Guangdong Provincial Key Laboratory on Functional Soft Condensed Matter, Materials and Energy School, Guangdong University of Technology, Panyu District, Guangzhou510006, China.
Department of Laboratory Medicine, Guangdong Second Provincial General Hospital, Guangzhou510317, China.
Langmuir. 2022 Dec 20;38(50):15559-15569. doi: 10.1021/acs.langmuir.2c02218. Epub 2022 Dec 12.
Emerging metal-organic framework (MOF)-based mimic enzymes have been exploited to design a colorimetric sensor for the detection of biomolecules. However, it is challenging to figure out the glutathione (GSH) detection method and the corresponding sensing mechanism using an MOF-based colorimetric sensor. In this work, a novel iron-copper MOF with high activity is synthesized by a wet-chemical method. A GSH colorimetric sensor based on the peroxidase-like properties of the iron-copper MOF is developed. Hydrogen peroxide is converted to hydroxyl radicals by the peroxidase-like properties of the iron-copper MOF mimic enzyme, which can catalyze the colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB (ox-TMB). The kinetic constant of the MOF mimic enzyme (0.02 mM for HO) is superior to horseradish peroxidase (HRP). The GSH content can be quantified by proposing a sensor based on the colorimetric method and color turn-off mechanism. The turn-off mechanism of GSH analysis includes two aspects. On the one hand, the blue ox-TMB can be deoxidized to colorless TMB by GSH. On the other hand, hydroxyl radicals (OH) can be consumed by GSH. The linear range and limit of detection are 2-20 and 0.439 μM, respectively. At the same time, GSH detection also shows good specificity and anti-interference characteristics. Therefore, MOF-based colorimetric sensors have been used to qualitatively and quantitatively measure GSH contents in human serum. The mechanism and application of the iron-copper MOF pave a way for the development of mimic enzymes with polymetallic active sites in the field of colorimetric sensing.
新兴的金属-有机骨架(MOF)模拟酶已被用于设计用于检测生物分子的比色传感器。然而,使用基于 MOF 的比色传感器找出谷胱甘肽(GSH)的检测方法和相应的传感机制具有挑战性。在这项工作中,通过湿化学方法合成了一种具有高活性的新型铁-铜 MOF。开发了一种基于铁-铜 MOF 过氧化物酶样性质的 GSH 比色传感器。过氧化物酶样性质的铁-铜 MOF 模拟酶将过氧化氢转化为羟基自由基,该自由基可以催化无色 3,3',5,5'-四甲基联苯胺(TMB)转化为蓝色氧化 TMB(ox-TMB)。MOF 模拟酶的动力学常数(HO 为 0.02 mM)优于辣根过氧化物酶(HRP)。通过提出基于比色法和颜色关闭机制的传感器,可以定量测定 GSH 含量。GSH 分析的关闭机制包括两个方面。一方面,GSH 可以将蓝色 ox-TMB 还原为无色 TMB。另一方面,GSH 可以消耗羟基自由基(OH)。线性范围和检测限分别为 2-20 和 0.439 μM。同时,GSH 检测还表现出良好的特异性和抗干扰特性。因此,基于 MOF 的比色传感器已用于定性和定量测定人血清中的 GSH 含量。铁-铜 MOF 的机制和应用为比色传感领域中具有多金属活性位点的模拟酶的发展铺平了道路。