Guo Lan, Liang Maosheng, Wang Xiuli, Kong Rongmei, Chen Guang, Xia Lian, Qu Fengli
Key Laboratory of Life-Organic Analysis of Shandong Province, Qufu Normal University Qufu 273165 China
Chem Sci. 2020 Jan 29;11(9):2407-2413. doi: 10.1039/d0sc00030b.
In this study, a novel lanthanide-doped nanoprobe for monitoring dipicolinic acid (DPA), a unique biomarker of , was constructed by coordination of Tb with l-histidine (His) functionalized ZIF-8 (His@ZIF-8). After being functionalized with His, the resultant His@ZIF-8 had abundant carboxyl and amino groups, which like tongs help His@ZIF-8 "grasp" Tb firmly to form a stable lanthanide-doped nanoparticle (His@ZIF-8/Tb). Owing to the unsaturated coordination of Tb with the amino acid group, the resultant His@ZIF-8/Tb showed reserved response sites of Tb to DPA because of its unique molecular structure. After the His@ZIF-8/Tb coordination with DPA, the intrinsic fluorescence emission of the Tb ions was triggered through energy transfer, leading to bright yellow green luminescence owing to the antenna role of DPA. Benefitting from the His functionalization and the characteristics of ZIF-8, especially the high porosity and large surface area, the developed His@ZIF-8/Tb sensing platform exhibited attractive features as a fluorescent sensor for monitoring DPA such as fast response kinetics (10 s), high sensitivity and selectivity, and being portable, easy to operate, economical and secure. This sensor platform showed a satisfactory linear relationship ( = 0.999) ranging from 0.08 to 10 μmol L and an ultralow limit of detection (LOD) of 0.02 μmol L. This strategy for the design of functionalized MOFs to construct sensing probes and the resultant His@ZIF-8/Tb would provide a potential strategy for the exploitation of other functionalized materials used in other research fields and promising fluorescence platforms for the detection of other targets.
在本研究中，通过将铽（Tb）与 l-组氨酸（His）功能化的沸石咪唑酯骨架材料-8（His@ZIF-8）配位，构建了一种用于监测独特生物标志物吡啶二羧酸（DPA）的新型镧系元素掺杂纳米探针。用 His 功能化后，所得的 His@ZIF-8 具有丰富的羧基和氨基，它们就像钳子一样帮助 His@ZIF-8 牢固地“抓住”Tb，形成稳定的镧系元素掺杂纳米颗粒（His@ZIF-8/Tb）。由于 Tb 与氨基酸基团的不饱和配位，所得的 His@ZIF-8/Tb 因其独特的分子结构而显示出 Tb 对 DPA 的保留响应位点。His@ZIF-8/Tb 与 DPA 配位后，通过能量转移触发了 Tb 离子的固有荧光发射，由于 DPA 的天线作用，导致发出亮黄绿色荧光。得益于 His 功能化和 ZIF-8 的特性，特别是高孔隙率和大表面积，所开发的 His@ZIF-8/Tb 传感平台作为监测 DPA 的荧光传感器具有吸引人的特性，如快速响应动力学（10 秒）、高灵敏度和选择性，以及便携、易于操作、经济和安全。该传感器平台在 0.08 至 10 μmol/L 范围内显示出令人满意的线性关系（R² = 0.999），检测限（LOD）超低，为 0.02 μmol/L。这种设计功能化金属有机框架以构建传感探针的策略以及所得的 His@ZIF-8/Tb 将为开发用于其他研究领域的其他功能化材料提供潜在策略，并为检测其他目标提供有前景的荧光平台。
