The dynamic NMR （DNMR） method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants, 12-s-12 and 14-s-14 （s 2, 3 a...The dynamic NMR （DNMR） method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants, 12-s-12 and 14-s-14 （s 2, 3 and 4）. The escape rate constant, k^- , was derived based on the simplified equations of DNMR theory, and the apparent activation energy of escape, Ea^- , was obtained based on the Arrhenius equation through temperature variation experiments. Results show that the orders of magnitude of k^- for 14-s-14 and 12-s-12 are respectively 10 and 103 s-1, Ea^- of 14-s-14 and 12-s-12 are respectively 54.04-73.64 and 33.42-47.09 kJ/rnol. Furthermore, k increases and Ea^- decreases with the spacer length growing. In combination with the rnicro-polarity measurements, it was revealed that molecules of 14-s-14 and 12-s-12 have to experience conformation changes when escaping from the rnicelles. The two-step molecular exchange mechanism for Gemini surfactants was therefore supported.展开更多
The critical aggregation concentration（CAC） of four with three kinds of conventional surfactants, namely,two cationic surfactants [hexadecyltrimethyl ammonium bromide（CTAB） and tetradecyltrimethyl ammonium bromide...The critical aggregation concentration（CAC） of four with three kinds of conventional surfactants, namely,two cationic surfactants [hexadecyltrimethyl ammonium bromide（CTAB） and tetradecyltrimethyl ammonium bromide（TTAB）], one anionic surfactant [sodium dodecyl sulfate（SDS）], and a nonionic surfactant [Triton X-100（TX-100）], were determined by variation of ^1H chemical shifts with surfactant concentrations. Results show that the CAC values of protons at different positions of the same molecule are different, and those of the terminal methyl protons are the lowest, respectively, which suggests that the terminal groups of the alkyl chains aggregates first during micellization. Measurement of the transverse relaxation time（T2） of different protons in SDS also show that the terminal methyl protons start to decrease with the increase in concentration first, which supports the above mentioned tendency.展开更多
基金supported by the National Natural Science Foundation of China (No.21375145)
文摘The dynamic NMR （DNMR） method was used to detect kinetic parameters of the molecular exchange process between monomers in bulk solution and those in the micelle for Gemini surfactants, 12-s-12 and 14-s-14 （s 2, 3 and 4）. The escape rate constant, k^- , was derived based on the simplified equations of DNMR theory, and the apparent activation energy of escape, Ea^- , was obtained based on the Arrhenius equation through temperature variation experiments. Results show that the orders of magnitude of k^- for 14-s-14 and 12-s-12 are respectively 10 and 103 s-1, Ea^- of 14-s-14 and 12-s-12 are respectively 54.04-73.64 and 33.42-47.09 kJ/rnol. Furthermore, k increases and Ea^- decreases with the spacer length growing. In combination with the rnicro-polarity measurements, it was revealed that molecules of 14-s-14 and 12-s-12 have to experience conformation changes when escaping from the rnicelles. The two-step molecular exchange mechanism for Gemini surfactants was therefore supported.
基金supported by the National Natural Science Foundation of China(Nos.21375145,21221064)
文摘The critical aggregation concentration（CAC） of four with three kinds of conventional surfactants, namely,two cationic surfactants [hexadecyltrimethyl ammonium bromide（CTAB） and tetradecyltrimethyl ammonium bromide（TTAB）], one anionic surfactant [sodium dodecyl sulfate（SDS）], and a nonionic surfactant [Triton X-100（TX-100）], were determined by variation of ^1H chemical shifts with surfactant concentrations. Results show that the CAC values of protons at different positions of the same molecule are different, and those of the terminal methyl protons are the lowest, respectively, which suggests that the terminal groups of the alkyl chains aggregates first during micellization. Measurement of the transverse relaxation time（T2） of different protons in SDS also show that the terminal methyl protons start to decrease with the increase in concentration first, which supports the above mentioned tendency.
