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Probing Dynamics and Mechanism of Exchange Process of Quaternary Ammonium Dimeric Surfactants, 14-s-14, in the Presence of Conventional Surfactants B

Liu, Jun, Jiang, Yan, Chen, Hong, Mao, Shi Zhen, Du, You Ru, Liu, Mai Li
The Journal of physical chemistry 2012 v.116 no.51 pp. 14859-14868
ammonium, cationic surfactants, electrostatic interactions, fluorescence, hydrophobic bonding, micelles, nonionic surfactants, nuclear magnetic resonance spectroscopy, octoxynol, sodium dodecyl sulfate
In this Article, we investigated effects of different types of conventional surfactants on exchange dynamics of quaternary ammonium dimeric surfactants, with chemical formula C₁₄H₂₉N⁺(CH₃)₂– (CH₂)ₛ–N⁺(CH₃)₂C₁₄H₂₉·2Br–, or 14-s-14 for short. Two nonionic surfactants, TritonX-100 (TX-100) and polyethylene glycol (23) laurylether (Brij-35), and one cationic surfactant, n-tetradecyltrimethyl ammonium bromide (TTAB), and one ionic surfactant, sodium dodecyl sulfate (SDS) were chosen as typical conventional surfactants. Exchange rates of 14-s-14 (s = 2, 3, and 4) between the micelle form and monomer in solution were detected by two NMR methods: one-dimensional (1D) line shape analysis and two-dimensional (2D) exchange spectroscopy (EXSY). Results show that the nonionic surfactants (TX-100 and Brij-35), the cationic surfactant (TTAB), and the ionic surfactant (SDS) respectively accelerated, barely influenced, and slowed the exchange rate of 14-s-14. The effect mechanism was investigated by the self-diffusion experiment, relaxation time measurements (T₂/T₁), the fluorescence experiment (I₁/I₃) and observed chemical shift variations. Results reveal that, nonionic conventional surfactants (TX-100 and Brij-35) loosened the molecule arrangement and decreased hydrophobic interactions in the micelle, and thus accelerated the exchange rate of 14-s-14. The cationic conventional surfactant (TTAB) barely changed the molecule arrangement and thus barely influenced the exchange rate of 14-s-14. The ionic conventional surfactant (SDS) introduced the electrostatic attraction effect, tightened the molecule arrangement, and increased hydrophobic interactions in the micelle, and thus slowed down the exchange rate of 14-s-14. Additionally, the two-step exchange mechanism of 14-s-14 in the mixed solution was revealed through interesting variation tendencies of exchange rates of 14-s-14.