15-冠-5)>h_xx(12-冠-4), 表明冠醚环越大, 疏水-疏水作用越强, 存在显著的大环疏水效应.

关键词: 冠醚, 二甲基甲酰胺+水混合物, 稀释焓, 焓对作用, 疏水-亲水平衡, 大环疏水效应, 等温滴定微量热法

Abstract:

The dilution enthalpies of four crown ethers, namely 12-crown-4, 15-crown-5, 18-crown-6, and 4,13-diaza-18-crown-6, in pure water and mixtures of N,N-dimethylformamide (DMF) and water of various mass fraction (w=0-0.3) were determined at 298.15 K by isothermal titration microcalorimetry. The corresponding enthalpic pairwise interaction coefficients (h_xx) were evaluated according to the McMillan-Mayer theory. Values of h_xx were all positive and large, which indicates that hydrophobic components predominate in crown-crown self-interactions. There are two main kinds of mechanisms: (1) When hydrophobic-hydrophobic interactions occur, cosphere overlapping reduces the formation of water structure, which makes a positive contribution to h_xx. (2) Hydrophobic-hydrophilic interactions increasingly destroy the water structure because of cosphere overlapping, which also makes a positive contribution to h_xx. In addition, h_xx values of the four crown ethers follow the order: h_xx(18-crown-6)>h_xx(4,13-diaza-18-crown-6)≈ h_xx(15-crown-5) >h_xx(12-crown-4), which indicates that the larger the size of the crown ether ring, the stronger the hydrophobic-hydrophobic interaction; namely, that crown ethers are subject to macrocyclic hydrophobic effects.

Key words: Crown ether, N,N-dimethylformamide+H₂Omixture, Dilution enthalpy, Enthalpic pairwise interaction, Hydrophobic-hydrophilic equilibrium, Macrocyclic hydrophobic effect, Isothermal titration calorimetry

程维娜, 胡新根, 邵爽. 大环疏水效应: 冠醚在DMF+H₂O混合物中的焓对作用[J]. 物理化学学报, 2013, 29(10), 2114-2122. doi: 10.3866/PKU.WHXB201305103

CHENG Wei-Na, HU Xin-Gen, SHAO Shuang. Macrocyclic Hydrophobic Effect：Enthalpic Pairwise Interactions of Crown Ethers in Mixtures of DMF and Water[J]. Acta Phys. -Chim. Sin. 2013, 29(10), 2114-2122. doi: 10.3866/PKU.WHXB201305103

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201305103

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I10/2114

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大环疏水效应: 冠醚在DMF+H₂O混合物中的焓对作用

Macrocyclic Hydrophobic Effect：Enthalpic Pairwise Interactions of Crown Ethers in Mixtures of DMF and Water

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