黏弹性表面活性剂（VI）——智能蠕虫状胶束

doi:10.3969/j.issn.2097-2806.2026.06.001

摘要/Abstract

摘要：

智能蠕虫状胶束具备环境刺激响应、可逆溶胶-凝胶转变特性，是胶体化学、油气开采及生物医药交叉领域重点研究材料。本讲聚焦智能蠕虫状胶束调控机制、构筑路径、响应体系及应用场景，梳理智能响应底层逻辑：依托氢键、疏水作用等可逆非共价作用力，外界刺激可改变胶束临界堆积参数，驱动胶束形貌可逆转变，实现体系黏度可控调节。目前智能蠕虫状胶束主要依赖分子功能改性、响应助剂复配构筑。分类阐述了温度、pH、光、氧化-还原、烃类介质及多重耦合六大类响应体系的响应机理、微观结构演变与流变规律，对比不同体系性能优劣。现有体系中，烃响应胶束已规模化应用于油气储层改造，多耦合响应胶束适配生物医药、智能流变器件等高端场景。总结了智能蠕虫状胶束体系现有短板，指出了未来发展方向，为长效稳定、工况适配型智能蠕虫状胶束定向开发与产业化应用提供了一定的支撑。

关键词: 蠕虫状胶束, 自组装, 刺激响应, 溶胶-凝胶转变, 流变调控, 表面活性剂

Abstract:

Smart wormlike micelles （SWLMs） possess reversible stimulus-responsive assembly characteristics, which have become a research hotspot in colloid chemistry, oil and gas production, and biomedical fields. Based on the previous research series on wormlike micelles, this paper focuses on the intelligent design mechanism, construction strategies, classification systems and practical applications of SWLMs. The intelligent response of micelles relies on reversible non-covalent weak interactions and adjustable dynamic equilibrium, and external stimuli can change the critical packing parameter to realize reversible morphology transformation between spherical and wormlike micelles, further achieving sol-gel transition and rheological regulation. There are two mainstream construction approaches: Functional modification of surfactant molecules and regulation by the responsive hydrotropes. This paper systematically summarizes six typical stimulus-responsive systems, including temperature, pH, light, redox, hydrocarbon, and multi-coupled response systems, and clarifies their microstructural evolution and macroscopic rheological response mechanisms. Among them, hydrocarbon-responsive micelles have achieved large-scale commercial application in oilfield clean fracturing fluid, while pH, photo and redox-responsive systems show great potential in drug delivery, microfluidic control and green cleaning fields. At present, single-stimulus systems have limited application scenarios, and multi-stimulus coupled wormlike micelles developed via dynamic covalent bonds are the mainstream research direction. This review paper compares the advantages and limitations of different construction paths, analyzes the existing technical bottlenecks such as poor long-term stability of surfactant-hydrotrope systems and incomplete response reversibility of partial photo-responsive systems, and provides theoretical reference for the targeted molecular design and industrial application of high-performance SWLMs materials.

Key words: wormlike micelles, self-assembly, stimuli-responsive, sol-gel transition, rheology modifier, surfactant

中图分类号:

TQ423

楚宗霖, 姜展朋, 冯玉军. 黏弹性表面活性剂（VI）——智能蠕虫状胶束[J]. 日用化学工业（中英文）, 2026, 56(6): 695-705.

Zonglin Chu, Zhanpeng Jiang, Yujun Feng. Viscoelastic surfactants (VI) Smart wormlike micelles[J]. China Surfactant Detergent & Cosmetics, 2026, 56(6): 695-705.

图/表 6

图1

图2

图3

图4

图5

图6

参考文献 31

[1]	冯玉军. 黏弹性表面活性剂 (I)——百年胶束发展史及蠕虫状胶束的发现[J]. 日用化学工业(中英文), 2026, 56 (1) : 8-16.
[2]	冯玉军. 黏弹性表面活性剂(II)——蠕虫状胶束形成机理及体系构成[J]. 日用化学工业 (中英文), 2026, 56 (2) : 137-148.
[3]	冯玉军. 黏弹性表面活性剂(III)——稳态流变与剪切带现象[J]. 日用化学工业 (中英文), 2026, 56 (3) : 278-283.
[4]	冯玉军. 黏弹性表面活性剂(IV)——动态流变[J]. 日用化学工业 (中英文), 2026, 56 (4) : 425-432.
[5]	冯玉军. 黏弹性表面活性剂(V)——蠕虫状胶束与聚合物的相似点及差异性[J]. 日用化学工业(中英文), 2026, 56 (5) : 558-563.
[6]	Chu Z, Dreiss C A, Feng Y. Smart wormlike micelles[J]. Chemical Society Reviews, 2013, 42 (17) : 7174-7203. doi: 10.1039/c3cs35490c pmid: 23545844
[7]	Feng Y, Chu Z, Dreiss C A. Smart wormlike micelles: Design, characteristics and applications[M]. Springer, Heidelberg, 2015.
[8]	Sharma S C, Shrestha L K, Tsuchiya K, et al. Viscoelastic wormlike micelles of long polyoxyethylene chain phytosterol with lipophilic nonionic surfactant in aqueous solution[J]. Journal of Physical Chemistry B, 2009, 113 (10) : 3043-3050. doi: 10.1021/jp8102244
[9]	Hassan P A, Valaulikar B S, Manohar C, et al. Vesicle to micelle transition: Rheological investigations[J]. Langmuir, 1996, 12 (18) : 4350-4357. doi: 10.1021/la960269p
[10]	Mendes E, Oda R, Manohar C, et al. A small-angle neutron scattering study of a shear-induced vesicle to micelle transition in surfactant mixtures[J]. Journal of Physical Chemistry B, 1998, 102 (2) : 338-343. doi: 10.1021/jp972392a
[11]	Chu Z, Feng Y. Thermo-switchable surfactant gel[J]. Chemical Communications, 2011, 47 (25) : 7191-7193. doi: 10.1039/c1cc11428j pmid: 21544301
[12]	Greenhill-Hooper M J, O’Sullivan T P, Wheeler P A. The aggregation behavior of octadecylphenylalkoxysulfonates 1. temperature-dependence of the solution behavior[J]. Journal of Colloid and Interface Science, 1988, 124 (1) : 77-87. doi: 10.1016/0021-9797(88)90327-X
[13]	Tobita K, Sakai H, Kondo Y, et al. Thermoresponsive viscoelasticity of sodium 1-oxo-1- [4- (tridecafluorohexyl)phenyl] -2-hexanesulfonate aqueous solutions[J]. Langmuir, 1997, 13 (19) : 5054-5055. doi: 10.1021/la970347o
[14]	Maeda H, Yamamoto A, Souda M, et al. Effects of protonation on the viscoelastic properties of tetradecyldimethylamine oxide micelles[J]. Journal of Physical Chemistry B, 2001, 105 (23) : 5411-5418. doi: 10.1021/jp0101155
[15]	Lin Y, Han X, Huang J, et al. A facile route to design pH-responsive viscoelastic wormlike micelles: Smart use of hydrotropes[J]. Journal of Colloid and Interface Science, 2009, 330 (2) : 449-455. doi: 10.1016/j.jcis.2008.10.071 pmid: 19059596
[16]	Chu Z, Feng Y. pH-Switchable wormlike micelles[J]. Chemical Communications, 2010, (46) : 9028-9030.
[17]	Feng Y, Chu Z. pH-Tunable wormlike micelles based on an ultra-long-chain “pseudo” gemini surfactant[J]. Soft Matter, 2015, 11(23) : 4614-4620. doi: 10.1039/C5SM00677E
[18]	Sakai H, Orihara Y, Kodashima H, et al. Photoinduced reversible change of fluid viscosity[J]. Journal of American Chemical Society, 2005, 127 (39) : 13454-13455. doi: 10.1021/ja053323+
[19]	Ketner A M, Kumar R, Davies T S, et al. A simple class of photorheological fluids: Surfactant solutions with viscosity tunable by light[J]. Journal of American Chemical Society, 2007, 129 (6) : 1553-1559. doi: 10.1021/ja065053g
[20]	Kumar R, Raghavan S R. Photogelling fluids based on light-activated growth of zwitterionic wormlike micelles[J]. Soft Matter, 2009, 5 (4) : 797-803. doi: 10.1039/B809452G
[21]	Tsuchiya K, Orihara Y, Kondo Y, et al. Control of viscoelasticity using redox reaction[J]. Journal of American Chemical Society, 2004, 126(39) : 12282-12283. doi: 10.1021/ja0467162
[22]	Hoffmann H, Ebert G. Surfactants, micelles and fascinating phenomena[J]. Angewandte Chemie International Edition, 1988, 27(7) : 902-912.
[23]	Hoffmann H, Ulbricht W. The rheological behavior of different viscoelastic surfactant solutions[J]. Tenside, Surfactants and Detergents, 1987, 24 (1) : 23-31. doi: 10.1515/tsd-1987-240111
[24]	Molchanov V S, Philippova O E, Khokhlov A R, et al. Self-assembled networks highly responsive to hydrocarbons[J]. Langmuir, 2007, 23(1) : 105-111. pmid: 17190491
[25]	Philippova O E, Khokhlov A R. Smart polymers for oil production[J]. Petroleum Chemistry, 2010, 50: 266-270. doi: 10.1134/S0965544110040031
[26]	Shibaev A V, Tamm M V, Molchanov V S, et al. How a viscoelastic solution of wormlike micelles transforms into a microemulsion upon absorption of hydrocarbon: new insight[J]. Langmuir, 2014, 30 (13) :3705-3714. doi: 10.1021/la500484e pmid: 24617576
[27]	Jiang L X, Wang K, Ke F Y, et al. Endowing catanionic surfactant vesicles with dual responsive abilities via a noncovalent strategy: Introduction of a responser, sodium cholate[J]. Soft Matter, 2009, 5(3) : 599-606. doi: 10.1039/B813498G
[28]	Zhang Y, Han Y, Chu Z, et al. Thermally-induced structural transitions from fluids to hydrogels with pH-switchable anionic wormlike micelles[J]. Journal of Colloid and Interface Science, 2013, 394: 319-328. doi: 10.1016/j.jcis.2012.11.032
[29]	Yang Y, Dong J, Li X. Micelle to vesicle transitions of N-dodecyl- 1, ω-diaminoalkanes: Effects of pH, temperature and salt[J]. Journal of Colloid and Interface Science, 2012, 380 (1) : 83-89. doi: 10.1016/j.jcis.2012.04.068 pmid: 22647344
[30]	Ren G, Li B, Ren L, et al. pH-responsive nanoemulsions based on a dynamic covalent surfactant[J]. Nanomaterials, 2021, 11 (6) : 1390.
[31]	Minkenberg C B, Homan B, Boekhoven J, et al. Responsive wormlike micelles from dynamic covalent surfactants[J]. Langmuir, 2012, 28 (38) : 13570-13576. pmid: 22873840