Lin Xiaomei, Luo Fenqiang, Zheng Liyan, Gao Gongmin, Chi Yuwu
†MOE Key Laboratory of Analysis and Detection Technology for Food Safety, Fujian Provincial Key Laboratory of Analysis and Detection Technology for Food Safety, and College of Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China.
‡Key Laboratory of Medicinal Chemistry for Natural Resource (Yunnan University), Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kun-ming, Yunnan 650091, China.
Anal Chem. 2015;87(9):4864-70. doi: 10.1021/acs.analchem.5b00391. Epub 2015 Apr 24.
Metal-organic frameworks (MOFs) are microporous materials assembled from metal ions and organic linkers. Recently, many studies have been focused on the syntheses of MOFs with permanent porosity for various applications. However, no attention has been paid to controllable disassembly of MOFs and related applications. In this work, for the first time we synthesized novel tris(bipyridine)ruthenium(II)-functionalized MOFs (i.e., RuMOFs) that could be ion-responsively disassembled and release massive guest materials loaded in the frameworks. The synthesized RuMOFs exhibited much stability in aqueous solutions containing H(+), and many metal ions, but could be selectively and sensitively disassembled by Hg(2+) ions, resulting in the release of large quantities of Ru(bpy)3(2+). The target-responsive release mechanism was investigated and discussed in detail. On the basis of the ion-responsive disassembly and release, an ultrasensitive electrochemiluminescence sensing method for Hg(2+) has been developed with a very low limit of detection (5.3 × 10(-13) M). It was envisioned that the RuMOFs and similar target-responsive functional MOF materials would have promising applications in ultrasensitive and highly selective chemical sensing and even in accurately controllable drug delivering and releasing.
金属有机框架材料(MOFs)是由金属离子和有机连接体组装而成的微孔材料。近年来,许多研究聚焦于合成具有永久孔隙率的MOFs以用于各种应用。然而,MOFs的可控拆解及相关应用却未受到关注。在本工作中,我们首次合成了新型三联吡啶钌(II)功能化的MOFs(即RuMOFs),其能够对离子作出响应而拆解,并释放框架中负载的大量客体材料。所合成的RuMOFs在含有H(+)和多种金属离子的水溶液中表现出较高的稳定性,但能被Hg(2+)离子选择性且灵敏地拆解,从而释放出大量的Ru(bpy)3(2+)。对目标响应释放机制进行了详细研究和讨论。基于离子响应拆解和释放,开发了一种对Hg(2+)的超灵敏电化学发光传感方法,检测限极低(5.3×10(-13) M)。可以预见,RuMOFs及类似的目标响应功能化MOF材料在超灵敏和高选择性化学传感甚至精确可控的药物递送与释放方面将具有广阔的应用前景。