Tu Yan, Chen Qizhou, Shang Yazhuo, Teng Hongni, Liu Honglai
Key Laboratory for Advanced Materials, School of Chemistry & Molecular Engineering , East China University of Science and Technology , Shanghai 200237 , China.
Department of Applied Chemistry, College of Chemical and Environmental Engineering , Shandong University of Science and Technology , Qingdao 266510 , China.
Langmuir. 2019 Apr 2;35(13):4634-4645. doi: 10.1021/acs.langmuir.8b04290. Epub 2019 Mar 22.
The photoresponsive wormlike micelles constructed by Gemini surfactants and cinnamate derivatives play a great role in the field of smart materials. However, how the structure of cinnamate derivatives affects the photoresponsive behavior of micelles is still a hotspot for scientists to research. Here, three kinds of aromatic salts with different ortho-substituted groups including trans- o-methoxy cinnamate ( trans-OMCA), trans- o-hydroxy cinnamate ( trans-OHCA), and trans-cinnamate ( trans-CA) were introduced into Gemini surfactant 12-3-12·2Br aqueous solutions to construct photoresponsive wormlike micelles through their noncovalent interactions. Their properties were researched using the rheological method, cryo-transmission electron microscopy, and H NMR and two-dimensional nuclear Overhauser effect spectra. The results show that these cinnamate derivatives could well construct wormlike micelles with 12-3-12·2Br. Furthermore, subtle differences in the ortho substituents' structure have a significant effect on the photoresponsive behavior of formed wormlike micelles. Specifically, the zero viscosity (η) of 40 mM 12-3-12·2Br/24 mM trans-OHCA mixed solution decreases from 26.72 to 2.6 Pa·s with the shortening of the length of wormlike micelles after UV irradiation. Correspondingly, the η for the same ratio of 12-3-12·2Br/ trans-OMCA decreases from 2.42 to 0.06 Pa·s and the wormlike micelles are transited into rodlike micelles and even spherical micelles after the same UV irradiation time. However, the variation of wormlike micelles in the 12-3-12·2Br/ trans-CA system induced by UV light is not obvious with η being maintained at around 2.89 Pa·s. This study will help us better understand the effects of chemical groups on macrophenomena and microinteraction for micellar systems. It provides a theoretical basis for the construction of photoresponsive micelles, thus widening their application in the field of soft materials.
由 Gemini 表面活性剂和肉桂酸酯衍生物构建的光响应性蠕虫状胶束在智能材料领域发挥着重要作用。然而,肉桂酸酯衍生物的结构如何影响胶束的光响应行为仍是科学家们研究的热点。在此,将三种具有不同邻位取代基的芳盐,包括反式邻甲氧基肉桂酸酯(trans-OMCA)、反式邻羟基肉桂酸酯(trans-OHCA)和反式肉桂酸酯(trans-CA)引入 Gemini 表面活性剂 12-3-12·2Br 水溶液中,通过它们的非共价相互作用构建光响应性蠕虫状胶束。使用流变学方法、低温透射电子显微镜以及核磁共振氢谱和二维核 Overhauser 效应谱对其性质进行了研究。结果表明,这些肉桂酸酯衍生物能够与 12-3-12·2Br 很好地构建蠕虫状胶束。此外,邻位取代基结构的细微差异对形成的蠕虫状胶束的光响应行为有显著影响。具体而言,40 mM 12-3-12·2Br/24 mM trans-OHCA 混合溶液在紫外光照射后,随着蠕虫状胶束长度的缩短,其零粘度(η)从 26.72 降至 2.6 Pa·s。相应地,相同比例的 12-3-12·2Br/trans-OMCA 在相同的紫外光照射时间后,η 从 2.42 降至 0.06 Pa·s,蠕虫状胶束转变为棒状胶束甚至球形胶束。然而,在 12-3-12·2Br/trans-CA 体系中,紫外光诱导的蠕虫状胶束变化不明显,η 维持在 2.89 Pa·s 左右。这项研究将有助于我们更好地理解化学基团对胶束体系宏观现象和微观相互作用的影响。它为光响应性胶束的构建提供了理论基础,从而拓宽了其在软材料领域的应用。