Analytica chimica acta · 2025
Electronic reconfiguration enhanced oxidase-mimicking activity of Cu-Mn3O4 for colorimetric detection of total antioxidant capacity.
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Li Xiaoliang, Chen Zizhong, Sui Chengji, Wang Lin, Zheng Fengjia, Li Fenghua, Yang Xiaoxu, Jiao Yanni, Jiang Dafeng
Аннотация
BACKGROUND: The accurate determination of food's total antioxidant capacity is essential for assessing its nutritional quality and health benefits. Developing highly sensitive and rapid detection methods is crucial. Colorimetric detection can achieve extremely high sensitivity and visualization in the presence of a catalyst. As emerging catalysts, atomic nanozymes are nanomaterials with enzyme-like active sites at the atomic scale, demonstrating exceptional atomic efficiency and catalytic potential. However, achieving both high catalytic efficiency and low cost for these oxidase mimics remains a significant challenge.
RESULTS: This study developed a copper-doped Mn3O4 nanozyme (Cu-Mn3O4) with enhanced oxidase-like activity for measuring total antioxidant capacity without requiring hydrogen peroxide. The incorporation of Cu into the Mn3O4 structure modified its electronic properties, strengthening oxygen adsorption and facilitating electron transfer, which boosted the generation of reactive oxygen species for oxidizing the chromogenic substrate 3,3',5,5'-tetramethylbenzidine. The optimized Cu-Mn3O4 exhibited a 4.5-fold higher affinity for 3,3',5,5'-tetramethylbenzidine than pristine Mn3O4. A sensitive colorimetric assay was established based on antioxidant-induced suppression of the blue-colored product. The method detected ascorbic acid with a low limit of 0.009 μM and a wide linear range. It was successfully applied with a smartphone-based reader to determine the total antioxidant capacity of commercial beverages and fruit juices, demonstrating high reproducibility and strong correlation with a standard method.
SIGNIFICANCE: This work not only provides an effective strategy for designing advanced nanozymes through atomic-level doping and electronic structure modulation but also establishes a reliable, cost-effective, and practical platform for the rapid evaluation of antioxidant quality in food products. It opens new avenues for the development of next-generation nanozyme-based sensors for various analytical applications.
RESULTS: This study developed a copper-doped Mn3O4 nanozyme (Cu-Mn3O4) with enhanced oxidase-like activity for measuring total antioxidant capacity without requiring hydrogen peroxide. The incorporation of Cu into the Mn3O4 structure modified its electronic properties, strengthening oxygen adsorption and facilitating electron transfer, which boosted the generation of reactive oxygen species for oxidizing the chromogenic substrate 3,3',5,5'-tetramethylbenzidine. The optimized Cu-Mn3O4 exhibited a 4.5-fold higher affinity for 3,3',5,5'-tetramethylbenzidine than pristine Mn3O4. A sensitive colorimetric assay was established based on antioxidant-induced suppression of the blue-colored product. The method detected ascorbic acid with a low limit of 0.009 μM and a wide linear range. It was successfully applied with a smartphone-based reader to determine the total antioxidant capacity of commercial beverages and fruit juices, demonstrating high reproducibility and strong correlation with a standard method.
SIGNIFICANCE: This work not only provides an effective strategy for designing advanced nanozymes through atomic-level doping and electronic structure modulation but also establishes a reliable, cost-effective, and practical platform for the rapid evaluation of antioxidant quality in food products. It opens new avenues for the development of next-generation nanozyme-based sensors for various analytical applications.