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基于 Zn-MOFs 的荧光传感器用于选择性和高灵敏度检测 Fe 和四环素抗生素。

Zn-MOFs based luminescent sensors for selective and highly sensitive detection of Fe and tetracycline antibiotic.

机构信息

Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong, 266100, PR China.

State Key Laboratory of Microbial Technology, Shandong University, Qingdao, 266237, PR China.

出版信息

J Pharm Biomed Anal. 2020 Sep 5;188:113444. doi: 10.1016/j.jpba.2020.113444. Epub 2020 Jun 26.

Abstract

Either reduced or excessive metal ions level in biological systems might induce serious metabolic diseases, and the abuse of antibiotics has seriously affected the environment. Despite the significant progress in the development of fluorescence probes over the past decade, the ability to sensitively and selectively detect these metal ions and antibiotics remains a pressing problem. Herein, we demonstrated some effective fluorescence probes for sensing metal ions and antibiotics, six novel and stable Zn(II) metal-organic frameworks (Zn-MOFs), namely [Zn(L)(1,4-bimb)] (1), [Zn(L)(4,4'-bbibp)(HO)]·2(CHCN) (2), [Zn(HL)(4,4'-bidpe)] (3), [Zn(HL)(4,4'-bibp)] (4), [Zn(HL)(3,5'-bip)] (5) and [Zn(HL)(1,3'-bit)] (6) (flexible HL = 5-(2-carboxylphenoxy)isophthalic acid, semi-flexible 1,4-bimb = 1,4-bis(imidazol-l-ylmethyl) benzene, rigid 4,4'-bbibp = 4,4'-bis(benzoimidazo-1-ly)biphenyl, semi-flexible 4,4'-bidpe = 4,4'-bis(imidazolyl)diphenyl ether, rigid 4,4'-bibp = 4,4'-bis(imidazolyl)biphenyl, rigid 3,5'-bip = bis(1-imidazoly)pyridine and rigid 1,3-bit = 1,3-bis(l-imidazoly)toluene) have been successfully synthesized via solvothermal conditions and further characterized by IR spectra, elemental analysis, powder X-ray diffraction (PXRD), single-crystal X-ray diffraction, and thermogravimetric (TG) analysis. These Zn MOFs have exhibited diversely architectural frameworks via the assistant N-donor ligands: 1, 2, 5 and 6 show unprecedented topological networks, 1 affords a 3-nodal (3, 4, 4)-connect 2-fold interpenetrating topology structure with the Point Schläfli symbol of (5·6·7·9·10)(5·6·7)(5·7·8), 2 shows a 3-nodal (3, 4, 6)-c topology with (4·8)(4·8·10·12)(8), 5 and 6 display 3-nodal (2, 2, 4)-c topology with (2·4·6)(2)(4). 3 and 4 show 4-connected sql topology with (4·6). As expected, Zn MOFs 1-6 not only revealed a highly sensitive and selective fluorescence quenching effect on Fe ions in aqueous solution, but also toughed the interference of a myriad of other metal ions. It is noteworthy that they could also be used as luminescent sensors for detection of tetracycline antibiotic.

摘要

生物体内金属离子水平的降低或升高都可能导致严重的代谢疾病,而抗生素的滥用也严重影响了环境。尽管在过去十年中荧光探针的发展取得了显著进展,但仍然存在一个紧迫的问题,即能够灵敏和选择性地检测这些金属离子和抗生素。在这里,我们展示了一些用于检测金属离子和抗生素的有效荧光探针,六个新型且稳定的锌(II)金属有机框架(Zn-MOFs),分别为[Zn(L)(1,4-bimb)] (1)、[Zn(L)(4,4'-bbibp)(HO)]·2(CHCN) (2)、[Zn(HL)(4,4'-bidpe)] (3)、[Zn(HL)(4,4'-bibp)] (4)、[Zn(HL)(3,5'-bip)] (5)和[Zn(HL)(1,3'-bit)] (6)(柔性 HL = 5-(2-羧基苯氧基)间苯二甲酸,半刚性 1,4-bimb = 1,4-双(咪唑-1-基甲基)苯,刚性 4,4'-bbibp = 4,4'-双(苯并咪唑-1-基)联苯,半刚性 4,4'-bidpe = 4,4'-双(咪唑基)二苯基醚,刚性 4,4'-bibp = 4,4'-双(咪唑基)联苯,刚性 3,5'-bip = 双(1-咪唑基)吡啶,刚性 1,3-bit = 1,3-双(1-咪唑基)甲苯),通过溶剂热条件成功合成,并通过红外光谱、元素分析、粉末 X 射线衍射(PXRD)、单晶 X 射线衍射和热重(TG)分析进一步表征。这些 Zn MOFs 通过辅助 N-供体配体表现出不同的建筑结构:1、2、5 和 6 显示出前所未有的拓扑网络,1 提供了具有(5·6·7·9·10)(5·6·7)(5·7·8)点 Schläfli 符号的 3-节点(3、4、4)-连接 2 倍互穿拓扑结构,2 显示出具有(4·8)(4·8·10·12)(8)的 3-节点(3、4、6)-c 拓扑结构,5 和 6 显示出具有(2·4·6)(2)(4)的 3-节点(2、2、4)-c 拓扑结构。3 和 4 显示出具有(4·6)的 4-连接 sql 拓扑结构。正如预期的那样,Zn MOFs 1-6 不仅在水溶液中对 Fe 离子表现出高度灵敏和选择性的荧光猝灭效应,而且还能抵抗多种其他金属离子的干扰。值得注意的是,它们还可以用作检测四环素抗生素的发光传感器。

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