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通过将振动诱导发光与聚集诱导发光基序相结合构建具有橙红-白-蓝荧光响应的比率型汞/银探针。

Ratiometric Hg /Ag Probes with Orange Red-White-Blue Fluorescence Response Constructed by Integrating Vibration-Induced Emission with an Aggregation-Induced Emission Motif.

作者信息

Li Yiru, Liu Yang, Zhou Haitao, Chen Wei, Mei Ju, Su Jianhua

机构信息

Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science & Technology, Shanghai, 200237, P. R. China.

出版信息

Chemistry. 2017 Jul 12;23(39):9280-9287. doi: 10.1002/chem.201700945. Epub 2017 May 8.

DOI:10.1002/chem.201700945
PMID:28370705
Abstract

Two novel ratiometric fluorometric probes 6 a and 6 b have been designed and synthesized for the detection of Hg and Ag , respectively. Each of these probes is comprised of a 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) skeleton, a tetraphenylethylene (TPE) unit, and two thymine/adenine groups. In this proof-of-concept work, the DPAC unit featuring vibration-induced emission (VIE) characteristics serves as a dual-emission chromogen, whereas the TPE moiety, which is noted for its aggregation-induced emission (AIE) properties, functions mainly as a signal amplifier. The coordination between the thymine/adenine groups and Hg /Ag leads to the formation of aggregates, which restricts the intramolecular vibrations of DPAC and the intramolecular rotations of TPE, activating the AIE effect of TPE and resulting in the bent form of DPAC. Accordingly, the overall fluorescence changed from moderate orange-red (I ) to intense blue light (I ) passing through the white-light region, concurrently with an enhancement of fluorescence at 475 nm and a dramatic increase in the ratio of I /I . Furthermore, the superb sensitivity of 6 a/6 b towards Hg /Ag has been demonstrated by the detection limit, which is as low as 6.1 nm and 0.1 μm, respectively. Both of these values are below the maximum concentration in drinking water permitted by the U.S. Environmental Protection Agency, demonstrating their great potential to be applied for real-world metal-ion sensing.

摘要

已设计并合成了两种新型比率荧光探针6 a和6 b,分别用于检测汞和银。每种探针均由9,14-二苯基-9,14-二氢二苯并[a,c]吩嗪(DPAC)骨架、四苯乙烯(TPE)单元和两个胸腺嘧啶/腺嘌呤基团组成。在这项概念验证工作中,具有振动诱导发射(VIE)特性的DPAC单元用作双发射色原,而以聚集诱导发射(AIE)特性著称的TPE部分主要起信号放大器的作用。胸腺嘧啶/腺嘌呤基团与汞/银之间的配位导致聚集体的形成,这限制了DPAC的分子内振动和TPE的分子内旋转,激活了TPE的AIE效应并导致DPAC呈弯曲形式。因此,整体荧光从中等橙红色(I)变为强烈蓝光(I),经过白光区域,同时475 nm处的荧光增强,I/I的比率急剧增加。此外,6 a/6 b对汞/银的卓越灵敏度已通过检测限得到证明,检测限分别低至6.1 nm和0.1 μm。这两个值均低于美国环境保护局允许的饮用水最大浓度,表明它们在实际金属离子传感中具有巨大的应用潜力。

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