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

Abstract

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

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

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

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