9，10-二苯基蒽衍生物的制备及对铜离子上、下转换检测研究

doi:10.3964/j.issn.1000-0593(2019)12-3769-07

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摘要： Cu²⁺是人体正常代谢所必需的微量元素之一，但是过量的Cu²⁺会造成代谢紊乱，进而诱发各种疾病。长期以来，铜材料的过度使用和后处理不当导致生活环境中的Cu²⁺浓度超标，成为重金属污染物之一，因此生活环境中Cu²⁺含量的检测成为人们关注的热点。基于荧光探针的荧光光谱法由于选择性好、灵敏度高等优点被广泛应用于离子检测领域。利用荧光探针分子与待检测离子可发生选择性的弱相互作用，研究者们探索并设计了诸多可用于Cu²⁺检测的荧光探针。然而普通的荧光探针由于灵敏度较差或选择性不理想等问题缺乏实际应用价值。设计并合成了一种新的化学型荧光探针分子9,10-二(3’-羟基-4’-亚甲胺氨基硫脲苯基)蒽（b-HTPA）。该探针分子通过与Cu²⁺的络合作用，改变自身的电子排布结构，使得其荧光性能发生显著变化，由此对Cu²⁺产生灵敏的响应。通过上、下转换荧光光谱来研究b-HTPA对Cu²⁺检测的各项性能，并结合拟合计算得出最终结果。选择性研究结果表明，相比其他13种金属阳离子，Cu²⁺对b-HTPA荧光猝灭效果最为显著，空白探针分子荧光与加入Cu²⁺后的荧光强度比可达150∶1。灵敏性研究结果表明，b-HTPA对Cu²⁺的最低检测限为2.78×10^-7 mol·L^-1，远低于中国卫生部《生活饮用水卫生标准》（GB5749—2006），表现出良好的荧光响应灵敏性和理想的最低检测限。响应时间测试结果表明，b-HTPA与Cu²⁺在0~2 min时间范围内反应速率最大，并在约10 min后反应完全，说明b-HTPA在对Cu²⁺检测中可以短时间产生响应，降低实际应用中的检测时间和周期。还使用八乙基卟啉钯（PdOEP）作为光敏剂，以b-HTPA为湮灭剂，利用上转换荧光光谱对b-HTPA/PdOEP/Cu²⁺体系的灵敏性和检测限进行测试研究。结果表明，探针的上转换荧光强度随着Cu²⁺浓度的增加而降低，具有良好的响应性，通过拟合计算，得出b-HTPA对Cu²⁺的检测限为3.78×10^-6 mol·L^-1，低于《生活饮用水卫生标准》规定的检测下限。设计合成的新型荧光探针分子9,10-二(3-羟基-4-亚甲胺氨基硫脲苯基)蒽对Cu²⁺具有高选择性、高灵敏度和理想的检测限，且响应速度快，展现了上转换发光在检测领域具有应用潜力。

关键词：蒽衍生物；荧光探针；上转换；Cu²⁺；离子检测

Abstract：Cu²⁺ is one of the essential trace elements for human metabolism, while excess ingestion will cause metabolic disorders even diseases. However, Cu²⁺ has been elevated levels in living environment due to overuse and inappropriate reprocessing measures of copper, which makes Cu²⁺ one of the toxic heavy metal pollutions. Therefore, the continuous concern over Cu²⁺ pollution has been a hot issue and attracted interest in the detection methods for Cu²⁺. Fluorescent spectrometry based on fluorescence probe has been widely used in ion detection field owing to good selectivity and high sensitivity. So far, researchers have developed fluorescence probes for Cu²⁺ detection based on selectional weak interaction between probe molecules and ions to be measured. However, these strategies all involve selectivity or sensitivity drawbacks, making the probes difficult for practical applications. Here, we designed and synthesized a new molecule 9,10-bis (3’-hydroxy-4’-thiosemicarbazide) phenylanthracene (b-HTPA) as a fluorescence probe for Cu²⁺ detection. The electron configuration of b-HTPA would change through coordinating with Cu²⁺, which would cause the remarkable change of fluorescence property of the b-HTPA as responsiveness for Cu²⁺. Characterizations of the detection of b-HTPA for Cu²⁺ were mainly carried out by down/up conversion fluorescence spectral. Results of selectivity research showed that Cu²⁺ has the strongest fluorescence quenching effect compared with the other thirteen kinds of metal cations. Besides, upon addition of Cu²⁺about 150-fold decreasement of fluorescence intensity was observed compared to other metal cations. The results indicated the good selectivity of b-HTPA to Cu²⁺. Results of sensitivity research showed that the detection limit of b-HTPA to Cu²⁺ was 2.78×10^-7 mol·L^-1 which was much lower than the hygienic standard for drinking water (GB5749—2006), which indicated high fluorescent response sensitivity and ideal detection limit. The results of response time test revealed that interaction rate between b-HTPA and Cu²⁺ was very high in the first two minutes and completely reacted within ten minutes, which showed that b-HTPA could be capable of reacting intensively with Cu²⁺ in short time which may save detection period. Moreover, up-conversion fluorescence spectra were also used for the sensitivity evaluation of b-HTPA to Cu²⁺ with palladium(Ⅱ) octaetylporphyrin (PdOEP)as the sensitizer. The research results showed that intensity of up-conversion fluorescence obviously declined upon the addition of Cu²⁺ and the detection limit was 3.78×10^-6 mol·L^-1 which is also lower than the hygienic standard. This work designed and synthesized the 9,10-bis (3’-hydroxy-4’-thiosemicarbazide) phenylanthracene as a fluorescence probe for Cu²⁺ detection, and the probe was proved to have highly selective and sensitive. Moreover, the probe b-HTPA had ideal detection limit and short detection period, which gave it great potential in the field of Cu²⁺ detection.

Key words：Anthracene derivative; Fluorescence probe; Up-conversion; Cu²⁺; Ion detection

收稿日期: 2019-03-04 修订日期: 2019-07-02

中图分类号:

O657.3

基金资助: 国家自然科学基金项目(51603141, 51873145)，江苏省自然科学基金-优秀青年基金项目(BK20170065)，江苏省自然科学基金项目(BK20160358)，江苏省高校自然科学研究重大项目(17KJA430016)，江苏省“六大人才高峰”(XCL-79)，江苏省第五期“333工程”项目(BRA2018340)，江苏省高校“青蓝工程”项目资助

通讯作者: 韩鹏举，王筱梅 E-mail: wxyhpj@163.com; wangxiaomei@mail.usts.edu.cn

作者简介: 陈硕然，1987年生，苏州科技大学化学生物与材料工程学院教师 e-mail: chensr@mail.usts.edu.cn

引用本文:

陈硕然，黄苏琴，韩鹏举，叶常青，宋飒飒，王筱梅. 9，10-二苯基蒽衍生物的制备及对铜离子上、下转换检测研究[J]. 光谱学与光谱分析, 2019, 39(12): 3769-3775.
CHEN Shuo-ran, HUANG Su-qin, HAN Peng-ju, YE Chang-qing, SONG Sa-sa, WANG Xiao-mei. Preparation of 9,10-Diphenylanthracene Derivative and Its Detection for Cu²⁺ by Up/Down-Conversion. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2019, 39(12): 3769-3775.

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