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基于波长位移的视觉荧光传感法利用铕/钆金属有机框架通过pH触发检测天冬氨酸

Wavelength-shift-based visual fluorescence sensing of aspartic acids using Eu/Gd-MOF through pH triggering.

作者信息

Wen Xiaohui, Li Chenghui, Zhou Zexi, He Yujing, He Juan, Hou Xiandeng

机构信息

Analytical & Testing Center, Sichuan University, Chengdu, Sichuan, 610064, China.

College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, China.

出版信息

Talanta. 2023 Dec 1;265:124778. doi: 10.1016/j.talanta.2023.124778. Epub 2023 Jun 15.

Abstract

With the increasing demand for on-site detection, the current approach of building dual-emission or multi-emission luminescence sensors based on metal-organic frameworks (MOFs) which possess the capacity of self-reference for numerous non-analyte factors falls short of meeting sensing requirements. Therefore, we have designed a novel strategy for constructing wavelength shift-based luminescence sensor named Eu/Gd(TCPP), which exhibits dual-emitting from metal ions Eu and flexible rotating aggregation-induced emission (AIE) ligands HTCPP (2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine). This sensor was prepared by a simple, green and fast plasma synthesis method. It's worth noting that the fluorescence emission of Eu/Gd(TCPP) shows a specific wavelength shift from ligand peak, and a visual color change from red to blue within a pH range of 4 to 3. Moreover, various characterization data verified that the luminescence switching mechanism of Eu/Gd(TCPP) was attributed to the H-induced collapse of the Eu/Gd(TCPP) crystal structure, followed by untwisting of free ligands that lose rigid MOFs confinement. This hindered the antenna effect from HTCPP to Ln ions and restricted the rotation emission of ligand, resulting in the red-shifting of the ligand emission and corresponding luminescence switching. By tactfully utilizing the short-range pH response property of Eu/Gd(TCPP), highly sensitive and selective on-site visual detection of acidic aspartic acid can be achieved.

摘要

随着对现场检测需求的不断增加,目前基于金属有机框架(MOF)构建具有对多种非分析物因素进行自参照能力的双发射或多发射发光传感器的方法,已无法满足传感要求。因此,我们设计了一种构建基于波长 shift 的发光传感器 Eu/Gd(TCPP)的新策略,该传感器表现出金属离子 Eu 和柔性旋转聚集诱导发射(AIE)配体 HTCPP(2,3,5,6-四(4-羧基苯基)吡嗪)的双发射。这种传感器是通过一种简单、绿色且快速的等离子体合成方法制备的。值得注意的是,Eu/Gd(TCPP)的荧光发射显示出从配体峰的特定波长 shift,并且在 4 至 3 的 pH 范围内从红色到蓝色有视觉颜色变化。此外,各种表征数据证实 Eu/Gd(TCPP)的发光切换机制归因于 H 诱导的 Eu/Gd(TCPP)晶体结构的坍塌,随后是失去刚性 MOF 限制的游离配体的解扭曲。这阻碍了 HTCPP 对 Ln 离子的天线效应并限制了配体的旋转发射,导致配体发射的红移和相应的发光切换。通过巧妙利用 Eu/Gd(TCPP)的短程 pH 响应特性,可以实现对酸性天冬氨酸的高灵敏度和选择性现场视觉检测。

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