ROS-induced therapy can eradicate breast tumors when combined with thermal ablation, but excessive ROS also threatens peritumoral tissue with inflammation. To eradicate tumors and avoid inflammatory sequela, it is necessary to generate ROS in treatment stage and scavenge ROS in prognostic stage. However, it is a great challenge to reverse ROS in different stages. Herein, the “ROS switcher” of MnO2-coated Prussian blue (PM) is loaded in hyaluronic acid methacrylate (HAMA) hydrogel microspheres, combining ROS generation by Mn-mediated Fenton-like reaction, and ROS scavenging by Fe3+/2+ electron transfer. Firstly, it is ROS generator that oxidatively damages biomacromolecules in residual tumors, then it is ROS scavenger that reduces pro-inflammatory cytokines and oxidation stress in peritumoral skin. Glucose oxidase is immobilized in HAMA microspheres to enhance ROS supply by catalyzing glucose into H2O2, degrading MnO2 into Mn2+, and providing H2O2 for a Fenton-like reaction. After MnO2 degradation, Prussian blue is gradually exposed and scavenges ROS, thus defending oxidative skin damage and alleviating ROS-stimulated inflammation. In vitro results indicate that the microsphere supplied sustained ROS for up to 5 days, and H2O2-degraded PM (0.2 mg mL−1) scavenged 500 μM H2O2. In vivo results confirm that 4/6 breast tumors were eradicated while pro-inflammatory cytokines were significantly reduced with ROS level in peri-tumoral skin. In summary, ROS switcher is developed by Mn-mediated nano-shell peeling and achieves tumor eradication and post-operative skin repair after thermal ablation of the breast tumor.

中文翻译：

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通过 MnO2 涂层的普鲁士蓝负载透明质酸甲基丙烯酸酯水凝胶微球的活性氧切换器用于局部抗肿瘤治疗


ROS 诱导的疗法与热消融相结合可以根除乳腺肿瘤，但过量的 ROS 也会威胁瘤周组织发炎。为了根除肿瘤并避免炎症后遗症，需要在治疗阶段生成 ROS，在预后阶段清除 ROS。但是，在不同阶段逆转 ROS 是一个巨大的挑战。在此，MnO2 包被的普鲁士蓝 （PM） 的“ROS 切换器”负载在甲基丙烯酸透明质酸酯 （HAMA） 水凝胶微球中，结合了 Mn 介导的 Fenton 样反应的 ROS 生成和 Fe3+/2+ 电子转移的 ROS 清除。首先，是 ROS 发生器氧化损伤残留肿瘤中的生物大分子，然后是 ROS 清除剂减少瘤周皮肤中的促炎细胞因子和氧化应激葡萄糖氧化酶固定在 HAMA 微球中，通过催化葡萄糖转化为 H2O2，将 MnO2 降解成 Mn2+，并为 Fenton 样反应提供 H2O2 来增强 ROS 供应。MnO2 降解后，普鲁士蓝逐渐暴露并清除 ROS，从而保护氧化性皮肤损伤并减轻 ROS 刺激的炎症。体外结果表明，微球提供长达 5 天的持续 ROS，H2O2 降解的 PM （0.2 mg mL-1） 清除了 500 μM H 2 O 2 。体内结果证实，瘤周皮肤中 4/6 的乳腺肿瘤被根除，而促炎细胞因子随着 ROS 水平的升高而显著降低。综上所述，ROS switcher 是通过 Mn 介导的纳米壳剥离开发的，实现了乳腺肿瘤热消融后的肿瘤根除和术后皮肤修复。