Ye Jin, Li Chunsheng, Xu Jiating, Liu Shuang, Qu Jiawei, Wang Qiang, Cao Jun, Zhao Yanying, Li Chaorong, Yang Piaoping
Key Laboratory of Forest Plant Ecology, Ministry of Education, College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University, Harbin, 150001, P. R. China.
Heilongjiang Provincial Key Laboratory of Ecological Utilization of Forestry-Based Active Substances, Northeast Forestry University, Harbin, 150040, P. R. China.
Adv Mater. 2025 Jul;37(30):e2419673. doi: 10.1002/adma.202419673. Epub 2025 May 9.
Due to the enhanced flexibility of catalytic sites and synergistic effects between dual-atom active centers, dual-atom nanozymes stand out in the tumor catalytic therapy. However, precisely regulating the d-band centers of diatomic sites to break the linear-scaling relationship between intermediates remains a challenge. Herein, the hydrothermally mass-produced oxygen vacancies-engineered bimetallic silicate bio-nanoplatform with highly asymmetric O-bridged cerium─manganese (Ce─Mn) diatomic catalytic centers (CeMn-V DAs/EGCG@HA) is meticulously constructed by loading epigallocatechin-3-gallate (EGCG) and modifying with hyaluronic acid (HA) for multimodal synergistic cancer therapy. Theoretical calculations reveal that the introduction of Ce sites serves as secondary catalytic centers and upshifts d-band center of the Mn sites, thereby optimizing the adsorption/desorption of oxygen intermediates. The asymmetric Mn─O─Ce moiety facilitates electron transport within CeMn-V DAs, significantly enhancing peroxidase-like activities (K = 27.7 mM and V = 3.21×10 M s). Upon 650 nm laser irradiation, CeMn-V DAs/EGCG inhibits heat shock protein expression, enabling mild-photothermal (η = 36.1%) therapy, which can productively inhibit tumor growth in vivo, with an inhibition rate of up to 96.2%. Due to the ligand-field effect of EGCG-Mn/Ce complexes, high-valent metal ions are effectively reduced, sustaining an intrinsic self-driven cocatalytic cycle reaction. Overall, the construction of highly asymmetric bridged diatomic nanozymes will further promote the deep integration of nanotechnology and biology.
由于催化位点的灵活性增强以及双原子活性中心之间的协同效应，双原子纳米酶在肿瘤催化治疗中脱颖而出。然而，精确调节双原子位点的d带中心以打破中间体之间的线性标度关系仍然是一个挑战。在此，通过负载表没食子儿茶素-3-没食子酸酯（EGCG）并以透明质酸（HA）修饰，精心构建了具有高度不对称O桥联铈-锰（Ce-Mn）双原子催化中心的水热大量生产的氧空位工程化双金属硅酸盐生物纳米平台（CeMn-V DAs/EGCG@HA），用于多模式协同癌症治疗。理论计算表明，Ce位点的引入作为二级催化中心并使Mn位点的d带中心上移，从而优化了氧中间体的吸附/解吸。不对称的Mn-O-Ce部分促进了CeMn-V DAs内的电子传输，显著增强了过氧化物酶样活性（K = 27.7 mM且V = 3.21×10 M s）。在650 nm激光照射下，CeMn-V DAs/EGCG抑制热休克蛋白表达，实现温和光热（η = 36.1%）治疗，可有效抑制体内肿瘤生长，抑制率高达96.2%。由于EGCG-Mn/Ce配合物的配体场效应，高价金属离子被有效还原，维持了内在的自驱动共催化循环反应。总体而言，高度不对称桥联双原子纳米酶的构建将进一步促进纳米技术与生物学的深度融合。
