Zhong Qi, Wang Kangdong, Pan Gao, Peng Shuping, Shuai Cijun
Jiangxi Province Key Laboratory of Additive Manufacturing of Implantable Medical Device, Jiangxi University of Science and Technology, Nanchang 330013, China.
State Key Laboratory of Precision Manufacturing for Extreme Service Performance, College of Mechanical and Electrical Engineering, Central South University, Changsha 410083, China.
ACS Appl Mater Interfaces. 2024 Dec 4;16(48):65837-65849. doi: 10.1021/acsami.4c13630. Epub 2024 Nov 21.
CeO nanozymes have demonstrated the potential to enhance biological scaffolds with chemodynamic therapy. However, their catalytic efficacy is limited by the slow conversion of Ce to Ce and the lack of substrates like HO and H. To address these challenges, we adopted a dual-pronged strategy that utilized the plasmonic resonance of Au nanoparticles and their glucose-oxidase mimicry to boost electron and hydrogen transfer. Specifically, we integrated Au/CeO nanozymes into poly-l-lactic acid scaffolds via selective laser sintering. This conversion of Ce to Ce in the scaffolds enhanced the reduction of HO to a hydroxyl radical, inducing oxidative stress in tumor cells. The Au nanoparticles played a crucial role in boosting the Ce/Ce catalytic cycle by providing both the energy and the catalytic substrates. They recycled Ce back to Ce by exploiting plasmonic-induced hot electrons and catalyzed glucose oxidation to supply HO and H. Our nanoscale and atomic-scale simulations confirmed that the Au/CeO hybrid structure utilized near-field coupling to amplify the plasmonic resonance and the Au-O-Ce bridge reduced the electron transfer barrier. Consequently, the Au/CeO scaffold decreased the activation energy from 22.57 to 9.92 kJ/mol. These findings highlight the significant promise of the Au/CeO nanozyme scaffold for NIR-enhanced chemodynamic therapy.
二氧化铈纳米酶已显示出通过化学动力学疗法增强生物支架的潜力。然而，它们的催化效率受到铈（Ce）向铈（Ce）缓慢转化以及缺乏过氧化氢（HO）和氢（H）等底物的限制。为了应对这些挑战，我们采用了双管齐下的策略，利用金纳米颗粒的等离子体共振及其葡萄糖氧化酶模拟功能来促进电子和氢的转移。具体而言，我们通过选择性激光烧结将金/二氧化铈纳米酶整合到聚左旋乳酸支架中。支架中铈向铈的这种转化增强了过氧化氢向羟基自由基的还原，从而在肿瘤细胞中诱导氧化应激。金纳米颗粒通过提供能量和催化底物在促进铈/铈催化循环中发挥了关键作用。它们利用等离子体诱导的热电子将铈循环回铈，并催化葡萄糖氧化以提供过氧化氢和氢。我们的纳米级和原子级模拟证实，金/二氧化铈混合结构利用近场耦合放大了等离子体共振，并且金-氧-铈桥降低了电子转移势垒。因此，金/二氧化铈支架将活化能从22.57千焦/摩尔降低到9.92千焦/摩尔。这些发现突出了金/二氧化铈纳米酶支架在近红外增强化学动力学疗法方面的巨大前景。
