Abstract
The authors report on a low temperature method for large-scale fabrication of cuprous oxide nanocubes deposited on nitrogen-doped reduced graphene oxide (Cu2O/N-RGO). The material was deposited in a glassy carbon electrode (GCE) where it is found to display enhanced electrocatalytic activity for oxidation of diethylstilbestrol (DES). The morphology and composition of Cu2O/N-RGO were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and energy-dispersive spectroscopy. The results demonstrate that the RGO is doped with 3.5% of nitrogen (atomic ratio), and that nanostructured Cu2O particles with controlled cubical morphology and an average size of about 450 nm have been homogeneously deposited on the surface of N-RGO sheets. The oxidation peak of DES was recorded at 0.315 V (vs. saturated calomel electrode) using differential pulse voltammetry. Under the optimal conditions, the modified GCE displays a linear response in the 0.3 to 150 μM DES concentration range, and the limit of detection is 10 nM. The method was applied to the determination of DES in spiked milk, meat and urine samples and gave excellent selectivity, stability and reproducibility.
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References
Sai N, Ning B, Huang G, Wu Y, Zhou Z, Peng Y, Bai J, Yu G, Gao Z (2013) An imprinted crystalline colloidal array chemicalsensing material for detection of trace diethylstilbestrol. Analyst 138:2720–2728
Liu H, Xie C (2006) Determination of diethylstilbestrol in milk powder by high-performance liquid chromatography. Chin J Appl Prev Med 6:374–375
Yuan K, Kang H, Yue Z, Yang L, Lin L, Wang X, Luan T (2015) Determination of 13 endocrine disrupting chemicals in sediments by gas chromatography-mass spectrometry using subcritical water extraction coupled with dispersed liquid-liquid microextraction and derivatization. Anal Chim Acta 866:41–47
Qin Y, Zhang J, Li Y, Han Y, Zou N, Jiang Y, Shan J, Pan C (2016) Multiplug filtration cleanup method with multi-walled carbon nanotubes for the analysis of malachite green, diethylstilbestrol residues, and their metabolites in aquatic products by liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 408:5801–5809
Liu J, Lu W, Liu H, Wu X, Li J, Chen L (2016) Dispersive liquid-liquid microextraction for four phenolic environmental estrogens in water samples followed by determination using capillary electrophoresis. Electrophoresis 37:2502–2508
Kim Y, Jeon J, Chang J (2016) Molecularly imprinted fullerene-silica nanocomposite particles for sensitive and selective recognition of diethylstilbestrol. Mater Lett 182:235–239
Ji L, Wang Y, Wu K, Zhang W (2016) Simultaneous determination of environmental estrogens: diethylstilbestrol and estradiol using cu-BTC frameworks-sensitized electrode. Talanta 159:215–221
Zhang Y, Wang Q, Li J, Wang X, Liu K, Feng H, Jiang J, Li J, Qian D (2015) Facile fabrication of sandwich-structured Co3O4/N-rGO/AB hybrid with enhanced ORR electrocatalytic performances for metal-air batteries. RSC Adv 5:9057–9063
Li D, Duan X, Sun H, Kang J, Zhang H, Tade MO, Wang S (2017) Facile synthesis of nitrogen-doped graphene via low-temperature pyrolysis: the effects of precursors and annealing ambience on metal-free catalytic oxidation. Carbon 115:649–658
Li J, Xu Z, Liu M, Deng P, Tang S, Jiang J, Qian D, He L (2017) Ag/N-doped reduced graphene oxide incorporated with molecularly imprinted polymer: an advanced electrochemical sensing platform for salbutamol determination. Biosens Bioelectron 90:210–216
Tajabadi MT, Sookhakian M, Zalnezhad E, Yoon GH, Hamouda AMS, Azarang M, Basirun WJ, Alias Y (2016) Electrodeposition of flower-like platinum on electrophoretically grown nitrogen-doped graphene as a highly sensitive electrochemical non-enzymatic biosensor for hydrogen peroxide detection. Appl Surf Sci 386:418–426
Shen Y, Rao D, Bai W, Sheng Q, Zheng J (2017) Preparation of high-quality palladium nanocubes heavily deposited on nitrogen-doped graphene nanocomposites and their application for enhanced electrochemical sensing. Talanta 165:304–312
Jiang BB, Wei XW, Wu FH, Wu KL, Chen L, Yuan GZ, Dong C, Ye Y (2014) A non-enzymatic hydrogen peroxide sensor based on a glassy carbon electrodemodified with cuprous oxide and nitrogen-doped graphene in a nafion matrix. Microchim Acta 181:1463–1470
Velmurugan M, Karikalan N, Chen SM, Karuppiah C (2016) Core-shell like Cu2O nanocubes enfolded with co(OH)2 on reduced graphene oxide for the amperometric detection of caffeine. Microchim Acta 183:2713–2721
Yuan B, Xu C, Liu L, Zhang Q, Ji S, Pi L, Zhang D, Huo Q (2013) Cu2O/NiOx/graphene oxide modified glassy carbon electrode for the enhanced electrochemical oxidation of reduced glutathione and nonenzyme glucose sensor. Electrochim Acta 104:78–83
Ye X, Gu Y, Wang C (2012) Fabrication of the Cu2O/polyvinyl pyrrolidone-graphene modified glassy carbon-rotating disk electrode and its application for sensitive detection of herbicide paraquat. Sensors Actuators B Chem 173:530–539
Feng T, Chen X, Qiao X, Sun Z, Wang H, Qi Y, Hong C (2016) Graphene oxide supported rhombic dodecahedral Cu2O nanocrystals for the detection of carcinoembryonic antigen. Anal Biochem 494:101–107
Sivasubramanian R, Biji P (2016) Preparation of copper (I) oxide nanohexagon decorated reduced graphene oxide nanocomposite and its application in electrochemical sensing of dopamine. Mat Sci Eng B 210:10–18
Lu W, Sun Y, Dai H, Ni P, Jiang S, Wang Y, Li Z, Li Z (2016) Direct growth of pod-like Cu2O nanowire arrays on copper foam: highly sensitive and efficient nonenzymatic glucose and H2O2 biosensor. Sensors Actuators B Chem 231:860–866
Wu LN, Tan YL, Wang L, Sun SN, Qu ZY, Zhang JM, Fan YJ (2015) Dopamine sensor based on a hybrid material composed of cuprous oxide hollow microspheres and carbon black. Microchim Acta 182:1361–1369
Xu J, Dang DK, Chung JS, Hur SH, Choi WM, Kim EJ (2014) Sonochemical fabrication of Cu2O@C/graphene nanohybrid with a hierarchical architecture. J Solid State Chem 220:111–117
Li J, Liu J, Tan G, Jiang J, Peng S, Deng M, Qian D, Feng Y, Liu Y (2014) High-sensitivity paracetamol sensor based on Pd/graphene oxide nanocomposite as an enhanced electrochemical sensing platform. Biosens Bioelectron 54:468–475
Li J, Jiang J, Feng H, Xu Z, Tang S, Deng P, Qian D (2016) Facile synthesis of 3D porous nitrogen-doped graphene as an efficient electrocatalyst for adenine sensing. RSC Adv 6:31565–31573
Yang L, Lv J, Sui Y, Fu W, Zhou X, Ma J, Li Q, Sun M, Mu Y, Chen Y, Wang J, Yang H (2014) Ag–Cu2O composite microstructures with tunable ag contents: synthesis and surface-enhanced (resonance) Raman scattering (SE(R)RS) properties. RSC Adv 4:17249–17254
Zhu X, Lu L, Duan X, Zhang K, Xu J, Hu D, Sun H, Dong L, Gao Y, Wu Y (2014) Efficient synthesis of graphene–multiwalled carbon nanotubes nanocomposite and its application in electrochemical sensing of diethylstilbestrol. J Electroanal Chem 731:84–92
Aragão JS, Ribeiro FWP, Portela RR, Santos VN, Sousa CP, Becker H, Correia AN, Lima-Neto P (2017) Electrochemical determination diethylstilbestrol by a multi-walled carbon nanotube/cobalt phthalocyanine film electrode. Sensors Actuators B Chem 239:933–942
Biryol İ, Salcı B, Erdik E (2003) Voltammetric investigation of diethylstilbestrol. J Pharmaceut Biomed 32:1227–1234
Hu X, Zhang R (2016) Voltammetric determination of the endocrine disruptor diethylstilbestrol by using a glassy carbon electrode modified with a composite consisting of platinum nanoparticles and multiwalled carbon nanotubes. Microchim Acta 183:3069–3076
Fei J, Wen X, Yi L, Ge F, Zhang Y, Huang M, Chen X (2008) Electrochemical determination diethylstilbestrol by a single-walled carbon nanotube/platinum nanoparticle composite film electrode. J Appl Electrochem 38:1527–1533
Laviron E (1979) General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J Electroanal Chem 101:19–28
Lu D, Lin S, Wang L, Shi X, Wang C, Zhang Y (2012) Synthesis of cyclodextrin-reduced graphene oxide hybrid nanosheets for sensitivity enhanced electrochemical determination of diethylstilbestrol. Electrochim Acta 85:131–138
Zhang K, Duan X, Zhu X, Hu D, Xu J, Lu L, Sun H, Dong L (2014) Nanostructured graphene oxide-MWCNTs incorporatedpoly(3,4-ethylenedioxythiophene) with a high surface area for sensitive determination of diethylstilbestrol. Synth Met 195:36–43
Hu L, Cheng Q, Chen D, Ma M, Wu K (2015) Liquid-phase exfoliated graphene as highly-sensitive sensor for simultaneous determination of endocrine disruptors: diethylstilbestrol and estradiol. J Hazard Mater 283:157–163
Ma X, Chen M (2015) Electrochemical sensor based on graphene doped gold nanoparticles modified electrode for detection of diethylstilbestrol. Sensors Actuators B Chem 215:445–450
Xie X, Sun D, Liu G, Zeng Q (2014) Sensitive and rapid determination of diethylstilbestrol using mesoporous SBA-15 modified electrode. Anal Methods 6:1640–1644
Acknowledgements
This work was financially supported by National Natural Science Foundation of China (No. 21505035, 21171174, 21472038), Provincial Natural Science Foundation of Hunan (No. 2016JJ3028, 09JJ3024), Scientific Research Projects of Education Department of Hunan Province (No. 16A029) and Hengyang Normal University (No. 16D04), and the Aid Programs for Innovative Team and Key Discipline in Education Department of Hunan Province.
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Li, J., Jiang, J., Xu, Z. et al. Synthesis of a nanocomposite consisting of Cu2O and N-doped reduced graphene oxide with enhanced electrocatalytic activity for amperometric determination of diethylstilbestrol. Microchim Acta 184, 4331–4339 (2017). https://doi.org/10.1007/s00604-017-2452-4
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DOI: https://doi.org/10.1007/s00604-017-2452-4