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基于水合四磺酸锆-四苯基卟啉金属有机框架的荧光和比色双模式比率传感器用于铜离子的可视化检测

Fluorescence and Colorimetric Dual-Mode Ratiometric Sensor Based on Zr-Tetraphenylporphyrin Tetrasulfonic Acid Hydrate Metal-Organic Frameworks for Visual Detection of Copper Ions.

作者信息

Hou Jinjie, Jia Pei, Yang Kairong, Bu Tong, Zhao Shuang, Li Longwen, Wang Li

机构信息

College of Food Science and Engineering, Northwest A&F University, Yangling, Xianyang, Shaanxi 712100, China.

出版信息

ACS Appl Mater Interfaces. 2022 Mar 23;14(11):13848-13857. doi: 10.1021/acsami.1c23199. Epub 2022 Mar 14.

DOI:10.1021/acsami.1c23199
PMID:35286802
Abstract

As a special heavy metal ion, copper ions (Cu) play an indispensable role in the fields of environmental protection and safety. Their excessive intake not only easily leads to diseases but also affects human health. Therefore, it is particularly important to construct a facile, effective, and highly selective Cu probe. Herein, a novel Zr-tetraphenylporphyrin tetrasulfonic acid hydrate (TPPS) metal-organic framework (ZTM) was fabricated using TPPS as the ligand and exhibited strong red fluorescence with a high quantum yield of 12.22%. In addition, we designed a ratiometric fluorescent probe by introducing green fluorescein isothiocyanate (FITC), which was not subject to environmental interference and had high accuracy. When exposed to different amounts of Cu, the fluorescence emission at 667 nm from ZTMs is remarkably quenched, while that at 515 nm from FITC is enhanced, accompanied by a change in the solutions' fluorescence color from red to green under a UV lamp. Besides, the ZTMs solutions display an excellent ratiometric colorimetric response for Cu and produce an obvious color change (from green to colorless) that is visible to the naked eye. The fabricated ZTMs@FITC fluorescent probe exhibits distinguished performance for Cu detection with linear ranges of 0.1 to 5 μM and 5 to 50 μM, as well as a low detection limit of 5.61 nM. Moreover, a colorimetric sensor based on ZTMs exhibits a good linear range from 0.1 to 20 μM for Cu with the detection limit of 4.96 nM. Furthermore, the dual-signal ratiometric sensor has significant specificity for Cu and is successfully applied for monitoring Cu in water samples, which proves its practical application value in the environment and biological systems.

摘要

作为一种特殊的重金属离子,铜离子(Cu)在环境保护和安全领域发挥着不可或缺的作用。其过量摄入不仅容易导致疾病,还会影响人体健康。因此,构建一种简便、有效且具有高选择性的铜探针尤为重要。在此,以四苯基卟啉四磺酸水合物(TPPS)为配体制备了一种新型的锆基金属有机框架(ZTM),其具有较强的红色荧光,量子产率高达12.22%。此外,我们通过引入绿色异硫氰酸荧光素(FITC)设计了一种比率荧光探针,该探针不受环境干扰且具有较高的准确性。当暴露于不同量的铜时,ZTMs在667 nm处的荧光发射显著猝灭,而FITC在515 nm处的荧光增强,同时在紫外灯下溶液的荧光颜色从红色变为绿色。此外,ZTMs溶液对铜表现出优异的比率比色响应,并产生肉眼可见的明显颜色变化(从绿色变为无色)。所制备的ZTMs@FITC荧光探针在检测铜方面表现出卓越的性能,线性范围为0.1至5 μM和5至50 μM,检测限低至5.61 nM。此外,基于ZTMs的比色传感器对铜的线性范围为0.1至20 μM,检测限为4.96 nM。此外,这种双信号比率传感器对铜具有显著的特异性,并成功应用于监测水样中的铜,证明了其在环境和生物系统中的实际应用价值。

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