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Intrinsic peroxidase-like activity of Cu2ZnSn(SxSe1-x)4 nanocrystals, and their application to the colorimetric detection of H2O2

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Abstract

Nanocrystals (NCs) of type Cu2ZnSn(SxSe1-x)4 (CZTSSe) were prepared via a solvothermal approach. They are shown to be highly efficient peroxidase (POx) mimics for colorimetric detection of H2O2. By varying the molar ratio of S and Se during preparation, the NCs showed different crystal structures, morphologies, surface properties, and POx-like activities. Among them, the type CZTSSe-0.25 NCs exhibit the strongest POx-like activities towards the catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine in the presence of H2O2 to generate a blue product. The enhanced activity is attributed to its more negative potential and larger specific surface of the NCs. Based on these findings, a rapid and ultrasensitive method was developed for the visual and colorimetric determination of H2O2. The method is selective, and the NCs are reusable and long-term stable. The detection limit of H2O2 is 50 nM. Kinetic and active species trapping experiments were performed to elucidate the POx-like mechanism of the NCs.

Schematic presentation of the process of Cu2ZnSn(SxSe1-x)4 nanocrystals catalyzing the oxidation of peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H2O2 to induce a typical blue color reaction, which can be applied in colorimetric detection of H2O2.

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References

  1. Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang T, Feng J, Yang D, Perrett S, Yan X (2007) Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat Nanotechnol 2:577–583. https://doi.org/10.1038/nnano.2007.260

    Article  CAS  PubMed  Google Scholar 

  2. André R, Natálio F, Humanes M, Leppin J, Heinze K, Wever R, Schröder HC, Müller WEG, Tremel W (2011) V2O5 nanowires with an intrinsic peroxidase-like activity. Adv Funct Mater 21:501–509. https://doi.org/10.1002/adfm.201001302

    Article  CAS  Google Scholar 

  3. Yang Z, Ji H (2013) 2-Hydroxypropyl-β-cyclodextrin polymer as a mimetic enzyme for mediated synthesis of benzaldehyde in water. ACS Sustain Chem Eng 1:1172–1179. https://doi.org/10.1021/sc4001059

    Article  CAS  Google Scholar 

  4. Tan B, Zhao HM, Wu WH, Liu X, Zhang YB, Quan X (2017) Fe3O4-AuNPs anchored 2D metal-organic framework nanosheets with DNA regulated switchable peroxidase-like activity. Nanoscale 9:18699–18710. https://doi.org/10.1039/C7NR05541B

    Article  CAS  PubMed  Google Scholar 

  5. Čunderlová V, Hlaváček A, Horňáková V, Peterek M, Němeček D, Hampl A, Eyer L, Skládal P (2016) Catalytic nanocrystalline coordination polymers as an efficient peroxidase mimic for labeling and optical immunoassays. Microchim Acta 183:651–658. https://doi.org/10.1007/s00604-015-1697-z

    Article  CAS  Google Scholar 

  6. Nasir M, Nawaz MH, Yaqub M, Hayat A, Rahim A (2017) An overview on enzyme-mimicking nanomaterials for use in electrochemical and optical assays. Microchim Acta 184:323–342. https://doi.org/10.1007/s00604-016-2036-8

  7. Song YJ, Wei WL, Qu XG (2011) Colorimetric biosensing using smart materials. Adv Mater 23:4215–4236. https://doi.org/10.1002/adma.201101853

    Article  CAS  PubMed  Google Scholar 

  8. Wei H, Wang EK (2013) Nanomaterials with enzyme-like characteristics (nanozymes): next generation artificial enzymes. Chem Soc Rev 42:6060–6093. https://doi.org/10.1039/c3cs35486E

    Article  CAS  Google Scholar 

  9. Wang QQ, Wei H, Zhang ZQ, Wang EK, Dong SJ (2018) Nanozyme: an emerging alternative to natural enzyme for biosensing and immunoassay. TrAC Trends Anal Chem 105:218–224. https://doi.org/10.1016/j.trac.2018.05.012

    Article  CAS  Google Scholar 

  10. Ding CP, Yan YH, Xiang DS, Zhang CL, Xian YZ (2016) Magnetic Fe3S4 nanoparticles with peroxidase-like activity, and their use in a photometric enzymatic glucose assay. Microchim Acta 183:625–631. https://doi.org/10.1007/s00604-015-1690-6

    Article  CAS  Google Scholar 

  11. Yu YZ, Ju P, Zhang D, Han XX, Yin XF, Zheng L, Sun CJ (2016) Peroxidase-like activity of FeVO4 nanobelts and its analytical application for optical detection of hydrogen peroxide. Sensors Actuators B Chem 233:162–172. https://doi.org/10.1016/j.snb.2016.04.041

    Article  CAS  Google Scholar 

  12. Chang Q, Tang HQ (2014) Optical determination of glucose and hydrogen peroxide using a nanocomposite prepared from glucose oxidase and magnetite nanoparticles immobilized on graphene oxide. Microchim Acta 181:527–534. https://doi.org/10.1007/s00604-013-1145-x

    Article  CAS  Google Scholar 

  13. Lin TR, Zhong LS, Wang J, Guo LQ, Wu HY, Guo QQ, Fu FF, Chen GN (2014) Graphite-like carbon nitrides as peroxidase mimetics and their applications to glucose detection. Biosens Bioelectron 59:89–93. https://doi.org/10.1016/j.bios.2014.03.023

    Article  CAS  PubMed  Google Scholar 

  14. Guo SJ, Wang EK (2011) Noble metal nanomaterials: controllable synthesis and application in fuel cells and analytical sensors. Nano Today 6:240–264. https://doi.org/10.1016/j.nantod.2011.04.007

    Article  CAS  Google Scholar 

  15. Wang Y, Zhang D, Wang J (2018) Metastable α-AgVO3 microrods as peroxidase mimetics for colorimetric determination of H2O2. Microchim Acta 185(1). https://doi.org/10.1007/s00604-017-2562-z

  16. Qiao FM, Wang Z, Xu K, Ai SY (2015) Double enzymatic cascade reactions within FeSe-Pt@SiO2 nanospheres: synthesis and application toward colorimetric biosensing of H2O2 and glucose. Analyst 140:6684–6691. https://doi.org/10.1039/C5AN01268F

    Article  CAS  PubMed  Google Scholar 

  17. Wang N, Sun JC, Chen LJ, Fan H, Ai SY (2015) A Cu2(OH)3Cl-CeO2 nanocomposite with peroxidase-like activity, and its application to the determination of hydrogen peroxide, glucose and cholesterol. Microchim Acta 182:1733–1738. https://doi.org/10.1007/s00604-015-1506-8

    Article  CAS  Google Scholar 

  18. Qiao FM, Chen LJ, Li X, Li L, Ai SY (2014) Peroxidase-like activity of manganese selenide nanoparticles and its analytical application for visual detection of hydrogen peroxide and glucose. Sensors Actuators B Chem 193:255–262. https://doi.org/10.1016/j.snb.2013.11.108

    Article  CAS  Google Scholar 

  19. Chen Q, Chen J, Gao CJ, Zhang ML, Chen JY, Qiu HD (2015) Hemin-functionalized WS2 nanosheets as highly active peroxidase mimetics for label-free colorimetric detection of H2O2 and glucose. Analyst 140:2857–2863. https://doi.org/10.1039/c5an00031A

    Article  CAS  PubMed  Google Scholar 

  20. Lin Y, Ren J, Qu X (2014) Catalytically active nanomaterials: a promising candidate for artificial enzymes. Acc Chem Res 47:1097–1105. https://doi.org/10.1021/ar400250z

    Article  CAS  PubMed  Google Scholar 

  21. Wang B, Ju P, Zhang D, Han XX, Zheng L, Yin XF, Sun CJ (2016) Colorimetric detection of H2O2 using flower-like Fe2(MoO4)3 microparticles as a peroxidase mimic. Microchim Acta 183:3025–3033. https://doi.org/10.1007/s00604-016-1955-8

    Article  CAS  Google Scholar 

  22. Kim J, Hiroi H, Todorov TK, Gunawan O, Kuwahara M, Gokmen T, Nair D, Hopstaken M, Shin B, Lee YS, Wang W, Sugimoto H, Mitzi DB (2014) High efficiency Cu2ZnSn(S, Se)4 solar cells by applying a double In2S3/CdS emitter. Adv Mater 26:7427–7431. https://doi.org/10.1002/adma.201402373

    Article  CAS  PubMed  Google Scholar 

  23. Todorov TK, Tang J, Bag S, Gunawan O, Gokmen T, Zhu Y, Mitzi DB (2013) Beyond 11% efficiency: characteristics of state-of-the-art Cu2ZnSn(S,se)4 solar cells. Adv Energy Mater 3:34–38. https://doi.org/10.1002/aenm.201200348

    Article  CAS  Google Scholar 

  24. Li W, Han XX, Zhao Y, Gu YE, Yang SR, Tanaka T (2015) Mild solvothermal synthesis of Cu2ZnSn(SxSe1-x)4 nanocrystals with tunable phase structure and composition. J Power Sources 294:603–608. https://doi.org/10.1016/j.jpowsour.2015.06.103

    Article  CAS  Google Scholar 

  25. Wei H, Wang EK (2008) Fe3O4 magnetic nanoparticles as peroxidase mimetics and their applications in H2O2 and glucose detection. Anal Chem 80:2250–2254. https://doi.org/10.1021/ac702203f

    Article  CAS  PubMed  Google Scholar 

  26. Ju P, Yu YZ, Wang M, Zhao Y, Zhang D, Sun CJ, Han XX (2016) Synthesis of EDTA-assisted CeVO4 nanorods as robust peroxidase mimics towards colorimetric detection of H2O2. J Mater Chem B 4:316–6325. https://doi.org/10.1039/C6TB01881E

    Article  CAS  Google Scholar 

  27. Sun YX, Zhang YZ, Wang H, Xie M, Zong K, Zheng HJ, Shu YQ, Liu JB, Yan H, Zhu MK, Lau WM (2013) Novel non-hydrazine solution processing of earth-abundant Cu2ZnSn(S,se)4 absorbers for thin-film solar cells. J Mater Chem A 1:6880–6887. https://doi.org/10.1039/C3TA10566K

    Article  CAS  Google Scholar 

  28. Liang QS, Han L, Deng XL, Yao CG, Meng JL, Liu XJ, Meng J (2014) Compositionally tunable Cu2Sn(SxSe1-x)3 nanocrystals: facile direct solution-phase synthesis, characterization, and scalable procedure. CrystEngComm 16:4001–4007. https://doi.org/10.1039/C3CE42312C

    Article  CAS  Google Scholar 

  29. Ju P, Xiang YH, Xiang ZB, Wang M, Zhao Y, Zhang D, Yu JQ, Han XX (2016) BiOI hierarchical nanoflowers as novel robust peroxidase mimetics for colorimetric detection of H2O2. RSC Adv 6:17483–17493. https://doi.org/10.1039/C6RA00368K

    Article  CAS  Google Scholar 

  30. Chen LJ, Sun B, Wang X, Qiao FM, Ai SY (2013) 2D ultrathin nanosheets of Co-Al layered double hydroxides prepared in L-asparagine solution enhanced peroxidase-like activity and colorimetric detection of glucose. J Mater Chem B 1:2268–2274. https://doi.org/10.1039/C3TB00044C

    Article  CAS  Google Scholar 

  31. Qiao FM, Qi QQ, Wang ZZ, Xu K, Ai SY (2016) MnSe-loaded g-C3N4 nanocomposite with synergistic peroxidase-like catalysis: synthesis and application toward colorimetric biosensing of H2O2 and glucose. Sensors Actuators B Chem 229:379–386. https://doi.org/10.1016/j.snb.2015.12.109

    Article  CAS  Google Scholar 

  32. Wang N, Duan JZ, Shi WJ, Zhai XF, Guan F, Yang LH, Hou BR (2018) A 3-dimensional C/CeO2 hollow nanostructure framework as a peroxidase mimetic, and its application to the colorimetric determination of hydrogen peroxide. Microchim Acta 185:417. https://doi.org/10.1007/s00604-018-2957-5

    Article  CAS  Google Scholar 

  33. Shang J, Gao XH (2014) Nanoparticle counting: towards accurate determination of the molar concentration. Chem Soc Rev 43:7267–7278. https://doi.org/10.1039/C4CS00128A

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  34. Porter DJ, Bright HJ (1983) The mechanism of oxidation of nitroalkanes by horseradish peroxidase. J Biol Chem 258:9913–9924

    CAS  PubMed  Google Scholar 

  35. Bai J, Wu L, Wang X, Zhang HM (2015) Hemoglobin-graphene modified carbon fiber microelectrode for direct electrochemistry and electrochemical H2O2 sensing. Electrochim Acta 185:142–147. https://doi.org/10.1016/j.electacta.2015.10.100

    Article  CAS  Google Scholar 

  36. Gong T, Liu J, Wu Y, Xiao Y, Wang X, Yuan S (2017) Fluorescence enhancement of CdTe quantum dots by HBcAb-HRP for sensitive detection of H2O2 in human serum. Biosens Bioelectron 92:16–20. https://doi.org/10.1016/j.bios.2017.01.048

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

This work was supported by National Natural Science Foundation of China (51702328), Key Lab of Marine Bioactive Substance and Modern Analytical Technique, SOA (MBSMAT-2016-05), Natural Science Foundation of Shandong Province, China (ZR2017BD002), China Postdoctoral Science Foundation Funded Project (2017 M622179 and 2018 T110681), CAS “Light of West China” Program, Open Fund of Laboratory for Marine Ecology and Environmental Science, Pilot National Laboratory for Marine Science and Technology (Qingdao) (LMEES201802), National Natural Science Foundation of China (41776177), Open Foundation of Pilot National Laboratory for Marine Science and Technology (Qingdao) (QNLM2016ORP0410), and The Aoshan Scientific and Technological Innovation Project Financially Supported by Pilot National Laboratory for Marine Science and Technology (Qingdao) (2016ASKJ14). C.J. Sun would also like to thank support from Taishan Scholar and the Ministry of Human Resources and Social Security of China.

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Authors and Affiliations

  1. Institute of Marine Science and Technology, Shandong University, 72 Binhai Road, Qingdao, 266237, People’s Republic of China

    Peng Ju & Chi Wu

  2. Key Laboratory of Marine Bioactive Substances and Analytical Technology, Marine Ecology Center, The First Institute of Oceanography, State Oceanic Administration (SOA), 6 Xianxialing Road, Qingdao, 266061, People’s Republic of China

    Peng Ju, Jinfeng Ding, Bing Wang, Fenghua Jiang & Chengjun Sun

  3. Key Laboratory of Advanced Technologies of Materials, Ministry of Education, School of Materials Science and Engineering, Southwest Jiaotong University, 111 the Northbound 1 of the Second Ring Road, Chengdu, 610031, China

    Wen Li

  4. Institute of Semiconductor Materials, Jiangxi University of Science and Technology, 86 Hongqi Road, Ganzhou, 341000, People’s Republic of China

    Xiuxun Han

  5. Laboratory of Marine Drugs and Bioproducts, Pilot National Laboratory for Marine Science and Technology (Qingdao), 1 Wenhai Road, Qingdao, 266237, People’s Republic of China

    Chengjun Sun

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Ju, P., Ding, J., Wang, B. et al. Intrinsic peroxidase-like activity of Cu2ZnSn(SxSe1-x)4 nanocrystals, and their application to the colorimetric detection of H2O2. Microchim Acta 186, 118 (2019). https://doi.org/10.1007/s00604-018-3185-8

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