基于四苯乙烯结构的聚集诱导发光效应(AIE)有机多晶体合成: 分子构象和Cys检测性能研究

doi:10.6023/cjoc202509019

有机化学 ›› 2026, Vol. 46 ›› Issue (3): 934-940.DOI: 10.6023/cjoc202509019 上一篇下一篇

研究论文

基于四苯乙烯结构的聚集诱导发光效应(AIE)有机多晶体合成: 分子构象和Cys检测性能研究

张继东^a^,^*(), 王浩^a, 权校昕^a, 张胜海^a, 厍伟^b

^a 安康学院化学与环境学院陕西安康 725000
^b 包头师范学院化学学院内蒙古包头 014030

修回日期:2025-11-21 发布日期:2025-12-30
通讯作者: 张继东
基金资助:
陕西省重点研发计划(2023YBGY-152); 陕西省基础科学研究院科学研究计划(23JHQ033); 陕西省教育厅专项科研计划(23JK0274); 及陕西省大学生创新创业训练计划(S202311397067); 及陕西省大学生创新创业训练计划(S202411397065)

Synthesis of Aggregation-Induced Emission (AIE) Organic Polymorphs Based on Tetraphenylethene Structure: Research on Molecular Conformation and Detection Performance of Cys

Jidong Zhang^a^,^*(), Hao Wang^a, Xiaoxin Quan^a, Shenghai Zhang^a, Wei She^b

^a College of Chemistry and Environment, Ankang University, Ankang, Shaanxi 725000
^b Institute of Chemistry, Baotou Teachers College, Baotou, Inner Mongolia 014030

Revised:2025-11-21 Published:2025-12-30
Contact: Jidong Zhang
Supported by:
Shaanxi Provincial Key Research and Development Program(2023YBGY-152); Scientific Research Program of Shaanxi Academy of Basic Sciences(23JHQ033); Special Scientific Research Program of the Shaanxi Provincial Department of Education(23JK0274); Shaanxi Provincial College Students’ Innovation and Entrepreneurship Training Program(S202311397067); Shaanxi Provincial College Students’ Innovation and Entrepreneurship Training Program(S202411397065)

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摘要/Abstract

合成了一种具有聚集诱导发光效应(AIE)的基于四苯乙烯2,4-二硝基苯磺酰基衍生物TPE-1. 利用荧光发射光谱对TPE-1的AIE性能进行了研究. 经耐心结晶分离, 制备出了TPE-1s和TPE-1t多晶型物. 通过单晶X射线衍射分析, 明确了其分子构象与发光性能间的构效关系, 结构分析表明, TPE-1s 中TPE单元苯环和2,4-二硝基苯磺酰基单元之间的扭转角为80.399°, 而TPE-1t中该角度为48.956°. 分子力学分析显示, TPE单元类似螺旋桨样非平面结构导致不同的分子间相互作用, 例如TPE-1s中C—H…π相互作用键长为0.31097 nm, 而TPE-1t中C—H…π相互作用键长为0.27640 nm. 由于结构受扭转角的影响, 两种晶体分子形成不同的排列模式. 这些结果表明, 分子构象对发光性能具有显著影响: 分子构象扭曲程度较小的晶体, 其发光强度明显强于构象扭曲程度较大的晶体. 另外, TPE-1s在磷酸盐缓冲液(PBS)中对半胱氨酸(Cys)表现出良好的检测选择性与灵敏度, 其检出限为26.7 nmol/L.

关键词: 多晶体, 聚集诱导发光, 荧光探针, 半胱氨酸

A tetraphenylethene based 2,4-dinitrobenzenesulfonyl derivative TPE-1 with aggregation-induced emission (AIE) was synthesized. The AIE performance of TPE-1 was studied by fluorescence emission spectroscopy. After patient crystallization and separation of TPE-1, TPE-1s and TPE-1t polymorphs were prepared. Single crystal diffraction data were used to prove its structure-activity relationship. The most distinctive feature is that the torsional angle of TPE-1s between the benzene ring of the TPE unit and the 2,4-dinitrobenzenesulfonyl unit is 80.399°, while that of TPE-1t is 48.956°. Interestingly, the propeller- like non-planar structure of the TPE unit may lead to conformations of different intermolecular interactions, such as the C—H…π interaction in TPE-1s (0.3.1097 nm), and the C—H…π interaction in TPE-1t (0.27640 nm). Due to the influence of torsion angle on the structure, the two crystals form different arrangement patterns at the ends. These results inferred that the molecular conformation significantly affects the luminescence characteristics. Crystals with slightly distorted molecular conformations emit more strongly than those with severely distorted molecular conformations. In addition, TPE-1s demonstrated excellent selectivity and sensitivity in the detection of cysteine (Cys) in phosphate buffer solution (PBS), and the detection limit is 26.7 nmol/L.

Key words: polymorph, aggregation-induced emission (AIE), fluorescence probe, cysteine

引用此文

张继东, 王浩, 权校昕, 张胜海, 厍伟. 基于四苯乙烯结构的聚集诱导发光效应(AIE)有机多晶体合成: 分子构象和Cys检测性能研究[J]. 有机化学, 2026, 46(3): 934-940.

Jidong Zhang, Hao Wang, Xiaoxin Quan, Shenghai Zhang, Wei She. Synthesis of Aggregation-Induced Emission (AIE) Organic Polymorphs Based on Tetraphenylethene Structure: Research on Molecular Conformation and Detection Performance of Cys[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 934-940.

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图/表 6

图式1. 化合物TPE-1的合成路线

Scheme 1. Synthetic route of compound TPE-1

图1. (a) TPE-1在不同水体积分数的THF/H2O (10 µmol•L－1)中的荧光发射光谱(激发波发射光谱长为395 nm)和(b) TPE-1随着水体积分数变化在556 nm处的荧光发射强度

Figure 1. (a) Fluorescence emission spectra of TPE-1 in THF/H2O with different water fractions (10 µmol•L－1) (excitation wavelength is 395 nm) and (b) fluorescence emission intensity at 556 nm of TPE-1 as a function of water fraction

图2. (a) TPE-1s和(b) TPE-1t的晶体结构

Figure 2. Crystal structures of (a) TPE-1s and (b) TPE-1t

图3. (a) TPE-1s和(b) TPE-1t的分子堆积结构模式

Figure 3. Molecular packing structures of (a) TPE-1s and (b) TPE-1t

图4. (a)探针TPE-1s (10 μmol•L－1)在乙醇/PBS溶液中(V∶V=7∶3, pH=7.4)对不同浓度的Cys (0~5.0 equiv.)的荧光光谱图及(b)探针TPE-1s (10 μmol•L－1)在553 nm处荧光强度对不同Cys浓度的线性图(0~5 equiv.)

Figure 4. (a) Fluorescence emission spectra of 10 µmol•L－1 TPE-1s in C2H5OH/PBS (V∶V=7∶3, pH=7.4) solution upon addition of different concentrations of Cys (0~5.0 equiv.), and (b) the fluorescence intensity at 583 nm of probe TPE-1s (10 μmol•L－1) upon addition of different concentrations of Cys (0~5.0 equiv.)

图5.

Figure 5. (a, c) TPE-1s (b, d)TPE-1s＋Cys的SEM图像 SEM images of (a, c) TPE-1s and (b, d) TPE-1s＋Cys

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基于四苯乙烯结构的聚集诱导发光效应(AIE)有机多晶体合成: 分子构象和Cys检测性能研究

Synthesis of Aggregation-Induced Emission (AIE) Organic Polymorphs Based on Tetraphenylethene Structure: Research on Molecular Conformation and Detection Performance of Cys

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