Abstract
Electron spin echo modulation (ESEM) of x-doxylstearic acid spin probes (x-DSA, x = 5, 7, 10, 12, and 16) in mixed micellar solutions of ionic and nonionic surfactants has been studied as a function of the doxyl position along the alkyl chain of the stearic acid spin probe and of the mixed micellar composition. The mixed micellar systems investigated were sodium dodecyl sulfate (SDS) or dodecyltrimethylammonium chloride (DTAC) with hexakis(ethylene glycol) monododecyl ether (C[sub 12]E[sub 6]), selectively deuterated along the poly(ethylene glycol) group (C[sub 12]D[sub 6]) or along the alkyl chain ((CD)[sub 12]E[sub 6]) in H[sub 2]O and D[sub 2]O. The average probe conformation and probe location in the pure surfactants and in the mixed micelles are reported as a function of the doxyl position, x. Modulation effects due to the interactions of the probe unpaired electron with deuterium in D[sub 2]O give direct evidence that the hydration is maximized for an equimolar mixture of SDS/C[sub 12]E[sub 6] mixed micelles. It is also found that the polar head groups of SDS and DTAC surfactants are located in the ethylene oxide region of the C[sub 12]E[sub 6] surfactant. A comparative analysis of the deuterium modulation depth, arising from deuteriums located inmore » the alkyl chain or in the ethylene oxide groups of the nonionic surfactant, shows that SDS polar head groups are located at the surface of the mixed micelle, close to the second ethylene oxide group of C[sub 12]E[sub 6], while DTAC polar head groups are located deeper inside the mixed micelle, at the 5th-6th ethylene oxide group of the nonionic surfactant. These results provide an explanation at the molecular level of the different thermodynamical behavior found for mixed micelles of anionic-nonanionic and cationic-nonionic surfactants. 44 refs., 8 figs.« less
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