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Tetraphenylethene-based fluorescent probe with aggregation-induced emission behavior for Hg2+ detection and its application
Analytica Chimica Acta ( IF 5.7 ) Pub Date : 2021-01-06 , DOI: 10.1016/j.aca.2020.12.053
Muthusamy Selvaraj , Kanagaraj Rajalakshmi , Dae-Hwan Ahn , Su-Jin Yoon , Yun-Sik Nam , Yeonhee Lee , Yuanguo Xu , Jong-Won Song , Kang-Bong Lee

A tetraphenylethene (TPE) derivative was designed and synthesized upon conjugation with bis(thiophen-2-ylmethyl) amine (BTA) containing a mercury-binding moiety and further characterized by using Nuclear magnetic resonance (NMR), LC-MS, UV–Vis, and fluorescence spectroscopic methods. The resulting TPE-BTA exhibited comprehensive aggregation-induced emission while expressing a high quantum yield and emission intensity at 70% water fraction. The probe exhibited a good photochromic effect with a Stokes shift of 178 nm, and the emission intensity at 550 nm increased considerably with the color turning from dark green to bright green under a UV lamp upon the addition of 5 μM Hg2+. The lowest-energy conformation of the probe showed that two thiophene rings were perpendicular to the phenyl ring, while two BTA molecules were situated in a staggered form to each other. The sulfur and nitrogen atoms present in TPE-BTA were coordinated to the Hg2+ ion, and these binding sites were confirmed by the NMR parameters, X-ray photoelectron spectroscopy signals, and structural calculations. The binding of Hg2+ to TPE-BTA was believed to restrict the intramolecular motion of TPE-BTA, thus inducing it to shine brighter according to the unique aggregation-induced emission effect. The concentration of Hg2+ was determined based on the enhancement of the emission intensity, and the present probe showed an extremely high sensitivity with a limit of detection of 10.5 nM. Furthermore, TPE-BTA enabled selective detection of Hg2+ even in the presence of a 1000-fold excess of other interfering metal ions. The proposed method was successfully employed to determine Hg2+ in living HeLa cells and real water samples.



中文翻译:

具有聚集诱导发射行为的Hg 2+检测的基于四苯乙烯的荧光探针及其应用

设计并与含有汞结合部分的双(噻吩-2-基甲基)胺(BTA)偶联合成四苯乙烯(TPE)衍生物,并进一步利用核磁共振(NMR),LC-MS,UV-Vis进行表征,以及荧光光谱法。所得的TPE-BTA表现出全面的聚集诱导发射,同时在70%的水含量下表现出高量子产率和发射强度。加入5μMHg 2+后,该探针表现出良好的光致变色效果,斯托克斯位移为178 nm,550 nm处的发射强度随着颜色从深绿色变为亮绿色而显着增加。。探针的最低能量构象表明,两个噻吩环垂直于苯环,而两个BTA分子彼此交错排列。TPE-BTA中存在的硫和氮原子与Hg 2+离子配位,这些结合位点通过NMR参数,X射线光电子能谱信号和结构计算得到证实。据认为,Hg 2+与TPE-BTA的结合会限制TPE-BTA的分子内运动,从而根据独特的聚集诱导的发射效应使Hg 2+发光。汞2+的浓度基于发射强度的增强来确定离子强度,并且本探针显示出极高的灵敏度,检测极限为10.5 nM。此外,即使在其他干扰金属离子过量1000倍的情况下,TPE-BTA仍能够选择性检测Hg 2+。该方法成功地用于测定活HeLa细胞和真实水样中的Hg 2+

更新日期:2021-01-13
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