Yang Qi, Zhang Jiawei, Tang Yuxi, Ju Yan, Gao Xuejiao, Chu Chaoyang, Jia Huimin, He Weiwei
Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, College of Chemical and Materials Engineering, Xuchang University Xuchang Henan 461000 P. R. China
Henan Joint International Research Laboratory of Nanomaterials for Energy and Catalysis, Xuchang University Xuchang Henan 461000 China.
Chem Sci. 2025 May 21. doi: 10.1039/d5sc01799h.
Peroxidase (POD)-like nanozymes are attracting increasing attention in anti-tumor, antibacterial, disease diagnosis, and environmental applications. However, simultaneously improving the POD-like activity and stability of nanozymes remains a non-trivial challenge. Inspired by the excellent stability and multiple active sites of high-entropy alloys, we design a Ru-based (RuPtIrRhCu) high-entropy alloy nanozyme (HEAzyme) with improved catalytic activity and stability. Benefiting from the strong adsorption capacity of Ru toward hydrogen peroxide (HO)/hydroxyl (OH) and the collaborative effect induced by the multiple elements, an interesting "hydroxyl spillover" route is triggered on the RuPtIrRhCu HEAzymes. The efficient dissociated adsorption of HO and fast transfer of adsorbed hydroxyl (*OH, * denotes the adsorbed state) is achieved, resulting in boosted POD-like activity. The POD-like activity of the HEAzyme remained unchanged for 6 months, exhibiting outstanding stability. A multi-channel colorimetric sensor array was developed to specifically identify eight biological antioxidants, especially for the chiral recognition of l-cysteine (l-Cys) and d-cysteine (d-Cys). This study not only provides an effective, multi-site collaborative mechanism for improving POD-like activity and stability but also extends the horizons and perspectives in nanozymes.
类过氧化物酶（POD）纳米酶在抗肿瘤、抗菌、疾病诊断和环境应用等方面正受到越来越多的关注。然而，同时提高纳米酶的类POD活性和稳定性仍然是一项艰巨的挑战。受高熵合金优异稳定性和多个活性位点的启发，我们设计了一种具有提高的催化活性和稳定性的钌基（RuPtIrRhCu）高熵合金纳米酶（HEAzyme）。得益于Ru对过氧化氢（HO）/羟基（OH）的强吸附能力以及多种元素诱导的协同效应，在RuPtIrRhCu HEAzymes上触发了一条有趣的“羟基溢流”途径。实现了HO的高效解离吸附和吸附羟基（*OH，*表示吸附状态）的快速转移，从而提高了类POD活性。HEAzyme的类POD活性在6个月内保持不变，表现出出色的稳定性。开发了一种多通道比色传感器阵列，用于特异性识别八种生物抗氧化剂，特别是用于对l-半胱氨酸（l-Cys）和d-半胱氨酸（d-Cys）的手性识别。这项研究不仅为提高类POD活性和稳定性提供了一种有效的多位点协同机制，还拓展了纳米酶的视野和前景。
