Tu Rongxiu, Wang Yujun, Peng Jinyun, Hou Chuantao, Wang Zonghua
College of Chemistry and Chemical Engineering, Shandong Sino-Japanese Center for Collaborative Research of Carbon Nanomaterials, Instrumental Analysis Center of Qingdao University, Qingdao University, Qingdao 266071, P. R. China.
College of Chemistry and Chemical Engineering, Guangxi Normal University for Nationalities, Chongzuo 532200, P. R. China.
ACS Appl Mater Interfaces. 2021 Sep 1;13(34):40847-40852. doi: 10.1021/acsami.1c13601. Epub 2021 Aug 17.
The application of porphyrin metal-organic frameworks (MOFs) as a ratiometric electrochemical sensing platform is still unexplored. In this paper, we report a ratiometric electrochemical sensor by the integration of multiple redox centers into porphyrin MOFs for the detection of dissolved oxygen (DO). Specifically, the ferrocene (Fc) group was integrated into the nanosized PCN-222(Fe) (PCN = porous coordination networks) via acid-base reaction to synthesize the Fc@PCN-222(Fe) composite with two redox centers of the Fc group and Fe-porphyrin. The Fc group that is insensitive to DO serves as an internal reference, and the Fe-porphyrin in PCN-222(Fe) is a DO indicator. The ratios of the cathodic currents for the two redox centers exhibit a linear relationship with DO concentrations from 2.8 to 28.9 mg mL and a limit of detection of 0.3 mg mL. In addition, the ratiometric electrochemical sensor has high selectivity and stability for DO sensing results from the Fc@PCN-222(Fe) composite. Because there are numerous redox centers, such as methylene blue and thionine, which can be integrated into MOFs, many MOF-based ratiometric electrochemical sensors can be simply developed for high-performance biosensing.
卟啉金属有机框架材料（MOFs）作为一种比率型电化学传感平台的应用仍未得到探索。在本文中，我们报道了一种通过将多个氧化还原中心整合到卟啉MOFs中来检测溶解氧（DO）的比率型电化学传感器。具体而言，通过酸碱反应将二茂铁（Fc）基团整合到纳米尺寸的PCN-222(Fe)（PCN = 多孔配位网络）中，以合成具有Fc基团和铁卟啉两个氧化还原中心的Fc@PCN-222(Fe)复合材料。对DO不敏感的Fc基团用作内参，而PCN-222(Fe)中的铁卟啉是DO指示剂。两个氧化还原中心的阴极电流之比与DO浓度在2.8至28.9 mg/mL范围内呈线性关系，检测限为0.3 mg/mL。此外，基于Fc@PCN-222(Fe)复合材料的比率型电化学传感器对DO传感结果具有高选择性和稳定性。由于有许多氧化还原中心，如亚甲蓝和硫堇，可以整合到MOFs中，因此可以简单地开发许多基于MOF的比率型电化学传感器用于高性能生物传感。
