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Hydrothermal synthesis of nitrogen and copper co-doped carbon dots with intrinsic peroxidase-like activity for colorimetric discrimination of phenylenediamine isomers

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Carbon dots doped with nitrogen and copper have been synthesized via a hydrothermal method. They possess favorable peroxidase-like catalytic activity over a wide range of pH values and temperatures. Specifically, they were used to catalyze the oxidation of ortho- and para-phenylenediamine (OPD and PPD) by H2O2. The resulting products possess different colors (yellow for OPD and brown for PPD), which can be visually discriminated. The corresponding typical absorption peaks of oxidized products for OPD and PPD are at 413 nm and 500 nm, respectively. The method displays excellent discrimination ability and selectivity over potential interferents. The detection limits are 1.1 μM for OPD and 1.9 μM for PPD. The respective linear ranges are from 5 to 200 μM for OPD and from 2.5 to 700 μM for PPD. The method was applied to the quantification of OPD and PPD in spiked natural waters.

Schematic presentation of the synthesis of nitrogen and copper co-doped carbon dots (N,Cu-CDs) and their application as an enzyme mimic for colorimetric discrimination of ortho-, meta- and para-phenylenediamine (OPD, MPD and PPD).

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  1. Yan ZY, Yu Y, Chen JQ (2015) Glycine-functionalized carbon quantum dots as chemiluminescence sensitization for detection of m-phenylenediamine. Anal Methods 7(3):1133–1139

    Article  CAS  Google Scholar 

  2. Li N, Gu Y, Gao MM, Wang ZL, Xiao DL, Li Y, Lin R, He H (2015) Colorimetric determination of o-phenylenediamine in water samples based on the formation of silver nanoparticles as a colorimetric probe. Spectrochim Acta A 140:328–333

    Article  CAS  Google Scholar 

  3. Ngamdee K, Martwiset S, Tuntulani T, Ngeontae W (2012) Selective fluorescence sensors for p-phenylenediamine using formyl boronate ester with an assistance of micelles. Sensors Actuators B Chem 173:682–691

    Article  CAS  Google Scholar 

  4. Nezamzadeh-Ejhieh A, Salimi Z (2010) Heterogeneous photodegradation catalysis of o-phenylenediamine using CuO/X zeolite. Appl Catal A Gen 390(1–2):110–118

    Article  CAS  Google Scholar 

  5. Lee SJ, Nam YS, Nah IW, Lee YH, Lee KB (2017) Colorimetric determination of p-phenylenediamine using silver nanoparticles modified with poly (ethylene glycol) methyl ether thiol. J Nanosci Nanotechnol 17(5):3261–3267

    Article  CAS  Google Scholar 

  6. Ma PY, Liang FH, Wang D, Yang QQ, Cao BC, Song DQ, Gao DJ, Wang XH (2014) Selective determination of o-phenylenediamine by surface-enhanced Raman spectroscopy using silver nanoparticles decorated with α-cyclodextrin. Microchim Acta 182(1–2):167–174

    Google Scholar 

  7. Dong SQ, Chi LZ, Zhang S, He PG, Wang QJ, Fang YZ (2008) Simultaneous determination of phenylenediamine isomers and dihydroxybenzene isomers in hair dyes by capillary zone electrophoresis coupled with amperometric detection. Anal Bioanal Chem 391(2):653–659

    Article  CAS  Google Scholar 

  8. Hudari FF, Almeida LC, Silva BF, Zanoni MVB (2014) Voltammetric sensor for simultaneous determination of p-phenylenediamine and resorcinol in permanent hair dyeing and tap water by composite carbon nanotubes/chitosan modified electrode. Microchem J 116:261–268

    Article  CAS  Google Scholar 

  9. Guo DD, Lou CY, Wang NN, Chen ML, Zhang PM, Wu SC, Zhu Y (2017) Poly (styrene-divinyl benzene-glycidylmethacrylate) stationary phase grafted with poly amidoamine (PAMAM) dendrimers for rapid determination of phenylene diamine isomers in HPLC. Talanta 168:188–195

    Article  CAS  Google Scholar 

  10. Shi BF, Su YB, Zhang LL, Huang MJ, Li XF, Zhao SL (2016) Facilely prepared Fe3O4/nitrogen-doped graphene quantum dot hybrids as a robust nonenzymatic catalyst for visual discrimination of phenylenediamine isomers. Nanoscale 8(20):10814–10822

    Article  CAS  Google Scholar 

  11. Maria-Hormigos R, Jurado-Sanchez B, Escarpa A (2018) Self-propelled micromotors for naked-eye detection of phenylenediamines isomers. Anal Chem 90(16):9830–9837

    Article  CAS  Google Scholar 

  12. Sun HJ, Zhou Y, Ren JS, Qu XG (2018) Carbon nanozymes: enzymatic properties, catalytic mechanism, and applications. Angew Chem Int Ed 57(30):9224–9237

    Article  CAS  Google Scholar 

  13. Xie JX, Zhang XD, Wang H, Zheng HZ, Huang YM, Xie JX (2012) Analytical and environmental applications of nanoparticles as enzyme mimetics. TrAC Trend Anal Chem 39:114–129

    Article  CAS  Google Scholar 

  14. 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(2):323–342

    Article  CAS  Google Scholar 

  15. Lin LP, Song XH, Chen YY, Rong MC, Zhao TT, Wang YR, Chen X (2015) Intrinsic peroxidase-like catalytic activity of nitrogen-doped graphene quantum dots and their application in the colorimetric detection of H2O2 and glucose. Anal Chim Acta 869:89–95

    Article  CAS  Google Scholar 

  16. Liao H, Liu GJ, Liu Y, Li R, Fu WS, Hu LZ (2017) Aggregation-induced accelerating peroxidase-like activity of gold nanoclusters and their applications for colorimetric Pb2+ detection. Chem Commun 53:10160–10163

    Article  CAS  Google Scholar 

  17. Liao H, Hu LZ, Zhang YZ, Yu XR, Liu YL, Li R (2018) A highly selective colorimetric sulfide assay based on the inhibition of the peroxidase-like activity of copper nanoclusters. Microchim Acta 185:143

    Article  Google Scholar 

  18. Hu LZ, Liao H, Feng LY, Wang M, Fu WS (2018) Accelerating the peroxidase-like activity of gold nanoclusters at neutral pH for colorimetric detection of heparin and heparinase activity. Anal Chem 90(10):6247–6252

    Article  CAS  Google Scholar 

  19. Liu HM, Wang BC, Li DH, Zeng XY, Tang X, Gao QS, Cai JY, Cai HH (2018) MoS2 nanosheets with peroxidase mimicking activity as viable dual-mode optical probes for determination and imaging of intracellular hydrogen peroxide. Microchim Acta 185(6):287

    Article  Google Scholar 

  20. Tran HV, Nguyen TV, Nguyen ND, Piro B, Huynh CD (2018) A nanocomposite prepared from FeOOH and N-doped carbon nanosheets as a peroxidase mimic, and its application to enzymatic sensing of glucose in human urine. Microchim Acta 185:270

    Article  Google Scholar 

  21. Tang S, Wang M, Li G, Li X, Chen W, Zhang L (2018) Ultrasensitive colorimetric determination of silver(I) based on the peroxidase mimicking activity of a hybrid material composed of graphitic carbon nitride and platinum nanoparticles. Microchim Acta 185(5):273

    Article  Google Scholar 

  22. Lin LP, Luo YX, Tsai PY, Chen X (2018) Metal ions doped carbon quantum dots: synthesis, physicochemical properties, and their applications. TrAC Trend Anal Chem 103:87–101

    Article  CAS  Google Scholar 

  23. Huang HW, Liu LF, Zhang LY, Zhao Q, Zhou Y, Yuan SS, Tang ZL, Liu XY (2017) Peroxidase-like activity of ethylene diamine tetraacetic acid and its application for ultrasensitive detection of tumor biomarkers and circular tumor cells. Anal Chem 89(1):666–672

    Article  CAS  Google Scholar 

  24. Ren XL, Liu J, Ren J, Tang FQ, Meng XW (2015) One-pot synthesis of active copper-containing carbon dots with laccase-like activities. Nanoscale 7(46):19641–19646

    Article  CAS  Google Scholar 

  25. Durán GM, Benavidez TE, Contento AM, Ríos A, García CD (2017) Analysis of penicillamine using Cu-modified graphene quantum dots synthesized from uric acid as single precursor. J Pharm Anal 7(5):324–331

    Article  Google Scholar 

  26. Xia JB, Yuan SW, Wang Z, Kirklin S, Dorney B, Liu DJ, Yu LP (2010) Nanoporous polyporphyrin as adsorbent for hydrogen storage. Macromolecules 43(7):3325–3330

    Article  CAS  Google Scholar 

  27. Wu WT, Zhan LT, Fan WY, Song JZ, Li XM, Li ZT, Wang RQ, Zhang JQ, Zheng JT, Wu MB, Zeng HB (2015) Cu-N dopants boost electron transfer and photooxidation reactions of carbon dots. Angew Chem Int Ed 54(22):6540–6544

    Article  CAS  Google Scholar 

  28. Ma YS, Cen Y, Sohail M, Xu GH, Wei FD, Shi ML, Xu XM, Song YY, Ma YJ, Hu Q (2017) A ratiometric fluorescence universal platform based on N, Cu codoped carbon dots to detect metabolites participating in H2O2-generation reactions. ACS Appl Mater Interfaces 9(38):33011–33019

    Article  CAS  Google Scholar 

  29. Bao YW, Hua XW, Li YH, Jia HR, Wu FG (2018) Hyperthemia-promoted cytosolic and nuclear delivery of copper/carbon quantum dot-crosslinked nanosheets: multimodal imaging-guided photothermal cancer therapy. ACS Appl Mater Interfaces 10(2):1544–1555

    Article  CAS  Google Scholar 

  30. Guldi DM, Rahman GM, Jux N, Balbinot D, Hartnagel U, Tagmatarchis N, Prato M (2005) Functional single-wall carbon nanotube nanohybrids associating SWNTs with water-soluble enzyme model systems. J Am Chem Soc 127(27):9830–9838

    Article  CAS  Google Scholar 

  31. Luque GL, Rojas MI, Rivas GA, Leiva EPM (2010) The origin of the catalysis of hydrogen peroxide reduction by functionalized graphene surfaces: a density functional theory study. Electrochim Acta 56(1):523–530

    Article  CAS  Google Scholar 

  32. Tang YF, Allen BL, Kauffman DR, Star A (2009) Electrocatalytic activity of nitrogen-doped carbon nanotube cups. J Am Chem Soc 131(37):13200–13201

    Article  CAS  Google Scholar 

  33. Fornera S, Yazawa K, Walde P (2011) Spectrophotometric quantification of lactose in solution with a peroxidase-based enzymatic cascade reaction system. Anal Bioanal Chem 401:2307–2310

    Article  CAS  Google Scholar 

  34. Khattar R, Yadav A, Mathur P (2015) Copper (II) complexes as catalyst for the aerobic oxidation of o-phenylenediamine to 2, 3-diaminophenazine. Spectrochim Acta A 142:375–381

    Article  CAS  Google Scholar 

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This research work was financially supported by Nature Science Foundation from Science and Technology Department of Fujian Province (No. 2018J05013), Education Research Project for Young and Middle-aged Teachers of Fujian Province (No. JT180136), Outstanding Youth Research Training Program of Fujian Agriculture and Forestry University (xjq201818) and National Natural Science Foundation of China (No. 21876141), which are gratefully acknowledged.

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Correspondence to Liping Lin or Xi Chen.

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Lin, L., Xiao, Y., Wang, Y. et al. Hydrothermal synthesis of nitrogen and copper co-doped carbon dots with intrinsic peroxidase-like activity for colorimetric discrimination of phenylenediamine isomers. Microchim Acta 186, 288 (2019).

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