Structure and molecular dynamics of sodium dodecylsulfate micelles modified with hydrophilic short-chain imidazolium salts in aqueous solution.
This study uses pyrene solubilization and NMR experiments to investigate the effects of two hydrophilic short-chain ionic liquids (ILs), 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF4) and 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) on the micellization of sodium dodecylsulfate (SDS) in the aqueous phase. The results of the pyrene solubilization experiments indicate that the added short-chain ILs not only promote the micellization of SDS but also modify micelle properties. For NMR studies, the present study focuses on (1) the compositions and spatial arrangements of component molecules and (2) the molecular dynamics of DS(-) in the Rmim-modified SDS micelle. Using pulsed field gradient (PFG) NMR measurements, the composition of the Rmim-modified SDS micelle was calculated by the diffusion data and was found to be correlated with the [SDS]. Two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY) experiments confirm that the 1-alkyl-3-methylimidazolium cation (Rmim(+)) is located inside the Rmim-modified SDS micelle. Corresponding to the microstructure of the Rmim-modified SDS micelle, in terms of (1)H T1 relaxation, the fast motion of SDS α-CH2 and β-CH2 segments are markedly restricted by the attached Rmim(+) to the sulfate group of DS(-), whereas the central carbons and the terminal CH3 group of DS(-) are only slightly affected. The chemical shift analysis indicates that the surface of the Rmim-modified SDS micelle is dehydrated by the absorbed Rmim(+) and becomes more hydrophobic than that of the pure SDS micelle. Insertion of Rmim(+) into the Rmim-modified SDS micelle appears to be driven through the hydrophobic interaction, and it is shown to combine with SDS molecules to constitute the hydrophobic part of the Rmim-modified SDS micelle.
Department of Chemical Engineering, National Cheng Kung University, Tainan 70101, Taiwan.
Jia-Hsien
JH
Lin
Department of Chemical Engineering, National Cheng Kung University, Tainan 70101, Taiwan. Electronic address: sshou@mail.ncku.edu.tw.
Sheng-Shu
SS
Hou
Ionic liquid; Micellization; NMR; Pyrene; Sodium dodecylsulfate