三苯胺衍生物的合成及其基于聚集诱导发光(AIE)机理对汞离子“OFF-ON”荧光识别

doi:10.6023/cjoc202206043

有机化学 ›› 2023, Vol. 43 ›› Issue (1): 320-325.DOI: 10.6023/cjoc202206043 上一篇下一篇

研究简报

三苯胺衍生物的合成及其基于聚集诱导发光(AIE)机理对汞离子“OFF-ON”荧光识别

李阳阳^a, 孙小飞^a^,^*(), 胡晓玲^a, 任源远^b, 钟克利^a^,^*(), 燕小梅^c, 汤立军^a

a 渤海大学化学与材料工程学院食品科学与工程学院辽宁锦州 121013
b 中国水产科学研究院农业农村部水产品质量安全控制重点实验室北京 100141
c 大连医科大学检验医学院辽宁大连 116044

收稿日期:2022-06-22 修回日期:2022-08-01 发布日期:2022-09-01
通讯作者: 孙小飞, 钟克利
基金资助:
国家自然科学基金(22278038); 国家自然科学基金(32201948); 辽宁省自然科学基金(2020-MS-289); 辽宁省自然科学基金(20180551195); 农业农村部水产品质量安全控制重点实验室基金(2021C001); 辽宁省教育厅基本科研(LJKMZ20221480); 辽宁省教育厅基本科研(LJKQZ2021135)

Synthesis of Triphenylamine Derivative and Its Recognition for Hg²⁺ with “OFF-ON” Fluorescence Response Based on Aggregation-Induced Emission (AIE) Mechanism

Yangyang Li^a, Xiaofei Sun^a(), Xiaoling Hu^a, Yuanyuan Ren^b, Keli Zhong^a(), Xiaomei Yan^c, Lijun Tang^a

a College of Food Science and Technology, College of Chemistry and Materials Engineering, Bohai University, Jinzhou, Liaoning 121013
b Key Laboratory of Control of Quality and Safety for Aquatic Products, Ministry of Agriculture and Rural Affairs, hinese Academy of Fishery Sciences, Beijing 100141
c College of Laboratory Medicine, Dalian Medical University, Dalian, Liaoning 116044

Received:2022-06-22 Revised:2022-08-01 Published:2022-09-01
Contact: Xiaofei Sun, Keli Zhong
Supported by:
National Natural Science Foundation of China(22278038); National Natural Science Foundation of China(32201948); Natural Science Foundation of Liaoning Province(2020-MS-289); Natural Science Foundation of Liaoning Province(20180551195); Fund of Key Laboratory of Control of Quality and Safety for Aquatic Products, Ministry of Agriculture and Rural Affairs(2021C001); Scientific Research Fund of Liaoning Provincial Education Department(LJKMZ20221480); Scientific Research Fund of Liaoning Provincial Education Department(LJKQZ2021135)

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摘要/Abstract

汞离子(Hg²⁺)作为一种环境污染物不能被生物降解, 而且还会通过食物链积累, 对人体造成损害, 因此, 开发简单、有效检测Hg²⁺方法具有重要意义. 通过简单的两步反应合成了新颖的三苯胺衍生物Tbia, 该探针在羟乙基哌嗪乙硫磺酸(HEPES)溶液中可与Hg²⁺发生特异性反应, 释放出具有聚集诱导发光(AIE)特性的前体化合物, 从而实现对 Hg²⁺荧光“OFF-ON”识别. Tbia对Hg²⁺具有良好的选择性和灵敏度, 较宽的pH适用范围, 检测限仅为63 nmol/L. 此外, Tbia可被制成隐形墨水有望用于防伪包装, 利用负载Tbia的试纸可定性或粗定量检测Hg²⁺, Tbia还能检测真实水样中的Hg²⁺, 并可对活细胞中的Hg²⁺进行荧光成像.

关键词: 荧光探针, 聚集诱导发光(AIE), 识别, 汞离子, 多重应用

As an environmental pollutant, mercury ion (Hg²⁺) cannot be biodegraded, and will accumulate through the food chain and cause damage to human body. Therefore, it is of great significance to develop a simple and effective method for detecting Hg²⁺. In this paper, a novel triphenylamine derivative Tbia was synthesized by a simple two-step reaction. Tbia can react with Hg²⁺ specifically in hydroxyethylpiperazine ethane sulfonic acid (HEPES) solution and release the precursor compound with aggregation-induced emission (AIE) properties, which realized recognition of Hg²⁺ with “off-on” response. Tbia has good selectivity and sensitivity for Hg²⁺, a wide range of pH, and the detection limit of 63 nmol/L. In addition, Tbia can be prepared into invisible ink and is expected to be used in packaging of anti-counterfeiting. The test paper loaded with Tbia can be used for qualitative or roughly quantitative detection of Hg²⁺, and Tbia can detect Hg²⁺in real water samples as well as image of Hg²⁺ in living cells.

Key words: fluorescent probe, aggregation-induced emission (AIE), recognition, mercury ion, multiple applications

引用此文

李阳阳, 孙小飞, 胡晓玲, 任源远, 钟克利, 燕小梅, 汤立军. 三苯胺衍生物的合成及其基于聚集诱导发光(AIE)机理对汞离子“OFF-ON”荧光识别[J]. 有机化学, 2023, 43(1): 320-325.

Yangyang Li, Xiaofei Sun, Xiaoling Hu, Yuanyuan Ren, Keli Zhong, Xiaomei Yan, Lijun Tang. Synthesis of Triphenylamine Derivative and Its Recognition for Hg²⁺ with “OFF-ON” Fluorescence Response Based on Aggregation-Induced Emission (AIE) Mechanism[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 320-325.

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图/表 10

图式1. 探针Tbia的合成路线和识别Hg2+机理

Scheme 1. Synthesis route and mechanism of Tbia sensing Hg2+

图1. (a) TCHO (10 μmol/L)在C2H5OH/HEPES (pH=7.4)中不同水含量的荧光光谱(内插: TCHO在510 nm处荧光强度与水含量的关系); (b)激光照射TCHO和Tbia溶液的丁达尔现象照片

Figure 1. (a) Fluorescence spectrum of TCHO (10 μmol/L) in C2H5OH/HEPES (pH=7.4) with different water content (insert: the relationship between the fluorescence intensity (510 nm) of TCHO and the content of water); (b) Photograph of Tyndall phenomena of TCHO and Tbia in HEPES solution

图2. Tbia的HEPES溶液(10 μmol/L)加入阳离子后的荧光变化(内插图: Tbia溶液中加入Hg2+前后荧光颜色变化)

Figure 2. Fluorescence change of Tbia (10 μmol/L) after adding various cations in HEPES solution (inset: The fluorescent color changes of Tbia without and with Hg2+)

图3. Tbia的HEPES溶液(10 μmol/L)中加入0~22 μmol/L Hg2+的荧光变化(内插图: Tbia荧光强度与Hg2+浓度的线性关系)

Figure 3. Fluorescence emission change of Tbia with adding different concentrations of Hg2+ (0~22 μmol/L) in HEPES (pH=7.4) buffer (insert: the linear relationship between fluorescence intensity of Tbia and Hg2+ concentration)

图4. Tbia和Tbia+Hg2+在不同pH下的荧光强度变化

Figure 4. Fluorescence intensity changes of Tbia and Tbia+Hg2+ at different pH

图5. Tbia作为隐形墨水的应用, 印在硅胶板上的BHU字母在日光(a)和紫外光(b)下的印迹

Figure 5. Application of Tbia as invisible ink, the imprints of the BHU letters collected on a silica gel plate under daylight (a) and UV light (b)

图6. 负载Tbia试纸浸渍不同浓度Hg2+后在手提式紫外灯(365 nm)照射下的荧光照片

Figure 6. Fluorescent photographs of test strips loaded with Tbia with different concentrations of Hg2+ under portable UV light (365 nm)

图7. 在三种实际水样中Tbia (10 μmol/L)的荧光强度与Hg2+浓度(4~8 μmol/L)的线性关系

Figure 7. Linear relation between fluorescence intensities of Tbia (10 μmol/L) and concentration of Hg2+ (4~8 μmol/L) in three real water samples

Sample	Added/ (μmol•L^–1)	Found/ (μmol•L^–1)	Recovery rate/%	CV (n=3)
Tap water	4	4.11	102.7	0.08
	5	4.94	98.9	0.05
	6	5.97	99.5	0.06
Lake water	4	3.98	99.5	0.02
	5	5.04	100.7	0.02
	6	5.95	99.2	0.01
River water	4	4.01	100.2	0.05
	5	4.90	98.0	0.09
	6	6.07	101.2	0.04

表1. Tbia在实际水样中检测Hg2+的结果a

Table 1. Detection results of Hg2+ in water samples using Tbia

图8. 用Tbia (10 μmol/L)预处理MCF-7细胞与不同浓度(0、10、30、50、100 μmol/L)的Hg2+进一步孵育30 min后的明场(左)、蓝色通道(中)和叠加通道(右)的荧光成像

Figure 8. Images of bright channel (left), blue channel (middle) and merged channel (right) of MCF-7 cells pretreated with Tbia (10 μmol/L) and incubated with Hg2+ (0, 10, 30, 50, 100 μmol/L) for 30 min

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三苯胺衍生物的合成及其基于聚集诱导发光(AIE)机理对汞离子“OFF-ON”荧光识别

Synthesis of Triphenylamine Derivative and Its Recognition for Hg²⁺ with “OFF-ON” Fluorescence Response Based on Aggregation-Induced Emission (AIE) Mechanism

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