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Fundamental studies of reverse micellear aggreagates by multinuclear and multidimensional NMR spectroscopy




Sedgwick, Myles, author
Levinger, Nancy, advisor
Crans, Debbie, advisor
Henry, Chuck, committee member
Roess, Deborah, committee member
Van Orden, Alan, committee member

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Self-assembled reverse micellar aggregates using cationic, anionic and non-ionic surfactants have been investigated by multinuclear and multidimensional NMR. By utilizing 51V NMR chemical shifts and line widths of decavanadate, the local proton concentration and characteristics of the reverse micellar environment are measured. There is a distinct environmental change on the interior of the reverse micelle depending on the surfactant used. 51V NMR signals for decavanadate inside an Igepal CO-520, non-ionic surfactant, reverse micelle display sharp signals indicating the decavanadate experiences water like environment. Conversely, 51V NMR signals for decavanadate inside an Igepal CO-610/430 mixed reverse micelle show significant broadening of the decavanadate signal indicating that the environment inside the reverse micelle in which the decavanadate resides is more viscous. These data provide a description in that the water pool of non-ionic surfactants can be compared. Time resolved anisotropy decays, ultrafast time-resolved transient absorption, and 2D NMR spectroscopy have been used to study proton transfer reactions in the interiors of Igepal-CO 520, CTAB and AOT reverse micelles. For ѡ0 = 10 reverse micelles formed with anionic AOT surfactant, the HPTS proton transfer dynamics are similar to dynamics in bulk aqueous solution, and the corresponding 1H 2D NOESY NMR spectra display no cross peaks between HPTS and AOT consistent with the HPTS residing, well-hydrated by water, in the interior of the reverse micelle water pool. In contrast, ultrafast transient absorption experiments show no evidence for HPTS photoinduced proton transfer reaction in reverse micelles formed with the cationic CTAB surfactant. In CTAB reverse micelles, clear cross peaks between HPTS and CTAB in the 2D NMR spectra show that HPTS embeds in the interface. Similar behavior is observed for HPTS in Igepal reverse micelles as in CTAB reverse micelles and we interpret the slowed dynamics in the same manner. The 2D NMR spectra for HPTS in Igepal-CO 520 reverse micelles shows interaction that imply the HPTS molecule is rested near the interface inside the reverse micelle. Dynamic light scattering (DLS) and 1H NMR spectroscopic experiments suggest that the assembly of the reverse micellar aggregates depends on non-polar solvent and co-surfactant used. Two different self-assembled particles form in the AOT/cholesterol /water in cyclohexane, where in the similar system of AOT/cholesterol /water in 1-octanol there is only one particle present. In microemulsions employing 1-octanol as the continuous medium, AOT reverse micelles form in a dispersed solution of cholesterol in 1-octanol. Although the size distribution of self-assembled particles is well-known for many different systems, evidence for simultaneous formation of two distinctly sized particles in solution that are chemically different is unprecedented. By utilizing optical spectroscopic techniques, 2D NMR, and DLS, the structure of the non-ionic reverse micelles have been characterized. The impact of adding cholesterol, a biologically relevant molecule, has on the structure of the reverse micellar solutions has also been shown.


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reverse micelle


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