Yang Yan, Pang Jiandong, Li Yunwu, Sun Lei, Zhang Hao, Zhang Luyao, Xu Shuting, Jiang Taiwen
College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, P. R. China.
State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
Inorg Chem. 2021 Dec 20;60(24):19189-19196. doi: 10.1021/acs.inorgchem.1c02988. Epub 2021 Dec 5.
A novel europium-centered metal-organic framework fabricated from a symmetric and rigid ligand with tetracarboxylate groups, 2,6-di(2',5'-dicarboxylphenyl)pyridine (Hddpp), has been synthesized solvothermally. Characterized by single-crystal X-ray diffraction, compound features a 3D microporous structure with a butterfly-shaped trinuclear Eu(COO) secondary building unit. Interestingly, three kinds of 1D open channels viewed in different directions in compound are discovered, and the void ratio is calculated to be 47.5% by PLATON software. Solid-state luminescent experiments at 298 K reveal that compound displays naked-eye characteristic red emission of Eu ions monitoring the typical D → F transition. The exploration of luminescent sensing tests discloses that compound has an outstanding capacity for recognizing urinary 1-hydroxypyrene (1-HP) with a quite fast response and high sensitivity, giving the quenching efficiency of 98.2% after the immersion time for just 1 min and 73.2% with the amount of 1-HP only 0.05 mg/mL. To our knowledge, it is the first reported Eu-MOF as an extremely fast-responsive and highly sensitive luminescent sensor for 1-HP which is interference-free from other urinary components. Furthermore, the successful preparation of the luminescent test papers makes compound convenient, easy, and real-time in the application for sensing 1-HP in biomedical and biological fields.
通过溶剂热法合成了一种新型的以铕为中心的金属有机框架，该框架由具有四羧酸根基团的对称刚性配体2,6-二(2',5'-二羧基苯基)吡啶(Hddpp)构建而成。通过单晶X射线衍射对其进行表征，该化合物具有三维微孔结构，其中包含蝶形三核Eu(COO)二级结构单元。有趣的是，在该化合物中发现了从不同方向观察到的三种一维开放通道，通过PLATON软件计算得出其孔隙率为47.5%。298 K下的固态发光实验表明，该化合物呈现出铕离子肉眼可见的特征红色发射，监测典型的D→F跃迁。发光传感测试的探索表明，该化合物具有出色的识别尿中1-羟基芘(1-HP)的能力，响应速度相当快且灵敏度高，仅浸泡1分钟后的猝灭效率为98.2%，当1-HP含量仅为0.05 mg/mL时猝灭效率为73.2%。据我们所知，这是首次报道的作为对1-HP具有极快速响应和高灵敏度的发光传感器的铕基金属有机框架，且不受其他尿液成分的干扰。此外，发光测试纸的成功制备使得该化合物在生物医学和生物学领域检测1-HP的应用中方便、简易且实时。
