不同的锰氧化物纳米颗粒的抗氧化剂和促氧化剂活性之间的交叉及其生物学意义。,Journal of Materials Chemistry B

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不同的锰氧化物纳米颗粒的抗氧化剂和促氧化剂活性之间的交叉及其生物学意义。
Journal of Materials Chemistry B ( IF 6.1 ) Pub Date : 2020-01-22 , DOI: 10.1039/c9tb02524c
Xiumei Jiang ₁ , Patrick Gray ₁ , Mehulkumar Patel ₂ , Jiwen Zheng ₂ , Jun-Jie Yin ₁

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锰氧化物纳米颗粒（MnOx NPs）被认为具有几种酶样活性。然而，研究经常使用颜色变化或荧光来确定催化活性。尽管这些探针简单且灵敏，但这些方法可能会分散注意力，或者无法反映生物系统中的催化活性。为了解决这个问题，在这里，我们使用了电子自旋共振（ESR）光谱技术，该技术被证明可以有效地识别和量化在纳米材料催化的反应中产生/清除的自由基，从而系统地评估三种MnOx NP（MnO2， Mn2O3和Mn3O4 NPs）用于生物相关的抗氧化剂（抗坏血酸和谷胱甘肽（GSH））和活性氧（ROS）（过氧化氢（H2O2），超氧阴离子，和羟基自由基）。我们发现，所有三个MnOx NP都具有前氧化活性和抗氧化活性，包括类似氧化酶，过氧化氢酶和超氧化物歧化酶（SOD）的活性，但没有类似过氧化物酶或羟基自由基的清除活性。此外，这些MnOx NP之间对不同反应的催化活性也存在差异。Mn2O3表现出最强的抗坏血酸盐氧化活性，其次是MnO2和Mn3O4，而Mn3O4表现出比Mn2O3和MnO2对GSH的最强氧化效率。在H2O2的催化分解中，MnO2 NPs在生成分子氧方面比Mn2O3或Mn3O4表现出更高的效率。细胞研究表明，所有三种MnOx NPs诱导的细胞活力呈浓度依赖性降低，其中Mn3O4> Mn3O2> MnO2。在较低浓度（<100μM）下，与溶液中检测到的酶样活性一致，所有三个NP均显着降低H2O2诱导的Caco-2细胞的细胞毒性。我们的研究确定了MnOx NPs的多酶活性，并在不同价态的MnOx NPs之间表现出不同的酶样活性及其生物学意义。这些结果为安全有效地应用MnOx NPs作为清除ROS的生物医学纳米材料提供了有价值的信息。

"点击查看英文标题和摘要"

Crossover between anti- and pro-oxidant activities of different manganese oxide nanoparticles and their biological implications.

Manganese oxide nanoparticles (MnOx NPs) have been suggested to possess several enzyme-like activities. However, studies often used either color change or fluorescence to determine the catalytic activity. Despite the simplicity and sensitivity of these probes, these methods may give distracting artifacts or not reflect the catalytic activities in biological systems. To address this issue, herein, we used electron spin resonance (ESR) spectroscopy, a technique proven effective in identifying and quantifying the free radicals produced/scavenged in nanomaterial-catalyzed reactions, to systematically evaluate the catalytic activities of three MnOx NPs (MnO2, Mn2O3, and Mn3O4 NPs) towards biologically relevant antioxidants (ascorbate and glutathione (GSH)) and reactive oxygen species (ROS) (hydrogen peroxide (H2O2), superoxide anion, and hydroxyl radical). We found that all three MnOx NPs possess both pro- and anti-oxidant activities, including oxidase-, catalase-, and superoxide dismutase (SOD)-like activities but without peroxidase-like or hydroxyl radical scavenging activity. In addition, there are differences among these MnOx NPs in their catalytic activities towards different reactions. Mn2O3 shows the strongest ascorbate oxidation activity, followed by MnO2 and Mn3O4, while Mn3O4 shows the strongest oxidation efficiency towards GSH compared to Mn2O3 and MnO2. In the catalyzed decomposition of H2O2, MnO2 NPs show higher efficiency in the generation of molecular oxygen than Mn2O3 or Mn3O4. Cellular studies indicate that all three MnOx NPs induced concentration-dependent decreases in the cell viability, with Mn3O4 > Mn3O2 > MnO2. At lower concentrations (<100 μM), consistent with the enzyme-like activities detected in solution, all three NPs significantly decreased H2O2-induced cytotoxicity in Caco-2 cells. Our study determined the multi-enzymatic activities of MnOx NPs and exhibited differences among MnOx NPs of different valences in their enzyme-like activities and their biological implications; these results provide valuable information for safe and efficient applications of MnOx NPs as ROS-scavenging biomedical nanomaterials.

更新日期：2020-02-13

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