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。 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
References
[1]
2 Zhang Y. ; Zhang Y. ; Wang C. ; Liu X. ; Fang Y. ; Feng Y. Green Chem. 2016, 18 (2), 392. doi: 10.1039/C5GC01411E
[2]
4 Wu J. ; Xu Y. ; Dabros. T. ; Hamza H. Energy Fuels 2003, 17 (6), 1554. doi: 10.1021/ef030113e
[3]
7 Krebs T. ; Schro?n C. G. P. H. ; Boom R. M. Chem. Eng. Sci. 2012, 71, 118. doi: 10.1016/j.ces.2011.10.057
[4]
8 Zhang Y. ; Han Y. ; Chu Z. ; He S. ; Zhang J. ; Feng Y. J.Colloid Interface Sci. 2013, 394, 319. doi: 10.1016/j.jcis.2012.11.032
[5]
14 Xu H. B. Biological trace elements-selenium Wuhan: Huazhong institute of technology press, 1984, 104.
[6]
15 Combs Jr G. F. West.J. Med. 1990, 153 (2), 192.
[7]
17 Zhang Y. ; Yang C. ; Guo S. ; Chen H. ; Liu X. Chem. Commun. 2016, 52 (86), 12717. doi: 10.1039/C6CC06699B
[8]
28 Kong W. ; Guo S. ; Wu S. ; Liu X. ; Zhang Y. Langmuir 2016, 32 (38), 9846. doi: 10.1021/acs.langmuir.6b02616
[9]
29 Brown P. ; Butts C. P. ; Eastoe J. Soft Matter 2013, 9 (8), 2365. doi: 10.1039/C3SM27716J
[10]
30 Rosen M. J. ; Kunjappu J. T. Surfactants and Interfacial Phenomena 4th ed Hoboken, NJ: John Wiley & Son, 2012.
[11]
1 Liu Y. X. ; Jessop P. G. ; Cunningham M. ; Eckert C. A. ; Liotta C. L. Science 2006, 313, 958. doi: 10.1126/science.1128142
[12]
3 Zhang Y. ; Kong W. ; An P. ; He S. ; Liu X. Langmuir 2016, 32 (10), 2311. doi: 10.1021/acs.langmuir.5b04459
[13]
5 Feng X. ; Mussone P. ; Gao S. ; Wang S. ; Wu S.Y. ; Masliyah J. H. ; Xu Z. Langmuir 2010, 26 (5), 3050. doi: 10.1021/la9029563
[14]
6 Lin C. ; He G. ; Dong C. ; Liu H. ; Xiao G. ; Liu Y. Langmuir 2008, 24 (10), 5291. doi: 10.1021/la704079s
[15]
10 Brown P. ; Butts C. P. ; Cheng J. ; Eastoe J. ; Russell C. A. ; Smith G. N. Soft Matter 2012, 8 (29), 7545. doi: 10.1039/C2SM26077H
[16]
11 Zhang Y. ; Feng Y. ; Wang J. ; He S. ; Guo Z. ; Chu Z. ; Dreiss C. A. Chem. Commun. 2013, 49 (43), 4902. doi: 10.1039/C3CC41059E
[17]
12 Tsuchiya K. ; Orihara Y. ; Kondo Y. ; Yoshino N. ; Ohkubo T. ; Sakai H. ; Abe M. J.Am. Chem. Soc. 2004, 126 (39), 12282. doi: 10.1021/ja0467162
[18]
25 Sk?ld R. O. ; Tunius M. A. R. J.Colloid Interface Sci. 1992, 152 (1), 183. doi: 10.1016/0021-9797(92)90018-H
[19]
9 Takahashi Y. ; Koizumi N. ; Kondo Y. Langmuir 2016, 32 (3), 683. doi: 10.1021/acs.langmuir.5b03912
[20]
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. doi: 10.1016/j.jcis.2008.01.039
[21]
徐辉碧. 生物微量元素-硒, 武汉: 华中工学院出版社, 1984, 104.
[22]
16 Ip C. ; Hayes C. ; Budnick R. M. ; Ganther H. E. Cancer Res. 1991, 51 (2), 595.
[23]
18 Tan X. ; Yu Y. ; Liu K. ; Xu H. ; Liu D. ; Wang Z. ; Zhang X. Langmuir 2012, 28 (25), 9601. doi: 10.1021/la301703t
[24]
19 Wang L. ; Cao W. ; Yi Y. ; Xu H. Langmuir 2014, 30 (19), 5628. doi: 10.1021/la501054z
[25]
20 Xu H. ; Cao W. ; Zhang X. Acc. Chem. Res. 2013, 46 (7), 1647. doi: 10.1021/ar4000339
[26]
21 Wang Y. ; Xu H. ; Ma N. ; Wang Z. ; Zhang X. ; Liu J. ; Shen J. Langmuir 2006, 22 (13), 5552. doi: 10.1021/la060711w
[27]
22 Zhang Y. ; Kong W. ; Wang C. ; An P. ; Fang Y. ; Feng Y. ; Qin Z. ; Liu X. Soft Matter 2015, 11 (38), 7469. doi: 10.1039/C5SM01515D
[28]
23 Vermather M. ; Stiles P. ; Bachofer S. J. ; Simonis U. Langmuir 2002, 18 (4), 1030. doi: 10.1021/la0109765
[29]
24 Lin Y. ; Qiao Y. ; Yan Y. ; Huang J. Soft Matter 2009, 5 (16), 3047. doi: 10.1039/B906960G
[30]
26 Gallardo B. S. ; Hwa M. J. ; Abbott N. L. Langmuir 1995, 11 (11), 4209. doi: 10.1021/la00011a008
[31]
27 Szymanowski J. ; Szewczyk H. ; Hetper J. Tenside Deterg. 1981, 18, 333.