一种用于水相介质中Pd2+检测的新型荧光传感器

doi:10.16085/j.issn.1000-6613.2023-1687

摘要/Abstract

摘要：

设计并合成了一种新型四苯乙烯衍生物（TPE-H），该衍生物在THF/H₂O（0.5/9.5，体积比）溶液介质中显示出明亮的红色聚集诱导发射（AIE）特性。TPE-H通过荧光“开-关”策略选择性地鉴别Pd²⁺。该传感器具有出色的选择性和灵敏度，并在很宽的pH范围（4~10）内显示出出色的稳定性。对Pd²⁺检测的详细研究表明，Pd²⁺的检出限为9.81×10^-8mol/L。通过核磁共振氢谱、傅里叶红外光谱和质谱等测试确认了传感机理。在传感试纸和真实水样测试中，TPE-H对Pd²⁺具有良好的传感效果，误差较小。该研究不仅报道了一种有效的Pd²⁺荧光传感器，而且为在复杂环境中原位和实时传感Pd²⁺提出良好的应用前景。

关键词: 四苯乙烯, 聚集诱导发光, 离子检测, 钯离子, 荧光传感器

Abstract:

A novel tetraphenylethylene derivative (TPE-H) was designed and synthesized, which exhibited bright red aggregation induced emission (AIE) characteristics in THF/H₂O (0.5/9.5, volume ratio) solution medium. TPE-H selectively identified Pd²⁺ through a fluorescence "on-off" strategy. This sensor had excellent selectivity and sensitivity, and exhibited excellent stability over a wide pH range (4—10). Detailed research on Pd²⁺detection showed that the detection limit for Pd²⁺ was 9.81×10^-8mol/L. The sensing mechanism was confirmed through ¹H NMR, Fourier transform infrared spectroscopy spectroscopy and mass spectroscopy. In the sensing test paper and real water sample testing, TPE-H had good sensing effect on Pd²⁺ with small errors. This study not only reported an effective Pd²⁺ fluorescence sensor, but also proposed good application prospects for in-situ and real-time sensing of Pd²⁺ in complex environments.

Key words: tetraphenylethylene, aggregation-induced luminescence, ion detection, palladium ion, fluorescent sensors

中图分类号:

O625

江晟杰. 一种用于水相介质中Pd²⁺检测的新型荧光传感器[J]. 化工进展, 2024, 43(10): 5679-5685.

JIANG Shengjie. A novel fluorescent sensor for Pd²⁺detection in aqueous media[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5679-5685.

图/表 15

图1 TPE-H的合成路线图

图2 TPE-H（1×10-6mol/L）在含有不同体积分数的H2O的THF/H2O混合物中的荧光光谱[插图为不同H2O分数的THF/H2O溶液中荧光强度的比率变化（I/I0）]

图3 TPE-H（1.0×10-6mol/L）与不同金属离子（2.0×10-6mol/L）在THF中的荧光光谱（插图为含或不含Pd2+的TPE-H溶液的荧光照片）

图4 Pd2+浓度对传感器TPE-H（1.0×10-6mol/L）荧光强度的影响

图5 Pd2+等效浓度的传感器滴定的荧光强度

图6 化合物TPE-H（1×10-6mol/L）在不同pH下含有Pd2+或不含Pd2+（2×10-6mol/L）的荧光强度变化

图7 金属离子（1×10-6mol/L）和Pd2+共存时对探针荧光强度的影响

图8 TPE-H识别前后的红外对比图

图9 TPE-H+ Pd2+识别后的质谱图

图10 在TPE-H中添加1.0当量的Pd2+后的核磁氢谱对比图

图11 TPE-H和Pd2+的荧光滴定Job’s图

图12 TPE-H与Pd2+的结合模型

图13 加入Pd2+后TPE-H的LUMO和HOMO对比图

图14 紫外光（365nm）下TPE-H与相应离子的荧光照片1—TPE-H；2—Ag+；3—Cd2+；4—Cr3+；5—Fe3+；6—Hg2+；7—K+；8—Na+；9—Pb2+；10—Sr3+；11—Li+；12—Pd2+

表1 实际水样中Pd2+的回收结果

样品	加标量 /μmol·L^-1	检测总量 /μmol·L^-1	回收率 /%	标准偏差 /%
自来水	1	0.93	93	1.5
	2	1.96	98	1.9
	3	2.91	97	3.1
江水	1	0.96	96	2.1
	2	1.96	98	2.6
	3	2.94	98	1.6
湖水	1	0.91	91	2.3
	2	1.92	96	1.8
	3	2.94	98	3.2

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一种用于水相介质中Pd²⁺检测的新型荧光传感器

A novel fluorescent sensor for Pd²⁺detection in aqueous media

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