北京大学郭少军团队报道了用于催化治疗的双原子酶D带中心的精确调控。相关研究成果发表在2024年3月30日出版的《美国化学会杂志》。

基于单原子纳米酶的催化治疗在肿瘤催化治疗领域引起了极大的兴趣；然而，它们的发展受到纳米酶对底物（H₂O₂或O₂）低亲和力的影响，导致肿瘤微环境中缺乏催化活性。

该文中，研究人员报道了一种新的策略，用于精确调节双原子位点的d带中心，以增强金属原子位点和底物在一类富含氮的多孔碳双原子位点Fe–Mn（Fe₁Mn₁–NCe）上的亲和力，从而大大提高多种类酶催化活性。所制备的Fe₁Mn₁–NCe比Fe₁–NCe（Kcat/Km=2.41×10⁴ S^–1·M^–1）具有更高的催化效率（Kcat/Km=4.01×10⁵ S^–1），1年后活性保持率超过90%，是目前报道的双原子纳米酶中最好的。

理论计算表明，Mn的协同作用使Fe的d带中心从1.113 eV上升到0.564 eV，增强了对基体的吸附能力，从而加速了H₂O₂的离解，削弱了O₂上的O–O键。研究进一步证明，Fe₁Mn₁–NCe优越的类酶催化活性与光热疗法相结合，可以有效抑制体内肿瘤生长，抑制率高达95.74%，是迄今为止报道的双原子人工酶疗法中的最高值。

附：英文原文

Title: Precise Tuning of the D-Band Center of Dual-Atomic Enzymes for Catalytic Therapy

Author: Ruijin Zeng, Qian Gao, Limei Xiao, Weijun Wang, Yu Gu, Hengshuo Huang, Yingjun Tan, Dianping Tang, Shaojun Guo

Issue&Volume: March 30, 2024

Abstract: Single-atom nanozyme-based catalytic therapy is of great interest in the field of tumor catalytic therapy; however, their development suffers from the low affinity of nanozymes to the substrates (H2O2 or O2), leading to deficient catalytic activity in the tumor microenvironment. Herein, we report a new strategy for precisely tuning the d-band center of dual-atomic sites to enhance the affinity of metal atomic sites and substrates on a class of edge-rich N-doped porous carbon dual-atomic sites Fe–Mn (Fe1Mn1–NCe) for greatly boosting multiple-enzyme-like catalytic activities. The as-made Fe1Mn1–NCe achieved a much higher catalytic efficiency (Kcat/Km = 4.01 × 105 S–1·M–1) than Fe1–NCe (Kcat/Km = 2.41 × 104 S–1·M–1) with an outstanding stability of over 90% activity retention after 1 year, which is the best among the reported dual-atom nanozymes. Theoretical calculations reveal that the synergetic effect of Mn upshifts the d-band center of Fe from 1.113 to 0.564 eV and enhances the adsorption capacity for the substrate, thus accelerating the dissociation of H2O2 and weakening the O–O bond on O2. We further demonstrated that the superior enzyme-like catalytic activity of Fe1Mn1–NCe combined with photothermal therapy could effectively inhibit tumor growth in vivo, with an inhibition rate of up to 95.74%, which is the highest value among the dual-atom artificial enzyme therapies reported so far.

DOI: 10.1021/jacs.4c00791

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c00791