Abstract
This work reports the successful incorporation of Au and Ag nanoparticles within MIL-53(Fe) matrix which showed excellent morphological stability and dispersive capability as confirmed via various techniques. Au@MIL-53(Fe), Ag@MIL-53(Fe) were employed as a nanozyme (specifically mimicking peroxidase-like activity) for colorimetric detection of H2O2. The reaction mechanism of peroxidase-like activity was traced via radical studies, and hypothetical reaction routes were formulated for a better understanding of TMB (colorless) oxidation to oxo-TMB (blue). The study showed marked improvement in H2O2 detection with LOD of 0.0623 µM within a linear range (1–10 µM) (S/N = 3). The presence of H2O2 in spiked milk samples was analyzed and modeled through linear regression, and the resulting model was validated with an accuracy of 0.465–0.45% with RSD% lying within 1.93–3.81% for two different models falling within linear ranges (1–10 µM) and (10–100 µM), respectively. The value of activation energy for Au@MIL-53(Fe) was ca. 41.94 kJ.mol−1 which was found to be lower than pristine MIL-53(Fe) [ca. 49.36 kJ.mol−1]. Overall, Au@MIL-53(Fe) demonstrated an excellent colorimetric sensor for the detection of H2O2 both in model solution and in processed milk and could trace possible adulteration of milk. The material holds promise in the fabrication of various diagnostic prototypes for specific applications in food processing, and medical and environmental remediation.
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References
Abarghoei S, Fakhri N, Borghei YS, Hosseini M, Ganjali MR (2019) A colorimetric paper sensor for citrate as biomarker for early stage detection of prostate cancer based on peroxidase-like activity of cysteine-capped gold nanoclusters. Spectrochim Acta Part A Mol Biomol Spectrosc 210:251–259. https://doi.org/10.1016/j.saa.2018.11.026
Abbas ME, Luo W, Zhu L, Zou J, Tang H (2010) Fluorometric determination of hydrogen peroxide in milk by using a Fenton reaction system. Food Chem 120:327–331. https://doi.org/10.1016/j.foodchem.2009.10.024
Ai L, Li L, Zhang C, Fu J, Jiang J (2013) MIL-53(Fe): a metal-organic framework with intrinsic peroxidase-like catalytic activity for colorimetric biosensing. Chem Eur J 19:15105–15108. https://doi.org/10.1002/chem.201303051
Amin VM, Olson NF (1967) Spectrophotometric determination of hydrogen peroxide in milk. J Dairy Sci 50:461–464. https://doi.org/10.3168/jds.S0022-0302(67)87447-2
Bagheri N, Habibi B, Khataee A, Hassanzadeh J (2019) Application of surface molecular imprinted magnetic graphene oxide and high performance mimetic behavior of bi-metal ZnCo MOF for determination of atropine in human serum. Talanta 201:286–294. https://doi.org/10.1016/j.talanta.2019.04.023
Barreto JC, Smith GS, Strobel NHP, McQuillin PA, Miller TA (1994) Terephthalic acid: a dosimeter for the detection of hydroxyl radicals in vitro. Life Sci 56:PL89–PL96. https://doi.org/10.1016/0024-3205(94)00925-2
Bisswanger H (2014) Enzyme assays. Perspect Sci 1:41–55. https://doi.org/10.1016/j.pisc.2014.02.005
Bour JR, Wright AM, He X, Dincǎ M (2020) Bioinspired chemistry at MOF secondary building units. Chem Sci 11:1728–1737. https://doi.org/10.1039/c9sc06418d
Chen D, Li B, Jiang L, Duan D, Li Y, Wang J, He J, Zeng Y (2015) Highly efficient colorimetric detection of cancer cells utilizing Fe-MIL-101 with intrinsic peroxidase-like catalytic activity over a broad pH range. RSC Adv 5:97910–97917. https://doi.org/10.1039/c5ra18115a
Chen J, Shu Y, Li H, Xu Q, Hu X (2018) Nickel metal-organic framework 2D nanosheets with enhanced peroxidase nanozyme activity for colorimetric detection of H2O2. Talanta 189:254–261. https://doi.org/10.1016/j.talanta.2018.06.075
Du J-JJ, Yuan Y-PP, Sun J-XX, Peng F-MM, Jiang X, Qiu L-GG, Xie A-JJ, Shen Y-HH, Zhu J-FF (2011) New photocatalysts based on MIL-53 metal-organic frameworks for the decolorization of methylene blue dye. J Hazard Mater 190:945–951. https://doi.org/10.1016/j.jhazmat.2011.04.029
Gao Y, Li S, Li Y, Yao L, Zhang H (2017) Accelerated photocatalytic degradation of organic pollutant over metal-organic framework MIL-53(Fe) under visible LED light mediated by persulfate. Appl Catal B Environ 202:165–174. https://doi.org/10.1016/j.apcatb.2016.09.005
George P, Chaudhari K, Chowdhury P (2018) Influence of cation doping (Li+, Na+, K+) on photocatalytic activity of MIL-53(Fe). J Mater Sci 53:11694–11714. https://doi.org/10.1007/s10853-018-2443-9
Gilliland SE (1969) Enzymatic determination of residual hydrogen peroxide in milk. J Dairy Sci 52:321–324. https://doi.org/10.3168/jds.S0022-0302(69)86554-9
Guan H, Zhao Y, Zhang J, Liu Y, Yuan S, Zhang B (2018) Uniformly dispersed PtNi alloy nanoparticles in porous N-doped carbon nanofibers with high selectivity and stability for hydrogen peroxide detection. Sens Actuators B Chem 261:354–363. https://doi.org/10.1016/j.snb.2018.01.169
Gupta D (2015) Methods for determination of antioxidant capacity: A review. Int J Pharm Sci Res 6:546–566. https://doi.org/10.13040/IJPSR.0975-8232
HB Brooks, S Geeganage SD Kahl, C Montrose, S Sittampalam, MC Smith, JR Weidner 2004 Basics of enzymatic assays for HTS. Assay Guid Man 1–14. http://www.ncbi.nlm.nih.gov/pubmed/22553875
Horcajada P, Gref R, Baati T, Allan PK, Maurin G, Couvreur P, Férey G, Morris RE, Serre C (2012) Metal-organic frameworks in biomedicine. Chem Rev 112:1232–1268. https://doi.org/10.1021/cr200256v
Hu L, Liao H, Feng L, Wang M, Fu W (2018) Accelerating the peroxidase-like activity of gold nanoclusters at neutral pH for colorimetric detection of heparin and heparinase activity. Anal Chem 90:6247–6252. https://doi.org/10.1021/acs.analchem.8b00885
Ivanova AS, Merkuleva AD, Andreev SV, Sakharov KA (2019) Method for determination of hydrogen peroxide in adulterated milk using high performance liquid chromatography. Food Chem 283:431–436. https://doi.org/10.1016/j.foodchem.2019.01.051
Jiang B, Duan D, Gao L, Zhou M, Fan K, Tang Y, Xi J, Bi Y, Tong Z, Gao GF, Xie N, Tang A, Nie G, Liang M, Yan X (2018) Standardized assays for determining the catalytic activity and kinetics of peroxidase-like nanozymes. Nat Protoc 13:1506–1520. https://doi.org/10.1038/s41596-018-0001-1
Jiang D, Ni D, Rosenkrans ZT, Huang P, Yan X, Cai W (2019a) Nanozyme: new horizons for responsive biomedical applications. Chem Soc Rev 48:3683–3704. https://doi.org/10.1039/C8CS00718G
Jiang Y, Yang Q-M, Xu Q-J, Lu S-Y, Hu L-Y, Xu M-W, Liu Y-S (2019b) Metal organic framework MIL-53(Fe) as an efficient artificial oxidase for colorimetric detection of cellular biothiols. Anal Biochem 577:82–88. https://doi.org/10.1016/j.ab.2019.04.020
Kwon YS, Gromov AA, Strokova JI (2007) Passivation of the surface of aluminum nanopowders by protective coatings of the different chemical origin. Appl Surf Sci 253:5558–5564. https://doi.org/10.1016/j.apsusc.2006.12.124
Li T, Hu P, Li J, Huang P, Tong W, Gao C (2019) Enhanced peroxidase-like activity of Fe@PCN-224 nanoparticles and their applications for detection of H2O2 and glucose. Colloids Surfaces Physicochem Eng Asp 577:456–463. https://doi.org/10.1016/j.colsurfa.2019.06.012
Liang R, Jing F, Shen L, Qin N, Wu L (2015) MIL-53(Fe) as a highly efficient bifunctional photocatalyst for the simultaneous reduction of Cr(VI) and oxidation of dyes. J Hazard Mater 287:364–372. https://doi.org/10.1016/j.jhazmat.2015.01.048
Liang M, Yan X (2019) Nanozymes: from new concepts, mechanisms, and standards to applications. Acc Chem Res 52:2190–2200. https://doi.org/10.1021/acs.accounts.9b00140
Liu F, He J, Zeng M, Hao J, Guo Q, Song Y, Wang L (2016) Cu–hemin metal-organic frameworks with peroxidase-like activity as peroxidase mimics for colorimetric sensing of glucose. J Nanoparticle Res. https://doi.org/10.1007/s11051-016-3416-z
Liu YL, Zhao XJ, Yang XX, Li YF (2013) A nanosized metal-organic framework of Fe-MIL-88NH 2 as a novel peroxidase mimic used for colorimetric detection of glucose. Analyst 138:4526–4531. https://doi.org/10.1039/c3an00560g
Magri G (2014) Hydrogen peroxide solid-state sensors review. Phonology 31:525–556. https://doi.org/10.1017/S0952675714000244
Miao Z, Zhang D, Chen Q (2014) Non-enzymatic hydrogen peroxide sensors based on multi-wall carbon nanotube/Pt nanoparticle nanohybrids. Materials (basel) 7:2945–2955. https://doi.org/10.3390/ma7042945
Nguyen MTH, Nguyen QT (2014) Efficient refinement of a metal-organic framework MIL-53(Fe) by UV-vis irradiation in aqueous hydrogen peroxide solution. J Photochem Photobiol A Chem 288:55–59. https://doi.org/10.1016/j.jphotochem.2014.05.006
PF Fox 2003 The major constituents of milk, in: dairy process, Elsevier, pp 5–41. https://doi.org/10.1533/9781855737075.1.5
Ping J, Mao X, Fan K, Li D, Ru S, Wu J, Ying Y (2010) A Prussian blue-based amperometric sensor for the determination of hydrogen peroxide residues in milk. Ionics (kiel) 16:523–527. https://doi.org/10.1007/s11581-010-0418-1
Silva RAB, Montes RHO, Richter EM, Munoz RAA (2012) Rapid and selective determination of hydrogen peroxide residues in milk by batch injection analysis with amperometric detection. Food Chem 133:200–204. https://doi.org/10.1016/j.foodchem.2012.01.003
Singh P, Gandhi N (2015) Milk preservatives and adulterants: processing, regulatory and safety issues. Food Rev Int 31:236–261. https://doi.org/10.1080/87559129.2014.994818
Slavin YN, Asnis J, Häfeli UO, Bach H (2017) Metal nanoparticles: understanding the mechanisms behind antibacterial activity. J Nanobiotechnology. https://doi.org/10.1186/s12951-017-0308-z
Stewart S, Wei Q, Sun Y (2021) Surface chemistry of quantum-sized metal nanoparticles under light illumination. Chem Sci 12:1227–1239. https://doi.org/10.1039/d0sc04651e
Wang S, Xu D, Ma L, Qiu J, Wang X, Dong Q, Zhang Q, Pan J, Liu Q (2018) Ultrathin ZIF-67 nanosheets as a colorimetric biosensing platform for peroxidase-like catalysis. Anal Bioanal Chem 410:7145–7152. https://doi.org/10.1007/s00216-018-1317-y
Wang MQ, Zhang Y, Bao SJ, Yu YN, Ye C (2016b) Ni(II)-based metal-organic framework anchored on carbon nanotubes for highly sensitive non-enzymatic hydrogen peroxide sensing. Electrochim Acta 190:365–370. https://doi.org/10.1016/j.electacta.2015.12.199
X Wang, W Guo, Y Hu, J Wu, H Wei 2016a Nanozymes: next wave of artificial enzymes, Springer Heidelberg, https://doi.org/10.1007/978-3-662-53068-9
Xiao JD, Han L, Luo J, Yu SH, Jiang HL (2018) Integration of plasmonic effects and Schottky junctions into metal-organic framework composites: steering charge flow for enhanced visible-light photocatalysis. Angew Chemie Int Ed 57:1103–1107. https://doi.org/10.1002/anie.201711725
Yang Q, Xu Q, Jiang HL (2017) Metal-organic frameworks meet metal nanoparticles: synergistic effect for enhanced catalysis. Chem Soc Rev 46:4774–4808. https://doi.org/10.1039/c6cs00724d
Zhang C, Li H, Li C, Li Z (2019a) Fe-loaded MOF-545(Fe): peroxidase-like activity for dye degradation dyes and high adsorption for the removal of dyes from wastewater. Molecules 25:168. https://doi.org/10.3390/molecules25010168
Zhang Y, Song J, Pan Q, Zhang X, Shao W, Zhang X, Quan C, Zhang Y, Song J, Pan Q, Zhang X, Shao W, Zhang X, Quan C, Li J (2019b) An Au@NH2-MIL-125(Ti)-based multifunctional platform for colorimetric detections of biomolecules and Hg2+. J Mater Chem B 8:114–124. https://doi.org/10.1039/c9tb02183c
Zhang J-W, Zhang H-T, Du Z-Y, Wang X, Yu S-H, Jiang H-L (2014) Water-stable metal–organic frameworks with intrinsic peroxidase-like catalytic activity as a colorimetric biosensing platform. Chem Commun 50:1092–1094. https://doi.org/10.1039/C3CC48398C
Zheng HQ, Zeng YN, Chen J, Lin RG, Zhuang WE, Cao R, Lin ZJ (2019) Zr-based metal-organic frameworks with intrinsic peroxidase-like activity for ultradeep oxidative desulfurization: mechanism of H2O2 decomposition. Inorg Chem 58:6983–6992. https://doi.org/10.1021/acs.inorgchem.9b00604
Zhu L, Liu XQ, Jiang HL, Sun LB (2017) Metal-organic frameworks for heterogeneous basic catalysis. Chem Rev 117:8129–8176. https://doi.org/10.1021/acs.chemrev.7b00091
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We gratefully acknowledge the financial support provided by the Science and Engineering Research Board (Department of Science and Technology, Govt. of India) in developing our research facilities.
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George, P., Chowdhury, P. Au, Ag nanoparticles-doped MIL-53(Fe) in rapid and selective detection of hydrogen peroxide in milk samples. Chem. Pap. 77, 1361–1375 (2023). https://doi.org/10.1007/s11696-022-02558-6
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DOI: https://doi.org/10.1007/s11696-022-02558-6