传统的银纳米粒子（Ag NPs）具有高负载率和堆积现象，导致脱落导致生物毒性和催化效率低。这严重阻碍了它们在生物医学中的应用。在这里，我们通过结合埃洛石粘土纳米管（HNT）和十二氢十二硼酸盐（closo-[B12H12]2-）来改进高度分散的银纳米颗粒和银单原子（SA）的合成，以提高生物相容性并降低负载率。这种新型银单原子纳米酶与银纳米颗粒纳米酶一起避免了高温煅烧，同时通过 closo-[B12H12]2- 和 HNT 的还原性和配位稳定性保持了极高水平的银利用效率。通过理论计算和电子顺磁共振，我们证实HNT@B12H12@Ag纳米酶中的Ag SAzymes和Ag NPs都能够将H2O2分解为羟基自由基（·OH）。为了应用，我们在体外和体内研究了HNT@B12H12@Ag纳米酶在肿瘤细胞中的催化活性和抗肿瘤作用，并证实它通过·OH的生成有效抑制黑色素瘤的生长，且生物毒性有限。本研究提供了一种新颖的银纳米酶合成方法，增加了其临床应用的可能性。版权所有 © 2024 Elsevier B.V. 保留所有权利。

The conventional silver nanoparticles (Ag NPs) are characterized with high loading rate and stacking phenomenon, leading to shedding caused biotoxicity and low catalytic efficiency. This seriously hinders their application in biomedicine. Here, we modified the highly dispersible Ag NPs and Ag single-atoms (SAs) synthesis by combining the halloysite clay nanotubes (HNTs) and dodecahydro-dodecaborate (closo-[B12H12]2-) to increase the biocompatible properties and decrease the loading rate. This novel Ag single-atom nanoenzyme alongside Ag NPs nanoenzyme avoid the elevated-temperature calcination while maintaining the exceptionally high-level efficiency of Ag utilization via the reducibility and coordination stabilization of closo-[B12H12]2- and HNTs. With theoretical calculation and electron paramagnetic resonance, we confirmed that both Ag SAzymes and Ag NPs in HNT@B12H12@Ag nanoenzyme are capable decompose the H2O2 into hydroxyl radical (·OH). For the application, we investigated the catalytic activity in the tumor cells and antitumor effects of HNT@B12H12@Ag nanoenzyme both in vitro and in vivo, and confirmed that it effectively suppressed melanoma growth through ·OH generation, with limited biotoxicity. This study provides a novel Ag nanoenzyme synthesis approach to increase the possibility of its clinical application.Copyright © 2024 Elsevier B.V. All rights reserved.