TX-100和CTAB交换动力学的核磁共振研究
收稿日期: 2015-09-09
修回日期: 2016-07-11
网络出版日期: 2016-09-05
基金资助
国家自然科学基金资助项目（21375145）.
Exchange Kinetics of Surfactants TX-100 and CTAB Investigated by 1H NMR Spectroscopy
Received date: 2015-09-09
Revised date: 2016-07-11
Online published: 2016-09-05
运用核磁共振（NMR）方法分别测定了表面活性剂辛基苯聚氧乙烯醚（TX-100）和十六烷基三甲溴化铵（CTAB）在不同温度下的临界胶束浓度．阐述了应用1D NMR线型分析方法对表面活性剂快交换体系平均停留时间的定量测量．实验测量了TX-100和CTAB胶束溶液中表面活性剂分子在不同温度下的平均停留时间．结果显示，平均停留时间随温度的增加逐渐减小，说明TX-100和CTAB分子进出胶束的速率随温度的增加逐渐加快．利用阿伦尼乌斯公式拟合，获得了TX-100和CTAB的表观交换活化能，TX-100的表观交换活化能为17.6 kJ/mol，CTAB的表观交换活化能为75.3 kJ/mol．对TX-100和CTAB平均停留时间和表观交换活化能进行分析，得出平均停留时间和表观交换活化能与分子结构的关系：表观交换活化能反映的是疏水相互作用和静电斥力的大小；而平均停留时间不仅受活化能的影响，还与分子结构有关．
关键词： 液体核磁共振(liquid NMR); 1D线型分析; 表面活性剂; 平均停留时间; 表观交换活化能
俞刚金 , 刘君 , 毛诗珍 , 刘买利 , 杜有如 . TX-100和CTAB交换动力学的核磁共振研究[J]. 波谱学杂志, 2016 , 33(3) : 422 -431 . DOI: 10.11938/cjmr20160307
The critical micelle concentration (CMC) of Triton X-100 (TX-100) and cetyltrimethylammonium bromide (CTAB) was measured by nuclear magnetic resonance (NMR) technologies at different temperature. The average residence time of TX-100 and CTAB were determined by one-dimensional line shape analysis. The average residence time of both compounds decreased with increasing temperature, suggesting that the rate of TX-100 and CTAB molecules entering/leaving the micelles increased with temperature. The apparent activation energy of the exchange process was calculated with the Arrhenius equation, and found to be 17.6 kJ/mol for TX-100 and 75.3 kJ/mol for CTAB. The apparent activation energy likely reflected the strength of hydrophobic interaction; while the average residence time depended not only on the hydrophobic interaction but also on the molecular structure.
[1] Shchekin A K, Rusanov A I, Kuni F M. Kinetic theory of molecular mechanism of micellar relaxation[J]. Chem Lett, 2012, 41(10): 1 081-1 083.
[2] Grinin A P, Grebenkov D S. Study of relaxation in micellar solution by the numerical experiment[J]. Colloid, 2003, 65(5): 552-561.
[3] Aniansson E A G, Wall S N, Almgren M, et al. Theory of kinetics of micellar equilibria and quantitative interpretation of chemical relaxation studies of micellar solutions of ionic surfactants[J]. Phy Chem, 1976, 80(9): 905-922.
[4] Lang J, Zana R, Bauer R, et al. Chemical relaxation studies of micellar equilibria[J]. Phy Chem, 1975, 79(3): 276-283.
[5] Aniansso E, Wall S N. Kinetics of step-wise micelle association[J]. Phy Chem, 1974, 78(10): 1 024-1 030.
[6] Patist A, Kanicky J R, Shukla P K, et al. Importance of micellar kinetics in relation to technological processes[J]. Colloid Interface Sci, 2002, 245(1): 1-15.
[7] Patist A, Oh S G, Leung R, et al. Kinetics of micellization: Its significance to technological processes[J]. Colloids Surf A, 2001, 176(1): 3-16.
[8] Mijnlief P, Ditmarsc R. Rate of micelle formation of sodium alkyl sulphates in water[J]. Nature, 1965, 208(5 013): 889-891.
[9] Frindi M, Michels B, Zana R. Ultrasonic-absorption studies of surfactant exchange between micelles and the bulk phase in aqueous micellar solutions of amphoteric surfactants[J]. Phy Chem, 1994, 98(26): 6 607-6 611.
[10] Muller N. Kinetics of micelle dissociation by temperature-jump techniques-reinterpretation[J]. Phy Chem, 1972, 76(21): 3 017-3 020.
[11] Yasunaga T, Takeda K, Harada S. Kinetic study of sodium dodecyl sulfate micelle dissociation by a stopped-flow method[J]. Colloid Interface Sci, 1973, 42(2): 457-463.
[12] Bain A D, Rex D M, Smith R N. Fitting dynamic NMR lineshapes[J]. Magn Reson Chem, 2001, 39(3): 122-126.
[13] Rao B D N. Nuclear magnetic resonance line-shape analysis and determination of exchange rates[J]. Methods Enzymol, 1989, 176: 279-311.
[14] Sergeev N M. Dynamic nuclear magnetic resonance[J]. Russ Chem Rev, 1973, 42(5): 769-798.
[15] Li Nan(李楠), Sun Peng(孙鹏), Liu Mai-li(刘买利), et al. An NMR study of phosphatidylcholine small unilamellar vesicles(磷脂酰胆碱SUV的NMR研究)[J]. Chinese J Magn Reson(波谱学杂志), 2014, 31(4): 572-578.
[16] Li Chun-fa(李春发), Zhu Xue-rong(朱雪荣). An NMR and FT-IR study on polyether modified silicon surfactant(聚醚改性有机硅表面活性剂的核磁共振及红外光谱表征)[J]. Chinese J Magn Reson(波谱学杂志), 2014, 31(2): 222-231.
[17] Yang Chun-sheng(杨春升), Cui Xiao-hong(崔晓红), Jiang Yan(蒋艳), et al. Mixed micelles of sodium dodecyl sulfate and triton X-100 in aqueous solution studied by 1H NMR(表面活性剂SDS/TX-100混合体系的NMR研究)[J]. Chinese J Magn Reson(波谱学杂志), 2009, 26(4): 466-475.
[18] Huc I, Oda R. Gemini surfactants: Studying micellisation by 1H and 19F NMR spectroscopy[J]. Chem Commun, 1999, 20: 2 025-2 026.
[19] Cui X H, Yang X Y, Chen H, et al. NMR investigation of the exchange kinetics of quaternary ammonium dimeric surfactants C-14-s-C-14·2Br[J]. Phy Chem B, 2008, 112(10): 2 874-2 879.
[20] Liu J, Jiang Y, Chen H, et al. Probing dynamics and mechanism of exchange process of quaternary ammonium dimeric surfactants, 14-s-14, in the presence of conventional surfactants[J]. Phy Chem B, 2012, 116(51): 14 859-14 868.
[21] Jiang Y, Chen H, Mao S Z, et al. Dynamics of mixed surfactants in aqueous solutions[J]. Phy Chem B, 2011, 115(9): 1 986-1 990.
[22] Ramey K C, Louick D J, Whitehur P, et al. A Line width method for determining chemical exchange rates from NMR spectra[J]. Omr-Organic Magn Reson, 1971, 3(2): 201-216.
[23] Gutowsky H S, Holm C H. Rate processes and nuclear magnetic resonance spectra .2. Hindered internal rotation of amides[J]. Chem Phy, 1956, 25(6): 1 228-1 234.
[24] Shinoda K, Hutchinson E. Pseudo-phase separation model for thermodynamic calculations on micellar solutions[J]. Phy Chem, 1962, 66(4): 577-582.
[25] Zhang S H, Gao Y N, Dong B, et al. Interaction between the added long-chain ionic liquid 1-dodecyl-3-methylimidazolium tetrafluoroborate and triton X-100 in aqueous solutions[J]. Colloids Surf A, 2010, 372(1-3): 182-189.
[26] Ali A, Uzair S, Malik N A, et al. Study of interaction between cationic surfactants and cresol red dye by electrical conductivity and spectroscopy methods[J]. Mol Liq, 2014, 196: 395-403.
[27] Yuan H Z, Cheng G Z, Zhao S, et al. Conformational dependence of triton X-100 on environment studied by 2D NOESY and 1H NMR relaxation[J]. Langmuir, 2000, 16(7): 3 030-3 035.
/
| 〈 |
|
〉 |