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基于形成钯配合物的荧光化学传感器的合理设计。

Rational design of fluorescent chemosensor for Pd based on the formation of cyclopalladated complex.

机构信息

Hubei Key Lab on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, Hubei, China.

School of Chemical Engineering and Pharmacy, Wuhan Instituted and Technology, Wuhan, 400073, Hubei, China.

出版信息

Talanta. 2023 Feb 1;253:123967. doi: 10.1016/j.talanta.2022.123967. Epub 2022 Sep 27.

DOI:10.1016/j.talanta.2022.123967
PMID:36195028
Abstract

According to the assumption that the formation of C-Pd bond becomes a cyclopalladated complex (CPC), we designed and synthesized two C-N-N pincer ligands of BODIPY appended 2,2'-bipyridine derivatives (BP and BPB). It has been confirmed that the C-Pd bond does exist and plays a crucial role in "on-off" fluorescence behavior. Based on it, a coordination-induced fluorescence quenching sensor for Pd was constructed. The results indicated that BP possessed high sensitivity and specificity for Pd in solution. The limit of detection (LOD) of BP is determined to be 0.97 nM within a linear range between 1.0 and 50.0 nM, meanwhile, the platinum-group ions demonstrate no interference. The bio-imaging application of BP was investigated and it exhibited a promising vitro test for fluorescent imaging of Pd ions in MCF-7 cells. Meanwhile, BPB coated sensor label for Pd was set up. The visible color variation was displayed under UV light with increasing concentrations of Pd. Briefly speaking, fluorescence probes of BP and BPB offer new approaches for Pd detection in a lab and on-site test, as well as the vivo imaging. Then, with the aid of (TD)DFT calculation, the internal reason for the optical difference between the two ligands was disclosed. This concept of CPC containing a Pd-C covalent bond provides a promising perspective of coordination fluorescence sensors.

摘要

根据 C-Pd 键形成环钯化配合物(CPC)的假设,我们设计并合成了两种带有 BODIPY 的 2,2'-联吡啶衍生物(BP 和 BPB)的 C-N-N 三齿配体。已经证实 C-Pd 键确实存在,并在“开-关”荧光行为中起着关键作用。在此基础上,构建了一种用于 Pd 的配位诱导荧光猝灭传感器。结果表明,BP 在溶液中对 Pd 具有高灵敏度和特异性。BP 的检测限(LOD)在 1.0 至 50.0 nM 的线性范围内确定为 0.97 nM,同时,铂族离子没有干扰。研究了 BP 的生物成像应用,它在 MCF-7 细胞中对 Pd 离子的荧光成像表现出有前途的体外测试。同时,建立了 BPB 涂层传感器标记 Pd。随着 Pd 浓度的增加,在紫外光下显示出可见的颜色变化。简而言之,BP 和 BPB 的荧光探针为实验室和现场测试以及体内成像中的 Pd 检测提供了新的方法。然后,借助(TD)DFT 计算,揭示了两种配体之间光学差异的内在原因。这种含有 Pd-C 共价键的 CPC 概念为配位荧光传感器提供了一个有前途的视角。

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