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基于 4-(4-羧基苯氧基)苯二甲酸的 Zn(II)-金属有机框架作为用于检测丙酮和四环素的荧光传感器。

A Zn(II)-Metal-Organic Framework Based on 4-(4-Carboxy phenoxy) Phthalate Acid as Luminescent Sensor for Detection of Acetone and Tetracycline.

机构信息

Department of Chemistry, Capital Normal University, Beijing 100048, China.

出版信息

Molecules. 2023 Jan 19;28(3):999. doi: 10.3390/molecules28030999.

Abstract

As hazardous environmental pollutants, residual tetracycline (TC) and acetone are harmful to the ecosystem. Therefore, it is necessary to detect the presence of these pollutants in the environment. In this work, using Zn (II) salt, 4-(4-carboxy phenoxy) phthalic acid (HL), and 3,5-bis(1-imidazolyl) pyridine (BMP), a new metal-organic framework (Zn-MOF) known as [Zn(BMP)L(HO)]·2HO was synthesized using a one-pot hydrothermal method. The Zn-MOF has a three-dimensional framework based on the [Zn1NO] and [Zn2NO] nodes linked by a tridentate bridge BMP ligand and an L ligand with the μ:ηη/μ:ηη/μ:ηη coordination mode. There were two kinds of left- and right-handed helix chains, Zn1-BMP and Zn1-BMP-Zn1-L. The complex was stable in aqueous solutions with pH values of 4-10. The Zn-MOF exhibited a strong emission band centered at 385 nm owing to the π*→π electron transition of the ligand. It showed high luminescence in some common organic solvents as well as in the aqueous solutions of pH 4-10. Interestingly, TC and acetone effectively quenched the luminescence of the Zn-MOF in aqueous solution and enabled the Zn-MOF to be used as a sensor to detect TC and acetone. The detection limits of TC and acetone were observed to be 3.34 µM and 0.1597%, respectively. Even in acidic (pH = 4) and alkaline (pH = 10) conditions, the Zn-MOF showed a stable luminescence sensing capability to detect TC. Luminescence sensing of the Zn-MOF for TC in urine and aquaculture wastewater systems was not affected by the interfering agent. Furthermore, the mechanism of sensing TC was investigated in this study. Fluorescence resonance energy transfer and photoinduced electron transfer were found to be the possible quenching mechanisms via UV-Vis absorption spectra/the excitation spectra measurements and DFT calculations.

摘要

作为有害的环境污染物,残留的四环素(TC)和丙酮对生态系统有害。因此,有必要检测环境中这些污染物的存在。在这项工作中,使用 Zn(II)盐、4-(4-羧基苯氧基)邻苯二甲酸(HL)和 3,5-双(1-咪唑基)吡啶(BMP),通过一锅水热法合成了一种新的金属-有机骨架(Zn-MOF),称为[Zn(BMP)L(HO)]·2HO。Zn-MOF 具有基于[Zn1NO]和[Zn2NO]节点的三维骨架,由三齿桥联 BMP 配体和 L 配体以μ:ηη/μ:ηη/μ:ηη配位模式连接。有两种左手和右手螺旋链,Zn1-BMP 和 Zn1-BMP-Zn1-L。该配合物在 pH 值为 4-10 的水溶液中稳定。Zn-MOF 表现出强烈的发射带,中心位于 385nm,归因于配体的π*→π电子跃迁。它在一些常见的有机溶剂以及 pH 值为 4-10 的水溶液中表现出高发光性。有趣的是,TC 和丙酮有效地猝灭了水溶液中 Zn-MOF 的发光,使 Zn-MOF 能够用作检测 TC 和丙酮的传感器。TC 和丙酮的检测限分别观察到为 3.34µM 和 0.1597%。即使在酸性(pH = 4)和碱性(pH = 10)条件下,Zn-MOF 对 TC 的发光传感也表现出稳定的能力。尿液和水产养殖废水中 Zn-MOF 对 TC 的荧光传感不受干扰剂的影响。此外,本研究还研究了 Zn-MOF 对 TC 的传感机制。通过紫外-可见吸收光谱/激发光谱测量和 DFT 计算发现,荧光共振能量转移和光致电子转移是可能的猝灭机制。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6162/9921817/353dbe9b0b6e/molecules-28-00999-sch001.jpg

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