Tianjin Key Laboratory of Biosensing and Molecular Recognition, College of Chemistry, Nankai University, Tianjin, 300071, China.
Shanghai Frontiers Science Research Center for Druggability of Cardiovascular Noncoding RNA and College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai, 201620, China.
Anal Chim Acta. 2022 Apr 29;1204:339731. doi: 10.1016/j.aca.2022.339731. Epub 2022 Mar 16.
Copper levels in body fluids provide an important reference for the diagnosis of Wilson's disease, which associated with blood abnormalities, kidney and cardiovascular disease, and neuropathy. Metal-organic frameworks (MOF) can easily realize dual-emission from single excitation as ratiometric fluorescence sensing and visible detection platform with the intensity ratio of two emissions for simple, rapid, sensitive, and specific analysis of biological samples. Here, we rationally designed a dual-emission Eu-MOF with dual-ligand strategy, denoted as Eu-DATA/BDC. While terephthalic acid (HBDC) was selected to sensitize Eu ions for the antenna effect emission, 2,5-diaminoterephthalic acid (HDATA) maintained its own emission and was used to identify Cu ions. Thus, dual-emission from Eu-DATA/BDC and specific recognition of Cu ions were realized for ratiometric sensing of Cu ions. A wide linear concentration range (1-40 μM), low detection limit (0.15 μM), and fast response (less than 10 s) were realized. The color change also achieved the visible detection by naked eye. Copper levels were tested with human serum samples and compared to the ICP-OES results, confirmed the potential of Eu-DATA/BDC probe in the diagnosis of Wilson's disease. The response mechanism to Cu ions was proposed as electron transfer between host and guest for fluorescence quenching. Thus, dual-ligand is a simple and efficient strategy to prepared dual-emission Eu-MOF for the ratiometric sensing and visible detection.
体液中的铜水平为威尔逊病的诊断提供了重要参考，威尔逊病与血液异常、肾脏和心血管疾病以及神经病变有关。金属有机骨架 (MOF) 可以很容易地实现从单激发的双发射，作为比率荧光传感和可见检测平台，两个发射的强度比可用于对生物样品进行简单、快速、灵敏和特异性分析。在这里，我们合理设计了一种具有双配体策略的双发射 Eu-MOF，记为 Eu-DATA/BDC。虽然对苯二甲酸 (HBDC) 被选择用于敏化 Eu 离子以实现天线效应发射，但 2,5-二氨基对苯二甲酸 (HDATA) 保持其自身发射，并用于识别 Cu 离子。因此，Eu-DATA/BDC 实现了双发射，并对 Cu 离子进行了特异性识别，从而实现了 Cu 离子的比率传感。实现了宽线性浓度范围（1-40 μM）、低检测限（0.15 μM）和快速响应（小于 10 s）。通过肉眼还实现了颜色变化的可见检测。用人血清样本测试铜水平，并与 ICP-OES 结果进行比较，证实了 Eu-DATA/BDC 探针在威尔逊病诊断中的潜力。提出了对 Cu 离子的响应机制是主体和客体之间的电子转移导致荧光猝灭。因此，双配体是一种简单有效的策略，可用于制备用于比率传感和可见检测的双发射 Eu-MOF。
