Hydrophobic hydration of poly-N-isopropyl acrylamide: a matter of the mean energetic state of water.
Hydrophobic hydration of poly-N-isopropyl acrylamide: a matter of the mean energetic state of water.
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DOI：
10.1038/srep04377
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发表时间：
2014-03-14
影响因子：
4.6
通讯作者：
Trappe V
中科院分区：
文献类型：
--
作者：
Bischofberger I;Calzolari DC;De Los Rios P;Jelezarov I;Trappe V
疏水实体的疏水性有利水合作用（称为疏水性水合作用）影响许多两亲物在水中的相行为。在这里，我们展示了实验证据表明，疏水水化强烈决定的平均能量的水介质。我们调查的两亲性聚合物，聚-N-异丙基丙烯酰胺（PNiPAM），在含有少量的醇的水溶液中的聚集和崩溃，并发现定义的PNiPAM的相变的热力学特性演变相对于溶剂组合物，在该组合物中的水/醇混合物的过量混合焓变得最小。溶剂能量学和溶液热力学之间的这种相关性延伸到含有中性有机溶质的其他混合物，所述中性有机溶质被认为是诱导氢键合的水网络的加强的亲液剂。这表示作为控制PNiPAM的相行为的关键参数的水的能量学，并且确定水/kosmotrope混合物的过量混合焓作为疏水组件上的kosmotrope效应的计量器。
The enthalpically favoured hydration of hydrophobic entities, termed hydrophobic hydration, impacts the phase behaviour of numerous amphiphiles in water. Here, we show experimental evidence that hydrophobic hydration is strongly determined by the mean energetics of the aqueous medium. We investigate the aggregation and collapse of an amphiphilic polymer, poly-N-isopropyl acrylamide (PNiPAM), in aqueous solutions containing small amounts of alcohol and find that the thermodynamic characteristics defining the phase transitions of PNiPAM evolve relative to the solvent composition at which the excess mixing enthalpy of the water/alcohol mixtures becomes minimal. Such correlation between solvent energetics and solution thermodynamics extends to other mixtures containing neutral organic solutes that are considered as kosmotropes to induce a strengthening of the hydrogen bonded water network. This denotes the energetics of water as a key parameter controlling the phase behaviour of PNiPAM and identifies the excess mixing enthalpy of water/kosmotrope mixtures as a gauge of the kosmotropic effect on hydrophobic assemblies.
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