刺激响应性聚集诱导发光凝胶因子的设计、合成及性能

doi:10.16085/j.issn.1000-6613.2022-1471

化工进展 ›› 2023, Vol. 42 ›› Issue (6): 3105-3113.DOI: 10.16085/j.issn.1000-6613.2022-1471

刺激响应性聚集诱导发光凝胶因子的设计、合成及性能

裴强¹(), 胡文静¹, 聂丽珠¹, 史亚楠¹, 丁爱祥²

^1.信阳师范学院化学化工学院，河南信阳 464000
^2.厦门大学柔性电子(未来技术)研究院，福建厦门 361005

收稿日期:2022-08-09 修回日期:2022-11-16 出版日期:2023-06-25 发布日期:2023-06-29
通讯作者: 裴强
作者简介:裴强（1980—），男，博士，副教授，研究方向为超分子自组装。E-mail：peiqiangxynu@163.com。
基金资助:
信阳师范学院博士科研启动基金(18077);信阳师范学院南湖学者计划(2020);河南省高校重点科研项目(19A150042);河南省重点科研项目基础研究项目(22ZX002)

Design, synthesis and properties of stimuli-responsive AIE gelator

PEI Qiang¹(), HU Wenjing¹, NIE Lizhu¹, SHI Yanan¹, DING Aixiang²

^1.College of Chemistry and Chemical Engineering, Xinyang Normal University, Xinyang 464000, Henan, China
^2.Institute of Flexible Electronics (IFE, Future Technologies), Xiamen University, Xiamen 361005, Fujian, China

Received:2022-08-09 Revised:2022-11-16 Online:2023-06-25 Published:2023-06-29
Contact: PEI Qiang

摘要/Abstract

摘要：

与聚合物凝胶相比，有机小分子凝胶易于化学改性，具有更好的刺激响应，在众多领域显示出巨大的应用潜力。本文以没食子酸、单羧基四苯乙烯为基本原料，合成得到一种兼具聚集诱导发光性质和还原刺激响应性凝胶因子G1。凝胶因子G1能在环己烷和二甲基亚砜（DMSO）中自组装形成凝胶，临界成胶浓度分别为5.6mg/mL和16.7mg/mL。紫外光谱、荧光光谱、红外光谱、变温核磁、X射线衍射（XRD）研究结果表明，π-π堆积和氢键作用是凝胶因子G1 形成凝胶的主要驱动力。此外，接触角研究结果表明，凝胶因子G1在DMSO中形成的干凝胶薄膜的接触角高达137°，表明其具有较强的疏水性，在刺激响应性荧光疏水材料领域有着潜在的应用价值。

关键词: 有机凝胶, 聚集诱导发光, 还原响应性, 疏水材料

Abstract:

Compared with polymer gels, small organic molecule-based gels possess easy modification, have better stimuli response, and show great application potential in many fields. In this work, gallic acid and mono-carboxy tetraphenylene were used as the starting materials to synthesize a gelator G1 with both aggregation-induced emission property and reduction responsiveness. The gelator G1 can self-assemble into gels in cyclohexane and dimethyl sulfoxide (DMSO), and the critical gelation concentrations were 5.6mg/mL and 16.7mg/mL, respectively. The results of UV-vis spectroscopy, fluorescence spectroscopy, infrared spectroscopy, temperature-dependent NMR study and XRD study indicated that π-π stacking and hydrogen bonding were the main driving forces for the formation of the gel. In addition, the results of the contact angle study indicated that the contact angle of the xerogel films derived from the DMSO gels was as high as 137°, suggesting strong hydrophobicity of the xerogel films, which can be potentially applied in the field of stimuli-responsive fluorescent hydrophobic materials.

Key words: organogel, aggregation-induced emission, reduction responsiveness, hydrophobic material

中图分类号:

O641.3

裴强, 胡文静, 聂丽珠, 史亚楠, 丁爱祥. 刺激响应性聚集诱导发光凝胶因子的设计、合成及性能[J]. 化工进展, 2023, 42(6): 3105-3113.

PEI Qiang, HU Wenjing, NIE Lizhu, SHI Yanan, DING Aixiang. Design, synthesis and properties of stimuli-responsive AIE gelator[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3105-3113.

图/表 9

图1 化合物G1和G2的分子结构

图2 G1和G2的合成路线图

表1 凝胶因子G1和G2在不同溶剂中的凝胶性能

溶剂	G1	G2
环己烷	G(5.6)	S
苯	S	S
甲苯	S	S
二甲苯	S	S
乙腈	P	I
乙酸乙酯	P	P
丙酮	S	P
四氢呋喃	S	S
甲醇	P	P
DMSO	G (16.7)	P
DMF	S	S
二氯甲烷	S	S
氯仿	S	S
H₂O	I	I

图3 凝胶因子G1还原刺激响应图（DMSO，18mg/mL）

图4 凝胶因子G1在不同溶剂中的紫外-可见光谱、发光图和荧光光谱

图5 凝胶因子G1的干凝胶红外光谱图和变温核磁谱

图6 凝胶因子G1的干凝胶XRD图

图7 凝胶因子G1的干凝胶形貌及干凝胶薄膜接触角和发光图（365nm）

图 8 凝胶因子G1自组装形成凝胶的机理

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刺激响应性聚集诱导发光凝胶因子的设计、合成及性能

Design, synthesis and properties of stimuli-responsive AIE gelator

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