离子交换设计三维 CoFe₂O₄ 纳米酶用于抗坏血酸的超灵敏比色传感

Ion exchange design of three-dimensional CoFe₂O₄ nanozyme for ultrasensitive colorimetric sensing of ascorbic acid

摘要

过渡双金属氧化物具有丰富的价态、良好的生物相容性以及优异的催化活性,在众多材料中脱颖而出。以ZIF-67为前驱体,经离子交换合成钴铁普鲁士蓝类似物(Co-Fe PBA),通过一步热解制备了一种 CoFe₂O₄ 中空纳米笼。CoFe₂O₄ 中Co、Fe双金属提供了大量的活性位点,而纳米笼结构提供了一个反应空腔,腔内含有大量活性氧,可快速氧化底物。CoFe₂O₄ 表现出优异的类过氧化物酶活性,在H₂O₂ 的存在下,能有效催化3,3',5,5'-四甲基联苯胺(TMB)氧化生成蓝色产物oxTMB。抗坏血酸(AA)具有抗氧化性,可抑制 CoFe₂O₄ 的催化作用,并将oxTMB还原为TMB。基于这一原理,将CoFe₂O₄ 纳米酶与TMB、H₂O₂ 结合,构建了一种比色传感平台,可快速、精准检测饮料中的AA的浓度。该平台具有较高的灵敏度和选择性,线性范围为1~500 μ mol/L,检测限为0.39 μ mol/L。这项工作拓宽了双金属氧化物材料在生物传感领域的应用范围。

Abstract

Transition bimetallic oxides stand out among many materials with abundant valence states, good biocompatibility and satisfactory catalytic activity. A hollow nanocage CoFe₂O₄ was prepared by one-step pyrolysis of Cobalt-Iron Prussian Blue Analogue (Co-Fe PBA), which was synthesized by ion-exchange using ZIF-67 as a precursor. The Co and Fe bimetals in CoFe₂O₄ provide a large number of active sites, while the nanocage structure provides a reaction space containing a large amount of reactive oxygen species for the rapid oxidation of the substrate. CoFe₂O₄ exhibited superior peroxidase-like activity, effectively catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to produce the blue product oxTMB in the presence of H₂O₂. Due to the antioxidant properties of ascorbic acid (AA), it can inhibit the catalytic activity of CoFe₂O₄, reducing oxTMB back to TMB. Based on this principle, a colorimetric sensing platform was constructed by combining CoFe₂O₄ nanozyme with TMB and H₂O₂ for the rapid and accurate detection of AA molar concentration in beverages. This platform demonstrated high sensitivity and selectivity, with a linear range of 1-500 μ mol/L and a detection limit of 0.39 μ mol/L. This work broadens the application of bimetallic oxide materials in biosensing.

关键词

纳米酶 / 比色传感 / 抗坏血酸 / 金属有机框架 / ZIF-67衍生物

Key words

nanozyme / colorimetric sensing / ascorbic acid / metal-organic framework / ZIF-67 derivative

参考文献

[1] ALI A, SAKHAWAT R, WASEEM K, et al. Potential of ascorbic acid in human health against different diseases: an updated narrative review[J]. International Journal of Food Properties, 2024, 27(1): 493-515.

[2] 岳晓月, 吴朝云, 闫曙亮, 等. 基于 CeO₂/CoOOH 纳米酶的比色分析法快速检测水果中抗坏血酸[J]. 食品科学, 2024, 45(24): 250-258.

[3] YUE X Y, WU Z Y, YAN S L, et al. Colorimetric method based on CeO₂/CoOOH nanozyme for rapid detection of ascorbic acid in fruits[J]. Food Science, 2024, 45(24): 250-258.

[4] 郑鹏来, 钱慧, 李益, 等. 基于 Au@ZIF-67/rGO 纳米复合材料构建的电化学传感器在抗坏血酸检测中的应用[J]. 印染助剂, 2023, 40(10): 6-11.

[5] ZHENG P L, QIAN H, LI Y, et al. Electrochemical sensor based on Au@ZIF-67/rGO nanocomposites in the detection of ascorbic acid[J]. Textile Auxiliaries, 2023, 40(10): 6-11.

[6] 吴凡, 卢朝粉, 李佳昕, 等. 基于CoFe(Ⅲ)PBA/GO 过氧化物模拟酶化学发光法检测 H₂O₂ 和抗坏血酸[J]. 分析试验室, 2022, 41(2): 147-151.

[7] WU F, LU C F, LI J X, et al. Chemiluminescence detection of hydrogen peroxide and ascorbic acid based on CoFe(Ⅲ)PBA/GO mimetic peroxidase[J]. Chinese Journal of Analysis Laboratory, 2022, 41(2): 147-151.

[8] 舒开继, 黄选忠. 离子色谱法测定药品中抗坏血酸[J]. 化学分析计量, 2022, 31(10): 35-39.

[9] SHU K J, HUANG X Z. Determination of ascorbic acid in pharmaceuticals by ion chromatography[J]. Chemical Analysis and Meterage, 2022, 31(10): 35-39.

[10] 曹程程, 林祥芳, 任晨宇, 等. 聚腺嘌呤保护的金纳米团簇与金属有机框架材料ZIF-8复合物的聚集诱导发光增强及用于抗坏血酸的高灵敏荧光检测[J]. 分析化学, 2022, 50(6): 932-939.

[11] CAO C C, LIN X F, REN C Y, et al. Polyadenine-capped gold nanoclusters incorporated into zeolitic imidazolate framework-8 with aggregation-induced fluorescence emission enhancement for high-sensitivity fluorescence detection of ascorbic acid[J]. Chinese Journal of Analytical Chemistry, 2022, 50(6): 932-939.

[12] ZHANG S, LI Y, ZHUANG X, et al. Nano-metal-organic frameworks isolated in mesoporous structures[J]. Advanced Materials, 2025, 37(9): 2418344-2418356.

[13] FU L, ZHOU J, ZHOU Z, et al. Unlocking catalytic potential: encasing CoP nanoparticles within mesoporous CoFeP nanocubes for enhanced oxygen evolution reaction[J]. ACS Nano, 2023, 17(22): 22744-22754.

[14] WANG X, HAO L, ZHANG Z, et al. Design three-dimensional CoFe₂O₄ nanocage via ion exchange route for ultra-sensitive electrochemical sensing of nitrobenzene[J]. Ceramics International, 2023, 49(11, Part B): 18699-18707.

[15] ZHOU S, YE Z, HU S, et al. Designed formation of Co₃O₄/ZnCo₂O₄/CuO hollow polyhedral nanocages derived from zeolitic imidazolate framework-67 for high-performance supercapacitors[J]. Nanoscale, 2018, 10(33): 15771-15781.

[16] 任芝军, 沈峻峰, 吕龙义, 等. 新型CoFe₂O₄-EPS磁性氧化还原介体的制备及优化[J]. 水处理技术, 2026, 52(2): 86-92.

[17] REN Z J, SHEN J F, LÜ L Y, et al. Preparation and optimization of novel CoFe₂O₄-EPS magnetic redox mediators[J]. Technology of Water Treatment, 2026, 52(2): 86-92.

[18] ZHANG C L, LU B R, CAO F H, et al. Hierarchically structured Co₃O₄ @ carbon porous fibers derived from electrospun ZIF-67/PAN nanofibers as anodes for lithium ion batteries[J]. Journal of Materials Chemistry A, 2018, 6(27): 12962-12968.

[19] OJHA V H, KANT K M. Investigation of structural and magnetic properties of strained CoFe₂O₄ nanoparticles[J]. Journal of Physics and Chemistry of Solids, 2021, 148: 109655-109664.

[20] LI Y, LU X, TIAN Q, et al. A simple way for preparing CoFe₂O₄-based composite with improved lithium storage[J]. Applied Surface Science, 2022, 593: 153433-153443.

[21] CHEN Q, ZHANG X, LI S, et al. MOF-derived Co₃O₄@Co-Fe oxide double-shelled nanocages as multi-functional specific peroxidase-like nanozyme catalysts for chemo/biosensing and dye degradation[J]. Chemical Engineering Journal, 2020, 395: 125130-125139.

[22] 孙迪, 杨学文, 王辉, 等. 基于多功能适配体磁性COF-CuO/Au纳米酶的双信号比色/荧光法检测海产品中副溶血性弧菌[J]. 食品科学, 2026, 47(6): 23-40.

[23] SUN D, YANG X W, WANG H, et al. Dual-signal colorimetric/fluorescent detection of vibrio parahaemolyticus in seafood using a multifunctional aptamer-conjugated magnetic covalent organic framework-CuO/Au nanozyme[J]. Food Science, 2026, 47(6): 23-40.

[24] MU J, WANG Y, ZHAO M, et al. Intrinsic peroxidase-like activity and catalase-like activity of Co₃O₄ nanoparticles[J]. Chemical Communications, 2012, 48(19): 2540-2542.

[25] SU L, FENG J, ZHOU X, et al. Colorimetric detection of urine glucose based ZnFe₂O₄ magnetic nanoparticles[J]. Analytical Chemistry, 2012, 84(13): 5753-5758.

[26] FAN S, ZHAO M, DING L, et al. Preparation of Co₃O₄/crumpled graphene microsphere as peroxidase mimetic for colorimetric assay of ascorbic acid[J]. Biosensors and Bioelectronics, 2017, 89: 846-852.

[27] YANG W, LI J, WANG M, et al. A colorimetric strategy for ascorbic acid sensing based on the peroxidase-like activity of core-shell Fe₃O₄/CoFe-LDH hybrid[J]. Colloids and Surfaces B: Biointerfaces, 2020, 188: 110742-110750.

[28] LAI X, LI R, ZHANG B, et al. Colorimetric strategy of Fe/Co-doped porphyrin metal-organic frameworks with enzyme-like activity for the detection of ascorbic acid[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 680: 132645-132652.

[29] WU T, MA Z, LI P, et al. Colorimetric detection of ascorbic acid and alkaline phosphatase activity based on the novel oxidase mimetic of Fe-Co bimetallic alloy encapsulated porous carbon nanocages[J]. Talanta, 2019, 202: 354-361.

[30] ZHANG C, NAN Z. Improvement of Fe_0.8Ni_0.2S₂ peroxidase-like activity through the accelerated conversion from Fe³⁺ to Fe²⁺ [J]. The Journal of Physical Chemistry C, 2022, 126(9): 4355-4364.

[31] SHEN L, KHAN M A, WU X, et al. Fe-N-C single-atom nanozymes based sensor array for dual signal selective determination of antioxidants[J]. Biosensors and Bioelectronics, 2022, 205: 114097-114105.

[32] YANG L Y, KONG J, XIAO D X, et al. Respiratory-responsive active elimination of microbe and pesticide residue on fruits[J]. Food Chemistry, 2026, 508: 148374.

[33] NING Y, SUN Y, YANG X, et al. Defect-rich CoFe-layered double hydroxides as superior peroxidase-like nanozymes for the detection of ascorbic acid[J]. ACS Applied Materials & Interfaces, 2023, 15(22): 26263-26272.

[34] WANG X, HAN Q, CAI S, et al. Excellent peroxidase mimicking property of CuO/Pt nanocomposites and their application as an ascorbic acid sensor[J]. Analyst, 2017, 142(13): 2500-2506.

基金资助

山东省重点研发计划(重大科技创新工程)项目(2021ZDPT03)