Ruthenium(II) Complex-Grafted Hollow Hierarchical Metal–Organic Frameworks with Superior Electrochemiluminescence Performance for Sensitive Assay of Thrombin

作者：Wei Huang, Gui-Bing Hu, Wenbin Liang, Jun-Mao Wang, Meiling Lü, Ruo Yuan, Dong‐Rong Xiao · 发表于：Analytical Chemistry · 年份：2021 · DOI：10.1021/acs.analchem.1c00636 · 被引用次数：78 · 研究领域：Advanced biosensing and bioanalysis techniques、Anodic Oxide Films and Nanostructures、Corrosion Behavior and Inhibition

Metal–organic frameworks (MOFs) with porous structures exhibit favorable promise in synthesizing high-performance electrochemiluminescence (ECL) materials, yet their micropores and narrow channels not only restrict the loading capacity of ECL luminophores but also constrain the diffusion of coreactants, ions, and electrons. Hence, we developed a new and simple hydrothermal etching strategy for the fabrication of a hollow hierarchical MOF (HH-UiO-66-NH 2 ) with a hierarchical-pore shell, which was employed as a carrier to graft Ru(bpy) 2 (mcpbpy) 2+ (bpy = 2,2′-bipyridine, mcpbpy = 4-(4′-methyl-[2,2′-bipyridin]-4-yl) butanoic acid) onto the coordinatively unsaturated Zr 6 nodes of HH-UiO-66-NH 2, creating the Ru-complex-grafted HH-UiO-66-NH 2 (abbreviated as HH-Ru-UiO-66-NH 2 ). Impressively, the HH-Ru-UiO-66-NH 2 presented brilliant ECL emission. On the one hand, the HH-UiO-66-NH 2 with a hierarchical-pore shell and hollow cavity was conducive to immobilize the Ru(bpy) 2 (mcpbpy) 2+ of large steric hindrance into the interior of the MOF, markedly improving the load number of luminophores. On the other hand, the hierarchical-pore shell of HH-UiO-66-NH 2 permitted fast diffusion of coreactants, ions, and electrons that facilitated the excitation of more grafted luminophores and greatly enhanced the utilization ratio of ECL luminophores. Inspired by the superior ECL performance of HH-Ru-UiO-66-NH 2, an ECL sensing platform was constructed on the basis of HH-Ru-UiO-66-NH 2 as an ...