Abstract
A Cu2+-modified carboxylated hollow carbon nanospheres (Cu2+-HCNSs-COOH) was designed with enhanced peroxidase-like activity for the detection of hydrogen peroxide (H2O2) and degradation of methylene blue (MB). Hollow polymer nanospheres were fabricated from aniline, pyrrole, Triton-100, and ammonium persulfate via confined interfacial copolymerization reaction, which can be pyrolyzed to create HCNSs with the hollow gap diameter of about 20 nm under high temperature. Combining the synergistic effect of coordination and electrostatic interaction, Cu2+-HCNSs-COOH was constructed by anchoring Cu2+ on the surface of HCNSs-COOH. Furthermore, Cu2+-HCNSs-COOH has higher affinity for 3,3′,5,5′-tetramethylbenzidine and H2O2 of 0.20 mM and 0.88 mM, respectively. Based on the rapid response of Cu2+-HCNSs-COOH to H2O2, we constructed a colorimetric sensing platform by detecting the absorbance of the 3,3′,5,5′-tetramethylbenzidine-H2O2 system at 652 nm for quantifying H2O2, which holds good linear relationship between 1 and 150 μM and has a detection limit of 0.61 μM. We also investigated the degradation of MB in the presence of Cu2+-HCNSs-COOH and H2O2, which can degrade 80.7% pollutants within 30 min. This research developed an unusual nanozyme for bioassays and water pollution treatment, which broadened the way for the rapid development of clinical diagnostics and water pollution treatment.
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References
Wei H, Wang E (2013) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. Chem Soc Rev 42:6060–6093
Wu J, Wang X, Wang Q, Lou Z, Li S, Zhu Y, Qin L, Wei H (2019) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II). Chem Soc Rev 48:1004–1076
Wang X, Hua Y, Wei H (2016) Nanozymes in bionanotechnology: from sensing to therapeutics and beyond. Inorg Chem Front 3:41–60
Huang Y, Ren J, Qu X (2019) Nanozymes: classification, catalytic mechanisms, activity regulation, and applications. Chem Rev 119:4357–4412
Wang H, Wan K, Shi X (2018) Recent advances in nanozyme research. Adv Mater 1805368
Zhou Y, Liu B, Yang R, Liu J (2017) Filling in the gaps between nanozymes and enzymes: challenges and opportunities. Bioconjug Chem 28:2903–2909
Wen W, Yan X, Zhu C, Du D, Lin Y (2017) Recent advances in electrochemical immunosensors. Anal Chem 89:138–156
Wang Q, Wei H, Zhang Z, Wang E, Dong S (2018) Nanozyme: an emerging alternative to natural enzyme for biosensing and immunoassay. Trends Anal Chem 105:218–224
Chikkaveeraiah B, Bhirde A, Morgan N, Eden H, Chen X (2012) Electrochemical immunosensors for detection of cancer protein biomarkers. ACS Nano 6:6546–6561
Rica R, Stevens M (2012) Plasmonic ELISA for the ultrasensitive detection of disease biomarkers with the naked eye. Nat Nanotechnol 7:821–824
Zhang H, Liang X, Han L, Li F (2018) “Non-naked” gold with glucose oxidase-like activity: a nanozyme for tandem catalysis. Small 14(44):1803256
Zhao Y, Yang M, Fu Q, Ouyang H, Wen W, Song Y, Zhu C, Lin Y, Du D (2018) A Nanozyme- and ambient light-based smartphone platform for simultaneous detection of dual biomarkers from exposure to organophosphorus pesticides. Anal Chem 90:7391–7398
Zeng R, Luo Z, Zhang L, Tang D (2018) Platinum Nanozyme-catalyzed gas generation for pressure-based bioassay using polyaniline nanowires-functionalized graphene oxide framework. Anal Chem 90:12299–12306
Chauhan S, Hosseinzadeh P, Lu Y, Blackburn N (2016) Stopped-flow studies of the reduction of the copper centers suggest a bifurcated Electron transfer pathway in peptidylglycine monooxygenase. Biochemistry 55:2008–2021
Bhagi-Damodaran A, Michael M, Zhu Q, Reed J, Sandovall B, Mirts E, Chakraborty S, Moënne-Loccoz P, Zhang Y, Lu Y (2017) Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases. Nat Chem 9:257–263
Clark K, Tian S, Donk W, Lu Y (2017) Probing the role of the backbone carbonyl interaction with the CuA center in azurin by replacing the peptide bond with an ester linkage. Chem Commun 53:224–227
Yang N, Waldvogel S, Jiang X (2016) Electrochemistry of carbon dioxide on carbon electrodes. ACS Appl Mater Interfaces 8:28357–28371
Du Y, Guo S (2016) Chemically doped fluorescent carbon and graphene quantum dots for bioimaging, sensor, catalytic and photoelectronic applications. Nanoscale 8:2532–2543
Sun H, Zhou Y, Ren J, Qu X (2018) Carbon Nanozymes: enzymatic properties, catalytic mechanism, and applications. Angew Chem Int Ed 57:9224–9237
Garg B, Bisht T (2016) Carbon Nanodots as peroxidase nanozymes for biosensing. Molecules 21:1653
Ren H, Zhang Y, Liu L, Li Y, Wang D, Zhang R, Zhang W, Li Y, Ye B (2019) Synthesis of hollow Mo2C/carbon spheres, and their application to simultaneous electrochemical detection of hydroquinone, catechol, and resorcinol. Microchim Acta 186:306
Zhao Y, **e H, Zhao M, Li H, Chen X, Cai Z, Song H (2019) Core-shell hollow spheres of type C@MoS2 for use in surface-assisted laser desorption/ionization time of flight mass spectrometry of small molecules. Microchim Acta 186:830
Zhang L, Yang X, Li Y, Zheng W, Jiang X (2017) Hollow carbon nanospheres as a versatile platform for co-delivery of siRNA and chemotherapeutics. Carbon 121:79–89
Yang X, Li Y, Zhang P, Sun L, Ren X, Mi H (2020) Hierarchical hollow carbon spheres: novel synthesis strategy, pore structure engineering and application for micro-supercapacitor. Carbon 157:70–79
Fan K, ** J, Fan L, Wang P, Zhu C, Tang Y, Xu X, Liang M, Jiang B, Yan X, Gao L (2018) In vivo guiding nitrogen-doped carbon nanozyme for tumor catalytic therapy. Nat Commun 9:1440
Sang Y, Huang Y, Li W, Ren J, Qu X (2018) Bioinspired design of Fe3+-doped mesoporous carbon nanospheres for enhanced nanozyme activity. Chem Eur J 24:7259–7263
Zhu J, Nie W, Wang Q, Li J, Li H, Wen W, Bao T, **ong H, Zhang X, Wang S (2018) In situ growth of copper oxide-graphite carbon nitride nanocomposites with peroxidase-mimicking activity for electrocatalytic and colorimetric detection of hydrogen peroxide. Carbon 129:29–37
Zhu J, Peng X, Nie W, Wang Y, Gao J, Wen W, Selvaraj J, Zhang X, Wang S (2019) Hollow copper sulfide nanocubes as multifunctional nanozymes for colorimetric detection of dopamine and electrochemical detection of glucose. Biosens Bioelectron 141:111450
Xu F, Tang Z, Huang S, Chen L, Liang Y, Mai W, Zhong H, Fu R, Wu D (2015) Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage. Nat Commun 6:7221
Zhou C, Han J, Song G, Guo R (2008) Fabrication of poly(aniline-co-pyrrole) hollow nanospheres with triton X-100 micelles as templates. J Polym Sci Pol Chem 46:3563–3572
Stejskal J, Sapurina I (2004) On the origin of colloidal particles in the dispersion polymerization of aniline. J Colloid Interface Sci 274:489–495
Stejskal J, Spirkova M, Riede A, Helmstedt M, Mokreva P, Prokes J (1999) Polyaniline dispersions 8. The control of particle morphology. Polymer 40:2487–2492
Zeng S, Yao Y, Huang L, Wu H, Peng B, Zhang Q, Li X, Yu L, Liu S, Tu W, Lan T, Zeng X, Zou J (2018) Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres and their application in lithium-sulfur batteries. Chem Eur J 24:1988–1997
Wang S, Cazelles R, Liao W, Vázquez-González M, Zoabi A, Abu-Reziq R, Willner I (2017) Mimicking horseradish peroxidase and NADH peroxidase by heterogeneous Cu2+-modified graphene oxide nanoparticles. Nano Lett 17:2043–2048
Vázquez-González M, Liao W, Cazelles R, Wang S, Yu X, Gutkin V, Willner I (2017) Mimicking horseradish peroxidase functions using Cu2+-modified carbon nitride nanoparticles or Cu2+-modified carbon dots as heterogeneous catalysts. ACS Nano 11:3247–3253
Chen W, Vázquez-González M, Kozell A, Cecconello A, Willner I (2018) Cu2+-modified metal-organic framework nanoparticles: a peroxidase-mimicking nanoenzyme. Small 14:1703149
**ong Y, Qin Y, Su L, Ye F (2017) Bioinspired synthesis of Cu2+-modified covalent triazine framework: a new highly efficient and promising peroxidase mimic. Chem Eur J 23:11037–11045
Ju E, Dong K, Chen Z, Liu Z, Liu C, Huang Y, Wang Z, Pu F, Ren J, Qu X (2016) Copper(II)–graphitic carbon nitride triggered synergy: improved ROS generation and reduced glutathione levels for enhanced photodynamic therapy. Angew Chem Int Ed 55:11467–11471
Funding
This work was partly financially supported by the National Natural Science Foundation of China (Nos. 21775033, 22076041) and the Open Project Funding of the State Key Laboratory of Biocatalysis and Enzyme Engineering (SKLBEE2019016).
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Zhu, J., Luo, G., **, X. et al. Cu2+-modified hollow carbon nanospheres: an unusual nanozyme with enhanced peroxidase-like activity. Microchim Acta 188, 8 (2021). https://doi.org/10.1007/s00604-020-04690-0
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DOI: https://doi.org/10.1007/s00604-020-04690-0