Soft Matter · 2018 · 21 citations · 78 references
Natural SciencesBiophysicsChemistryBiophysical ChemistrySupramolecular ChemistrySurface ScienceHydration EffectsInterfacial PhenomenaIntermolecular ForcesSolution ChemistrySolvation EffectsSurfactantsInterfacial PropertiesInterfacial StructureInterfacial SurfactantsInterfacial Water StructureIonic SurfactantsMicellesReverse MicellesSurfactant Interactions
The behavior of the interfacial water entrapped in reverse micelles (RMs) that were formed by the ionic liquid-like surfactant 1-butyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate (bmim-AOT) was investigated with the use of UV-Vis absorption spectroscopy and nuclear magnetic resonance (NMR) relaxometry. The solvatochromism of two molecular probes, namely, 1-methyl-8-oxyquinolinium betaine (QB) and N,N,N',N'-tetramethylethylenediamine copper(ii)acetylacetonate tetraphenylborate ([Cu(acac)(tmen)][B(C6H5)4]), was investigated. As a comparison, the analog RMs formed by sodium 1,4-bis-2-ethylhexylsulfosuccinate (Na-AOT) were also explored. By varying the water content inside the RMs and consequently the different magnitude of the water-surfactant interactions at the interface, interesting properties were observed by comparing bmim-AOT and Na-AOT RMs. From the solvatochromic behavior of ([Cu(acac)(tmen)][B(C6H5)4]), we found that the interface in bmim-AOT RMs shows a smaller electron donating capacity than that in Na-AOT RMs. QB revealed that the interfacial region is a weaker hydrogen bond donor and less polar than the corresponding Na-AOT RMs. NMR experiments showed that the molecular motion of water in bmim-AOT RMs is less restricted than that of the water molecules confined in Na-AOT RMs. In summary, the results show how the nature of the bmim+ cation affects the interaction between the entrapped water and the RM interface, greatly modifying the interfacial water structure in comparison with the results known for Na-AOT.
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