检测人体血液中谷胱甘肽（GSH）浓度的能力提供了一种简单和非侵入性的方法来监测与心血管疾病、癌症和糖尿病相关的变化。我们通过生物矿化方法展示了利用具有催化活性的蛋白质导向的人工纳米酶花状纳米酶（apo-TF-MnOx NFs）的潜力，以产生用于GSH的简单可见的比色传感器。实验证明apo-TF-MnOx NFs表现出过氧化酶、催化酶和超氧化物歧化酶样活性，但最显著的特征是出色的过氧化酶样活性，可以高效催化3,3'，5,5'-四甲基苯胺（TMB）在过氧化氢（H2O2）存在下的氧化反应生成蓝色产物。一些结果还表明apo-TF-MnOx NFs具有更强的过氧化酶样活性，这通过米氏常数（Km）和最大初始速度（Vmax）得到证实。因此，我们利用过氧化酶样活性开发了一种GSH比色生物传感器。幸运的是，该比色平台在最佳条件下对H2O2和GSH的响应范围分别为5μМ至300μМ和0.5μМ至35μМ，检测限分别为3.29 μM和0.15 μM（信噪比为3）。通过对急性冠状动脉综合征患者血样的定性检测，证实了该简易方法的可行性。我们研究的一个重要结果是，在无侵入性治疗方面，对急性冠状动脉综合征和健康人群的GSH进行差别鉴定的能力，这是其他方法所不具备的优势。这项工作不仅提出了一种新型纳米酶，而且展示了apo-TF-MnOx NFs在构建生物传感器方面的多个优点。因此，我们相信具有强过氧化酶样活性的apo-TF-MnOx NFs可以被应用为纳米酶，并广泛应用于医学和生物传感器领域。版权所有 © 2023 Elsevier B.V.保留所有权利。

The ability to detect glutathione (GSH) concentrations in human blood offered a simple and non-invasive method to monitor changes associated with cardiovascular diseases, cancers and diabetes. We showed the potential of employing catalytically active protein-directed nanoflower-like artificial nanozymes (apo-TF-MnOx NFs) by bio-mineralization method to produce simple and visible colorimetric sensor for GSH. The experiments proved that apo-TF-MnOx NFs exhibited peroxidase, catalase- and superoxide dismutase-like activities, but the most notable feature was the excellent peroxidase-like activity, which could efficiently catalyze the oxidation reaction of 3,3',5,5'- tetramethylbenzidine (TMB) in the existence of hydrogen peroxide (H2O2) to generate a blue product. Some outcomes also indicated that the apo-TF-MnOx NFs had stronger peroxidase-like activity, which was proved by the Michaelis-Menten constant (Km) and maximum initial velocity (Vmax). Hence, we used the peroxidase-like activity to develop a GSH colorimetric biosensor. Fortunately, the colorimetric platform exhibited a sensitive response to H2O2 and GSH in the range of 5 μМ to 300 μМ and 0.5 μМ to 35 μМ with a limit of detection of 3.29 μM and 0.15 μM (S/N = 3) under optimal conditions. The feasibility of the simple method was confirmed by qualitative detection of H2O2 and GSH in blood samples from acute coronary syndrome patients. A key outcome of our study was the ability to realized differential identification of GSH for acute coronary syndrome and healthy human without invasive treatment which was an advantage over other methods. This work not only proposed a new type of nanozymes, but also showed the multiple advantages of the apo-TF-MnOx NFs for the construction of biosensors. Thus, we believe that apo-TF-MnOx NFs with strong peroxidase-like activity can be employed as nanozymes and be widely applied in the fields of medicine and biological sensors.Copyright © 2023 Elsevier B.V. All rights reserved.