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一种水稳定的镧系配合物作为一种对 Fe、Cr(VI) 和 4-硝基苯酚具有多重响应的发光传感器。

A water-stable lanthanide coordination polymer as a multiresponsive luminescent sensor for Fe, Cr(vi) and 4-nitrophenol.

机构信息

Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Special Function Materials and Structure Design, Ministry of Education, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.

出版信息

Dalton Trans. 2018 Oct 2;47(38):13543-13549. doi: 10.1039/c8dt02202j.

Abstract

Constructing water stable lanthanide coordination polymers (Ln-CPs) is of great importance for practical applications in biological and environmental areas and necessary for systematic research on the relationship between the properties of Ln-CPs and structures of linker ligands. A two-dimensional (2D) Eu coordination polymer (Eu-CP) {[Eu(L)(HCOO)]·H2O}n (H2L = isomer of 5-((pyridin-3-yloxy)methyl)isophthalic acid) is synthesized by the reaction of Eu(NO3)3·6H2O and H2L and heating at 140 °C. Single crystal X-ray diffraction analysis indicates that the Eu-CP presents a 2D network structure formed by binuclear metal clusters and bridged linkers COO- and HCOO-. The luminescence properties of the Eu-CP are explored at room temperature in the solid-state. The Eu-CP emits bright and stable red light due to the antenna effect from the ligand to the metal ion. The characteristic emission peaks of Eu3+ can be observed in its spectra. The luminescence intensity of the Eu-CP can be sensitively quenched by inorganic ions Fe3+, CrO42-, and Cr2O72- and the organic molecule 4-nitrophenol (4-NP). The Eu-CP can be a multiresponsive luminescent sensor in the water phase. Solvent luminescence investigation and PXRD data demonstrate that the Eu-CP exhibits excellent water stability. Therefore, all the sensing experiments are carried out in the water system. This multi-responsive luminescent sensor can detect Fe3+, Cr(vi) or 4-NP with high sensitivity and low detection limits in aqueous solution. Furthermore, the mechanism for the selective sensing of Fe3+, Cr(vi) or 4-NP is also explored which can mainly be explained by energy competition between the absorption of the analytes and the excitation of the Eu-CP.

摘要

构建水稳定的镧系配合物(Ln-CPs)对于生物和环境领域的实际应用非常重要,并且对于研究 Ln-CPs 的性质与连接配体结构之间的关系也有必要。通过 Eu(NO3)3·6H2O 和 H2L(5-(吡啶-3-基氧基)甲基)间苯二甲酸异构体)的反应,并在 140°C 下加热,合成了二维(2D)Eu 配位聚合物(Eu-CP){[Eu(L)(HCOO)]·H2O}n。单晶 X 射线衍射分析表明,Eu-CP 呈现由双核金属簇和桥连配体 COO-和 HCOO-形成的 2D 网络结构。在室温下对 Eu-CP 的固态发光性质进行了探索。由于配体到金属离子的天线效应,Eu-CP 发射明亮稳定的红光。可以在其光谱中观察到 Eu3+的特征发射峰。Eu-CP 的发光强度可以被无机离子 Fe3+、CrO42-和 Cr2O72-以及有机分子 4-硝基苯酚(4-NP)灵敏地猝灭。Eu-CP 可以成为水相中的多响应发光传感器。溶剂发光研究和 PXRD 数据表明,Eu-CP 表现出优异的水稳定性。因此,所有的传感实验都是在水体系中进行的。这种多响应发光传感器可以在水溶液中以高灵敏度和低检测限检测 Fe3+、Cr(vi)或 4-NP。此外,还探索了选择性检测 Fe3+、Cr(vi)或 4-NP 的机制,这主要可以通过分析物的吸收与 Eu-CP 的激发之间的能量竞争来解释。

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