Research Center for Analytical Sciences, Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China.
Bayuquan Customs of the People's Republic of China, Yingkou 115000, China.
Mater Sci Eng C Mater Biol Appl. 2021 Oct;129:112404. doi: 10.1016/j.msec.2021.112404. Epub 2021 Sep 1.
Herein a nano-scale bimetallic Fe/Eu-MOF with a regular octahedral structure was synthesized for the first time. The synthesized Fe/Eu-MOF has both peroxidase-like activity and fluorescence properties. Fe/Eu-MOF can catalyze HO to oxidize the chromogenic substrate TMB to produce blue oxTMB, which has ultraviolet absorption at 652 nm. Unexpectedly, the generated oxTMB can effectively quench the fluorescence of the catalyst Fe/Eu-MOF at 450 nm. The quenching mechanism is mainly the internal filtration effect (IFE), accompanied by static quenching (SQE), Förster resonance energy transfer (FRET) and photoelectron transfer (PET). Fe/Eu-MOF has a high affinity for sodium pyrophosphate (PPi). PPi can be adsorbed to the surface of Fe/Eu-MOF, destroying the structure of Fe/Eu-MOF and inhibiting its catalytic activity, resulting in a decrease in UV absorbance and the decline of fluorescence quenching. In contrast, phosphoric acid (Pi) has almost no effect on the reaction system. Alkaline phosphatase (ALP) can catalyze the hydrolysis of PPi to Pi, thereby reducing the inhibitory effect of PPi. Based on this, we successfully constructed a dual-mode ALP sensor with high selectivity. The linear ranges based on the 652 nm absorption or the fluorescence detection are from 1 to 200 U/L, and the detection limits are 0.6 for the absorption method and 0.9 U/L for the fluorescence method, respectively.
本文首次合成了具有规则八面体结构的纳米级双金属 Fe/Eu-MOF。所合成的 Fe/Eu-MOF 具有过氧化物酶样活性和荧光性质。Fe/Eu-MOF 可以催化 HO 氧化显色底物 TMB 生成蓝色 oxTMB,oxTMB 在 652nm 处有紫外吸收。出人意料的是,生成的 oxTMB 可以有效地猝灭催化剂 Fe/Eu-MOF 在 450nm 处的荧光。猝灭机制主要是内部滤过效应(IFE),同时伴有静态猝灭(SQE)、Förster 共振能量转移(FRET)和光电子转移(PET)。Fe/Eu-MOF 对焦磷酸钠(PPi)具有高亲和力。PPi 可以被吸附到 Fe/Eu-MOF 的表面,破坏 Fe/Eu-MOF 的结构并抑制其催化活性,导致 UV 吸光度降低和荧光猝灭下降。相比之下,磷酸(Pi)对反应体系几乎没有影响。碱性磷酸酶(ALP)可以催化 PPi 的水解生成 Pi,从而减轻 PPi 的抑制作用。基于此,我们成功构建了一种具有高选择性的双模式 ALP 传感器。基于 652nm 吸收或荧光检测的线性范围分别为 1 至 200 U/L,检测限分别为吸收法的 0.6 U/L 和荧光法的 0.9 U/L。