The role of functional group concentration in solvation thermodynamics
The role of functional group concentration in solvation thermodynamics
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DOI：
10.1039/c0sc00209g
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发表时间：
2010-01-01
期刊：
影响因子：
8.4
通讯作者：
Vinter, Jeremy G.
中科院分区：
文献类型：
--
作者：
Buurma, Niklaas J.;Cook, Joanne L.;Vinter, Jeremy G.
利用分子识别探针的高通量实验揭示了溶剂官能团浓度与选择性溶剂化之间的简单关系。在1088种不同的烷烃-乙醚混合物中，用紫外可见光谱仪测定了三丁基氧膦与4-苯基偶氮苯酚氢键相互作用的1：1缔合常数。虽然络合物的稳定性如预期的那样随着更极性的醚类助溶剂浓度的增加而降低，但结果表明，决定溶剂化热力学的是官能团组成，而不是溶剂分子的组成或大体积液体的性质。因此，可以通过具有相同净浓度的醚氧官能团的聚醚和烷烃的适当混合物来重现简单醚的溶剂性质。结果表明，仅通过考虑溶剂中官能团的极性和浓度就可以在分子水平上理解溶剂化，因为这些参数影响局部溶剂化与溶质的相互作用。
High throughput experiments using a molecular recognition probe reveal a simple relationship between solvent functional group concentration and selective solvation. The 1 : 1 association constant for the H-bonding interaction between tri-n-butylphosphine oxide and 4-phenylazophenol was measured in 1088 different alkane-ether mixtures using a UV-Vis plate reader. Although the stability of the complex decreased with increasing concentration of the more polar ether cosolvent as expected, the results show that it is the functional group composition rather than the constitution of the solvent molecules or the properties of the bulk liquid that determines the solvation thermodynamics. Thus the solvent properties of a simple ether can be reproduced by an appropriate mixture of a polyether and an alkane that has the same net concentration of ether oxygen functional groups. The results suggest that solvation may be understood at the molecular level simply by considering the polarities and the concentrations of the functional groups present in the solvent, because these are the parameters that affect local solvation interactions with the solutes.