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基于强路易斯酸碱配位作用的矿石和水中钪的高选择性便携式荧光开启检测

Highly Selective and Portable Fluorescence Turn-On Detection of Sc in Ore and Water Based on Strong Lewis Acid-Base Coordination.

作者信息

Chen Xueshan, Zhang Zhankuo, Wu Yuke, Zhou Jinyan, Wei Yingnan, Zhang Jinyi, Zheng Chengbin

机构信息

Key Laboratory of Green Chemistry & Technology of MOE, College of Chemistry, Sichuan University, Chengdu, Sichuan 610065, China.

College of Chemistry and Material Science, Sichuan Normal University, Chengdu, Sichuan 610068, China.

出版信息

Anal Chem. 2024 Mar 19;96(11):4665-4672. doi: 10.1021/acs.analchem.3c05913. Epub 2024 Mar 8.

Abstract

Detecting scandium (Sc) with high selectivity and sensitivity is a challenging task due to its chemical similarity to other rare earth ions. Our findings show that the fluorescence of the complex fluorescent indicator calcein (CL) is quenched under acidic conditions (pH = 2), and Sc strongly inhibits this process. The results demonstrate that CL forms multimers and precipitates out of the solution under acidic conditions, while Sc causes a significant decrease in the scattering intensity of the solution. Additional experiments revealed that the strong Lewis acid nature of Sc complexes with the carboxyl groups of CL leads to increased dispersion of CL even under acidic conditions, thus enhancing its absorption and fluorescence. The complexation ratio of Sc and CL was investigated through spectral titrations and theoretical calculations. The interaction between Sc and CL is the strongest among rare earth and common metal ions due to the smallest ionic radius, resulting in high selectivity. The fluorescence turn-on strategy had a linear range of 0.04 to 2.25 μM under optimal conditions, with a detection limit of 20 nM for Sc. The combination of 3D printing and a smartphone program allows for portable on-site analysis of Sc. Mineral and water samples were used to demonstrate the potential of this strategy for the rapid, selective, and sensitive analysis of low levels of Sc.

摘要

由于钪(Sc)与其他稀土离子在化学性质上相似,因此高选择性和高灵敏度地检测钪是一项具有挑战性的任务。我们的研究结果表明,复合荧光指示剂钙黄绿素(CL)在酸性条件下(pH = 2)荧光淬灭,而钪强烈抑制这一过程。结果表明,CL在酸性条件下形成多聚体并从溶液中沉淀出来,而钪会导致溶液散射强度显著降低。进一步的实验表明,钪配合物与CL羧基的强路易斯酸性导致即使在酸性条件下CL的分散性增加,从而增强其吸收和荧光。通过光谱滴定和理论计算研究了钪与CL的络合比。由于离子半径最小,钪与CL之间的相互作用在稀土和常见金属离子中最强,从而具有高选择性。在最佳条件下,荧光开启策略的线性范围为0.04至2.25 μM,钪的检测限为20 nM。3D打印与智能手机程序相结合,可实现钪的便携式现场分析。利用矿物和水样证明了该策略在快速、选择性和灵敏分析低含量钪方面的潜力。

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