含硒磺基甜菜碱表面活性剂界面性能的氧化-还原响应行为

doi:10.3866/PKU.WHXB201702222

摘要/Abstract

摘要：

硒，作为一种新的氧化-还原响应位点因其良好的生物相容性日益引起人们的关注，然而，对这种新型氧化-还原响应型表面活性剂的研究相对较少，尤其是其界面性能的智能调控。本文以含硒两性离子表面活性剂苄基十一烷基磺基甜菜碱（BSeUSB）为对象，研究了其分子结构、Krafft温度、表/界面张力及发泡和乳化性能的氧化-还原刺激响应行为。发现在极微量的H₂O₂（≤体系总质量的0.056%）氧化下，BSeUSB分子中疏水的-Se-C-键转变成了具有一定亲水能力的Se=O键，表面活性剂从单头单尾的还原态变成了类Bola型的氧化态，导致表面活性剂的Krafft温度由（23.5±0.5）℃下降至0℃以下，5.00 mmol·L^-1时的表/界面张力分别从45.15、5.52 mN·m^-1升高至61.63、18.38 mN·m^-1。宏观上，还原态具有良好的发泡和乳化性能，而氧化态的发泡和乳化能力几乎消失。再次加入极少量还原剂Na₂SO₃（≤体系总质量的0.060%）后，分子的微观结构和溶液性能又可恢复到初始状态。总之，通过极微量H₂O₂和Na₂SO₃的交替加入，我们实现了该表面活性剂界面性能的智能调控。

关键词: 氧化-还原响应, 含硒表面活性剂, 甜菜碱, 界面性能, 泡沫, 乳液

Abstract:

Because of good biocompatibility using Se atom as the redox-responsive group has aroused considerable attention. However, only a few efforts have been devoted to Se-containing surfactant, especially for smart control of interfacial properties. This paper focuses on the redox-responsive behaviors of molecular structure, Krafft temperature, Surface/interfacial tension, foaming and emulsification of Se-containing zwitterionic surfactant, benzylselanyl-undecyl-dimethyl ammonium propane sulfonate (BSeUSB). The results show that after oxidization with a trace of H₂O₂ (≤0.056% of total mass), reduced form BSeUSB with one hydrophilic head and one hydrophobic tail transformed to Bola-type oxidized form BSeUSB-Ox due to the presence of a new hydrophilic group (selenoxide). And thus Krafft temperature decreased from (23.5±0.5)℃ to less than 0℃. The surface/interfacial tension at 5.00 mmol·L^-1 increased from 45.15, 5.52 mN·m^-1 to 61.63, 18.38 mN·m^-1, respectively. Macroscopically, reduced form BSeUSB has good foaming and emulsification properties, while the foaming and emulsification abilities of oxidized form BSeUSB-Ox almost disappeared. Interestingly the molecular structure and the solution properties re-turned the initial states after reduction with a trace of Na₂SO₃ (≤0.060% of total mass). In a word, by the addition trace amounts of H₂O₂ and Na₂SO₃ alternately, we have achieved the smart control of the interfacial properties of the surfactant.

Key words: Redox-responsive, Se-containing surfactant, Betaine, Interfacial property, Foam, Emulsion

MSC2000:

O648

孔伟伟,郭爽,张永民,刘雪锋. 含硒磺基甜菜碱表面活性剂界面性能的氧化-还原响应行为[J]. 物理化学学报, 2017, 33(6): 1205-1213.

Wei-Wei KONG,Shuang GUO,Yong-Min ZHANG,Xue-Feng LIU. Redox-Responsive Interfacial Properties of Se-Containing Sulfobetaine Surfactant[J]. Acta Phys. -Chim. Sin., 2017, 33(6): 1205-1213.

参考文献

1	Liu Y. X. ; Jessop P. G. ; Cunningham M. ; Eckert C. A. ; Liotta C. L. Science 2006, 313, 958.
2	Zhang Y. ; Zhang Y. ; Wang C. ; Liu X. ; Fang Y. ; Feng Y. Green Chem. 2016, 18 (2), 392.
3	Zhang Y. ; Kong W. ; An P. ; He S. ; Liu X. Langmuir 2016, 32 (10), 2311.
4	Wu J. ; Xu Y. ; Dabros. T. ; Hamza H. Energy Fuels 2003, 17 (6), 1554.
5	Feng X. ; Mussone P. ; Gao S. ; Wang S. ; Wu S.Y. ; Masliyah J. H. ; Xu Z. Langmuir 2010, 26 (5), 3050.
6	Lin C. ; He G. ; Dong C. ; Liu H. ; Xiao G. ; Liu Y. Langmuir 2008, 24 (10), 5291.
7	Krebs T. ; Schro?n C. G. P. H. ; Boom R. M. Chem. Eng. Sci. 2012, 71, 118.
8	Zhang Y. ; Han Y. ; Chu Z. ; He S. ; Zhang J. ; Feng Y. J.Colloid Interface Sci. 2013, 394, 319.
9	Takahashi Y. ; Koizumi N. ; Kondo Y. Langmuir 2016, 32 (3), 683.
10	Brown P. ; Butts C. P. ; Cheng J. ; Eastoe J. ; Russell C. A. ; Smith G. N. Soft Matter 2012, 8 (29), 7545.
11	Zhang Y. ; Feng Y. ; Wang J. ; He S. ; Guo Z. ; Chu Z. ; Dreiss C. A. Chem. Commun. 2013, 49 (43), 4902.
12	Tsuchiya K. ; Orihara Y. ; Kondo Y. ; Yoshino N. ; Ohkubo T. ; Sakai H. ; Abe M. J.Am. Chem. Soc. 2004, 126 (39), 12282.
13	Fan H. ; Han F. ; Liu Z. ; Qin L. ; Li Z. ; Liang D. ; Ke F. ; Huang J. ; Fu H. J.Colloid Interface Sci. 2008, 321 (1), 227.
14	Xu H. B. Biological trace elements-selenium Wuhan: Huazhong institute of technology press, 1984, 104.
14	徐辉碧. 生物微量元素-硒, 武汉: 华中工学院出版社, 1984, 104.
15	Combs Jr G. F. West.J. Med. 1990, 153 (2), 192.
16	Ip C. ; Hayes C. ; Budnick R. M. ; Ganther H. E. Cancer Res. 1991, 51 (2), 595.
17	Zhang Y. ; Yang C. ; Guo S. ; Chen H. ; Liu X. Chem. Commun. 2016, 52 (86), 12717.
18	Tan X. ; Yu Y. ; Liu K. ; Xu H. ; Liu D. ; Wang Z. ; Zhang X. Langmuir 2012, 28 (25), 9601.
19	Wang L. ; Cao W. ; Yi Y. ; Xu H. Langmuir 2014, 30 (19), 5628.
20	Xu H. ; Cao W. ; Zhang X. Acc. Chem. Res. 2013, 46 (7), 1647.
21	Wang Y. ; Xu H. ; Ma N. ; Wang Z. ; Zhang X. ; Liu J. ; Shen J. Langmuir 2006, 22 (13), 5552.
22	Zhang Y. ; Kong W. ; Wang C. ; An P. ; Fang Y. ; Feng Y. ; Qin Z. ; Liu X. Soft Matter 2015, 11 (38), 7469.
23	Vermather M. ; Stiles P. ; Bachofer S. J. ; Simonis U. Langmuir 2002, 18 (4), 1030.
24	Lin Y. ; Qiao Y. ; Yan Y. ; Huang J. Soft Matter 2009, 5 (16), 3047.
25	Sk?ld R. O. ; Tunius M. A. R. J.Colloid Interface Sci. 1992, 152 (1), 183.
26	Gallardo B. S. ; Hwa M. J. ; Abbott N. L. Langmuir 1995, 11 (11), 4209.
27	Szymanowski J. ; Szewczyk H. ; Hetper J. Tenside Deterg. 1981, 18, 333.
28	Kong W. ; Guo S. ; Wu S. ; Liu X. ; Zhang Y. Langmuir 2016, 32 (38), 9846.
29	Brown P. ; Butts C. P. ; Eastoe J. Soft Matter 2013, 9 (8), 2365.
30	Rosen M. J. ; Kunjappu J. T. Surfactants and Interfacial Phenomena 4th ed Hoboken, NJ: John Wiley & Son, 2012.

[1]	龚铃堰, 廖广志, 陈权生, 栾和鑫, 冯玉军. 表面活性剂溶胀胶束：性能及应用[J]. 物理化学学报, 2019, 35(8): 816 -828 .
[2]	王喆,贾康乐,刘同庆,胡俊文,李学丰,董金凤. pH和光对复合型乳液拓扑结构的调控[J]. 物理化学学报, 2019, 35(1): 84 -91 .
[3]	吴文昊,黄心宇,姚锐敏,陈人杰,李凯,邹如强. 煤基碳泡沫/聚氨酯相变复合材料的制备及储热性能[J]. 物理化学学报, 2017, 33(1): 255 -261 .
[4]	孙小祥,陈宇,赵剑曦. 气相二氧化硅/季铵Gemini表面活性剂稳定的泡沫体系[J]. 物理化学学报, 2016, 32(8): 2045 -2051 .
[5]	吴伟,刘丹丹,徐志成,宫清涛,黄建滨,张磊,张路. 支链化甜菜碱和阳离子表面活性剂在聚甲基丙烯酸甲酯表面的吸附及其润湿性质[J]. 物理化学学报, 2016, 32(5): 1214 -1220 .
[6]	陈芳,陈助国,孙会昭,孟繁想,马晓燕. 阴离子对SiO₂-PNIPAM构筑温敏Pickering乳液稳定性的影响[J]. 物理化学学报, 2016, 32(3): 763 -770 .
[7]	林有铖,钟新仙,黄寒星,王红强,冯崎鹏,李庆余. 不同磺酸掺杂聚苯胺的制备及在超级电容器中的应用[J]. 物理化学学报, 2016, 32(2): 474 -480 .
[8]	梁梅清,殷鸿尧,冯玉军. 智能水基泡沫研究进展[J]. 物理化学学报, 2016, 32(11): 2652 -2662 .
[9]	陈香,潘建明,闫永胜. 埃洛石纳米管稳定的Pickering高内相乳液模板制备大孔聚合泡沫吸附分离三氟氯氰菊酯[J]. 物理化学学报, 2016, 32(11): 2794 -2802 .
[10]	朱庆宫,孙晓甫,康欣晨,马珺,钱庆利,韩布兴. 泡沫铜负载硫化亚铜电极高效电催化还原二氧化碳制备甲酸[J]. 物理化学学报, 2016, 32(1): 261 -266 .
[11]	张巧玲, 李磊, 刘有智, 魏冰, 郭加欣, 冯玉杰. TiO₂-SA纳米光催化材料接枝动力学、结构及性能[J]. 物理化学学报, 2015, 31(6): 1015 -1024 .
[12]	宋冰蕾,翟兆兰,赵剑曦,孙国静. Gemini表面活性剂/C₁₂E_n混合体系的界面吸附、扩张粘弹与泡沫稳定性[J]. 物理化学学报, 2015, 31(12): 2324 -2331 .
[13]	徐文丽, 陈庆德, 沈兴海. AOT微乳液中通过水化电子产额调控合成BaSO₄纳米纤维[J]. 物理化学学报, 2014, 30(6): 1194 -1200 .
[14]	冯星星, 谢菁, 胡庚申, 贾爱平, 谢冠群, 罗孟飞. 五乙烯六胺修饰的MCF基吸附剂的制备及其CO₂吸附性能研究[J]. 物理化学学报, 2013, 29(06): 1266 -1272 .
[15]	韩莹, 朱露, 沈明, 李恒恒. 新型双链表面活性剂DDOBA的合成与高单分散性憎水纳米金的制备[J]. 物理化学学报, 2013, 29(01): 131 -138 .