TX-100和CTAB交换动力学的核磁共振研究

doi:10.11938/cjmr20160307

波谱学杂志 ›› 2016, Vol. 33 ›› Issue (3): 422-431.doi: 10.11938/cjmr20160307

TX-100和CTAB交换动力学的核磁共振研究

俞刚金^1,2, 刘君¹, 毛诗珍¹, 刘买利¹, 杜有如¹

1. 波谱与原子分子物理国家重点实验室, 武汉磁共振中心(中国科学院武汉物理与数学研究所), 湖北武汉 430071;
2. 中国科学院大学, 北京 100049

收稿日期:2015-09-09 修回日期:2016-07-11 出版日期:2016-09-05 发布日期:2016-09-05
通讯作者: 毛诗珍,电话:027-87197126,E-mail:maosz@wipm.ac.cn;刘买利,电话:027-87197305,E-mail:ml.liu@wipm.ac.cn. E-mail:maosz@wipm.ac.cn;ml.liu@wipm.ac.cn
作者简介:俞刚金(1989-),男,湖北十堰人,博士研究生,分析化学专业.
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

YU Gang-jin^1,2, LIU Jun¹, MAO Shi-zhen¹, LIU Mai-li¹, DU You-ru¹

1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan (Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2015-09-09 Revised:2016-07-11 Online:2016-09-05 Published:2016-09-05

摘要/Abstract

摘要：

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

Abstract:

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.

Key words: liquid NMR, line shape analysis, surfactant, average residence time, apparent activation energy

中图分类号:

O482.53

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.

YU Gang-jin, LIU Jun, MAO Shi-zhen, LIU Mai-li, DU You-ru. Exchange Kinetics of Surfactants TX-100 and CTAB Investigated by ¹H NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2016, 33(3): 422-431.

参考文献

[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.

TX-100和CTAB交换动力学的核磁共振研究

Exchange Kinetics of Surfactants TX-100 and CTAB Investigated by ¹H NMR Spectroscopy

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	陈晓瑛, 俞刚金, 毛诗珍, 刘买利, 杜有如. 利用¹H NMR探究混合离子型/非离子型表面活性剂临界胶束浓度降低的实质[J]. 波谱学杂志, 2019, 36(2): 219-224.
[2]	陈晓瑛, 俞刚金, 毛诗珍, 刘买利, 杜有如. ¹H NMR探究空间效应对表面活性剂复配体系中协同作用的影响[J]. 波谱学杂志, 2018, 35(1): 75-80.
[3]	李双利, 朱勤俊, 刘买利, 杨运煌. 蛋白质分子核磁共振谱峰的特性及其化学位移归属[J]. 波谱学杂志, 2017, 34(2): 137-147.
[4]	张彬锋, 朱雪荣. 两种聚醚改性有机硅表面活性剂的NMR数据分析[J]. 波谱学杂志, 2016, 33(3): 432-441.
[5]	安志敏，马二倩，杨秋青*. 2-酮基-L-古龙酸结构发生改变的核磁共振研究[J]. 波谱学杂志, 2014, 31(3): 407-414.
[6]	李春发*，朱雪荣. 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]. 波谱学杂志, 2014, 31(2): 222-231.
[7]	安艳捧1,2，杨晓艳1,2，李洪德1,2，李宁1,2，唐惠儒1*. 大鼠尿液中N-氧化烟酰胺和伪尿嘧啶核苷的NMR分析[J]. 波谱学杂志, 2014, 31(2): 232-242.
[8]	杨春升, 崔晓红, 蒋艳, 毛诗珍, 刘买利. 表面活性剂SDS/TX-100混合体系的NMR研究[J]. 波谱学杂志, 2009, 26(4): 466-475.
[9]	作者：杨晓焱导师：刘买利. 单链和 gemini 表面活性剂的NMR研究[J]. 波谱学杂志, 2007, 24(3): 374-376.
[10]	作者：刘爱红导师：刘买利. 表面活性剂及水溶性功能高分子的NMR研究[J]. 波谱学杂志, 2007, 24(3): 377-379.
[11]	张红梅, 杨晓焱, 雷皓. 表面活性剂CTAB水溶液中的T₂弛豫分散研究[J]. 波谱学杂志, 2005, 22(3): 235-243.
[12]	刘爱红, 陈洪, 程功臻, 方小雯, 杨晓焱, 毛诗珍, 袁汉珍, 罗平亚, 杜有如. 季铵盐型双子表面活性剂16-4-16聚集状态的NMR研究[J]. 波谱学杂志, 2005, 22(2): 123-131.
[13]	刘爱红, 毛诗珍, 杜有如. 双子表面活性剂的NMR研究现状与展望[J]. 波谱学杂志, 2005, 22(2): 223-233.
[14]	杜定准. 表面活性剂全氟庚酸和全氟辛酸的¹⁹F NMR研究[J]. 波谱学杂志, 2003, 20(1): 29-36.
[15]	陆同兴, 崔执凤, 孙文斌, 张先焱. TX-100胶束中光解蒽醌的TR-ESR研究[J]. 波谱学杂志, 1999, 16(2): 103-108.

TX-100和CTAB交换动力学的核磁共振研究

Exchange Kinetics of Surfactants TX-100 and CTAB Investigated by 1H NMR Spectroscopy

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

Exchange Kinetics of Surfactants TX-100 and CTAB Investigated by ¹H NMR Spectroscopy