对氟离子呈现状态和比色响应的有机凝胶的研究进展

doi:10.11896/cldb.18030168

材料导报

2019, Vol. 33

Issue (9): 1583-1594 https://doi.org/10.11896/cldb.18030168

高分子与聚合物基复合材料

对氟离子呈现状态和比色响应的有机凝胶的研究进展

韦学玉¹, 杨晓凡², 白炳莲³, 徐晓平¹, 李济源¹, 刘志刚⁴

1.安徽工程大学建筑工程学院,芜湖 241000;
2.安徽工程大学生物与化学工程学院,芜湖 241000;
3.吉林大学物理学院,长春 130012;
4.宁波市自来水有限公司,宁波 315041

Advances in Organogels with State and Colorimetric Response to Fluoride

WEI Xueyu¹, YANG Xiaofan², BAI Binglian³, XU Xiaoping¹, LI Jiyuan¹, LIU Zhigang⁴

1.School of Architecture and Civil Engineering, Anhui Polytechnic University, Wuhu 241000;
2.College of Biological and Chemical Engineering, Anhui Polytechnic University, Wuhu 241000;
3.College of Physics, Jilin University, Changchun 130012;
4.Ningbo Water Supply Co. Ltd., Ningbo 315041

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摘要氟离子刺激响应的有机凝胶因子通过氢键识别或复合氟离子,使紫外吸收波长红移而发生颜色变化,实现比色响应;同时破坏凝胶形成的主要驱动力,诱导凝胶-溶胶转变,实现状态响应。能够响应外界氟离子刺激的有机凝胶在氟离子检测方面表现出明显的优势,具有方便快捷的肉眼检测效果,并且可以实现氟离子对准固体的检测,因此,具有氟离子刺激响应性的小分子有机凝胶受到人们越来越多的关注。
文献报道较多的氟离子响应有机凝胶只能对氟离子刺激呈现状态响应,即氟离子加入能够诱导凝胶-溶胶转变,却不能诱导体系颜色变化;或者只能对氟离子刺激呈现比色响应,即氟离子加入能够诱导体系颜色变化,却不能诱导凝胶-溶胶转变。而对氟离子具有双重响应性的有机凝胶在氟离子探测方面具有更明显的优势,可以同时表现出肉眼可见的状态响应(凝胶-溶胶)和比色响应(颜色变化)。
目前为止,对氟离子具有双重响应性的有机凝胶已经有一些报道。研究较多的是氢键型有机凝胶,凝胶因子中含有酰胺、酰腙、脲、酰肼等官能团,分子间氢键相互作用是凝胶形成的主要驱动力。由于氟离子有很强的电负性,能够与凝胶因子上的氢质子复合或发生去质子化,从而导致凝胶的破坏或颜色变化。因此,氟离子的响应机理基本上都是氢键相互作用和去质子化过程。但是凝胶因子与氟离子具体的响应过程千差万别,不仅与凝胶因子提供的氢键类型有直接关系,还与凝胶因子中的共轭基团、取代基性质和位置等有关。因此有必要对氟离子响应有机凝胶进行系统总结。
基于此,结合本课题组近期对氟离子响应有机凝胶的研究结果,对近年来文献报道的有关氟离子刺激响应的有机凝胶体系, 重点是近年来文献报道的对氟离子同时表现出肉眼可见的状态和比色响应的有机凝胶体系进行综述, 以期为新型氟离子响应有机凝胶体系的分子设计提供一些参考。

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关键词: 有机凝胶氟离子状态响应比色响应凝胶-溶胶转变

Abstract: The fluoride-responsive organogels, the recognization and combination of the gelators with fluoride anions through hydrogen bonding will induce the red shift of UV absorption wavelength and then the change of color, realizing the colorimetric response. At the same time, the main driving force of gel formation is destroyed, and the gel-sol transition is induced to achieve the state response. The fluoride-responsive organogels capable of responding to external fluoride anions show obvious advantages in fluoride anion detection, because the convenient and quick detection by naked eyes, and the detection of fluoride anions to quasi solid can be realized. Therefore, the fluoride-responsive organogels have attracted more and more attention.
It has been reported that many fluoride-responsive organogels only hold single response mode to fluoride anions. Specifically speaking, the addition of fluoride anions can only induce the gel-sol transition and fail to induce color change of the system, or it only bring about color change of the system rather than the gel-sol transition. Accordingly, the fluoride-responsive organogels capable of both response modes, namely presenting gel-sol transition and color changes, to fluoride anions are superior in fluoride detection.
Up to now, the researches on fluoride-responsive organogels with dual response modes to fluoride anions have been reported. Most researches focus on organogels based on intermolecular hydrogen bonding, their gelators contain functional groups like amide, hydrazone, urea, hydrazine, and so forth, and the main driving force for the formation of organogels lies in intermolecular hydrogen bonding interaction. Thanks to the strong electronegativity of fluoride anions, the deprotonation of gelators will take place, resulting in the destruction or color change of the organogels. Consequently, the response mechanism of fluorine ions primarily consists of hydrogen bonding interaction and deprotonation process. However, the responsive process of fluoride anions and gelators are quite different in various systems, which is not only directly related to the type of hydrogen bond provided by the gelators, but also affected by the conjugated groups, the nature and location of the substituents. Therefore, a comprehensive summary concerning the fluorine-responsive organogels is necessary.
Based on this, combining with the recent research results of our group on fluoride-responsive organogels, we summarize the fluoride-responsive organogels reported in the literatures in recent years, especially the organogel systems which showed both reversible color change and gel-sol transition by fluoride anions stimuli, for the sake of providing some references for molecular design of the organogels with fluoride anions response.

Key words: organogel fluorine anion state-response colorimetric-response gel-sol transition

发布日期: 2019-05-10

ZTFLH:

O621

基金资助: 吉林省自然科学基金(20170101112JC);安徽工程大学国家自然科学基金预研项目(zryy1310);安徽省自然科学基金(1808085ME133);安徽高校自然科学基金重点项目(KJ2017A119)

通讯作者: baibinglian@jlu.edu.cn

作者简介: 韦学玉,安徽工程大学建筑工程学院教师,2007年硕士毕业于宁夏大学。曾主持和参与省部级项目3项,公开发表研究论文十余篇。白炳莲,吉林大学物理学院教授。2007年博士毕业于吉林大学材料科学与工程学院。已发表SCI论文70余篇,目前主要从事刺激响应超分子凝胶研究。

引用本文:

韦学玉, 杨晓凡, 白炳莲, 徐晓平, 李济源, 刘志刚. 对氟离子呈现状态和比色响应的有机凝胶的研究进展[J]. 材料导报, 2019, 33(9): 1583-1594.
WEI Xueyu, YANG Xiaofan, BAI Binglian, XU Xiaoping, LI Jiyuan, LIU Zhigang. Advances in Organogels with State and Colorimetric Response to Fluoride. Materials Reports, 2019, 33(9): 1583-1594.

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http://www.mater-rep.com/CN/10.11896/cldb.18030168 或 http://www.mater-rep.com/CN/Y2019/V33/I9/1583

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