Development of an Electrochemical Sensor for the Determination of Carbaryl
Abstract
An electrochemical sensor was developed by modification of carbon paste electrode with graphene nanoplatelets and hemin for carbaryl analysis. The modified electrode was characterized for physical properties and electrochemical properties by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). This research investigated optimum experimental conditions as follows: amount of grapheme nanoplatelets at 10 µg/cm2, amount of hemin at 1 µg/cm2 on sensing area, pulse potential at 0.125 V, step potential at 0.010 V, scan rate at 0.010 v/s, phosphate buffer solution pH at 6.5. The designed electrochemical sensor yielded a linear range for carbaryl from 0.50 to 10.0 µM (r2 = 0.998) with a sensitivity of 0.70 µA-µM/cm2, a detection limit and a quantification limit of 0.25 and 0.50 µM, respectively. A reproducibility of 3.8 % RSD (3 sensors) and a repeatability of 2.6 %RSD (10 measurements) were obtained. Moreover, the proposed electrochemical sensor was validated to determine carbaryl in cauliflower and spiked cauliflower samples which showed the recovery percentage ranging from 96.7 to 103.5 %. The determination of carbaryl by the proposed electrochemical sensor was satisfactory comparable to the reference technique (high performance liquid chromatography, HPLC). These results indicated that the proposed electrochemical sensor could be applied for detection of carbaryl in real samples. Keywords : electrochemical sensor, carbaryl, graphene nanoplatelets, heminReferences
Ali, I., Mbianda, X. Y., Burakov, A., Galunin, E., Burakova, I., Mkrtchyan, E., ... & Grachev, V. (2019). Graphene
based adsorbents for remediation of noxious pollutants from wastewater. Environment international, 127, 160-180.
Cao, H., Sun, X., Zhang, Y., Hu, C., & Jia, N. (2012). Electrochemical sensing based on hemin-ordered
mesoporous carbon nanocomposites for hydrogen peroxide. Analytical Methods, 4(8), 2412-2416.
Cheng, L., Yan, K., & Zhang, J. (2016). Integration of graphene-hemin hybrid materials in an electroenzymatic
system for degradation of diclofenac. Electrochimica Acta, 190, 980-987.
Dogheim, S. M., El-Marsafy, A. M., Salama, E. Y., Gadalla, S. A., & Nabil, Y. M. (2002). Monitoring of pesticide
residues in Egyptian fruits and vegetables during 1997. Food Additives & Contaminants, 19(11),
1015-1027.
Ensafi, A. A., Nasr-Esfahani, P., & Rezaei, B. (2018). Metronidazole determination with an extremely sensitive and
selective electrochemical sensor based on graphene nanoplatelets and molecularly imprinted polymers on graphene quantum dots. Sensors and Actuators B: Chemical, 270, 192-199.
Fan, Y., Lai, K., Rasco, B. A., & Huang, Y. (2015). Determination of carbaryl pesticide in Fuji apples using surface-
enhanced Raman spectroscopy coupled with multivariate analysis. LWT-Food Science and Technology, 60(1), 352-357.
Grenoble, D. C., & Drickamer, H. G. (1968). The effect of pressure on the oxidation state of iron. 3. Hemin and
hematin. Proceedings of the National Academy of Sciences of the United States of America, 61(4), 1177.
Hashemi, P., Karimian, N., Khoshsafar, H., Arduini, F., Mesri, M., Afkhami, A., & Bagheri, H. (2019). Reduced
graphene oxide decorated on Cu/CuO-Ag nanocomposite as a high-performance material for the construction of a non-enzymatic sensor: Application to the determination of carbaryl and fenamiphos pesticides. Materials Science and Engineering: C, 102, 764-772.
Hulanicki, A., Glab, S., & Ingman, F. O. L. K. E. (1991). Chemical sensors: definitions and classification. Pure and
Applied Chemistry, 63(9), 1247-1250.
Moraes, F. C., Mascaro, L. H., Machado, S. A., & Brett, C. M. (2009). Direct electrochemical determination of
carbaryl using a multi-walled carbon nanotube/cobalt phthalocyanine modified electrode. Talanta, 79(5), 1406-1411.
Murillo Pulgarín, J. A., García Bermejo, L. F., & Carrasquero Durán, A. (2018). Simultaneous chemiluminescent
determination of carbaryl and 1-naphthol in soils using a flow-injection system. International Journal of Environmental Analytical Chemistry, 98(2), 111-123
Oh-Shin, Y. S., Ko, M., & Shin, H. S. (1997). Simultaneous quantification of insecticides including carbaryl in
drinking water by gas chromatography using dual electron-capture and nitrogen–phosphorus detection. Journal of Chromatography A, 769(2), 285-291.
Promsuwan, K., Kachatong, N., & Limbut, W. (2019). Simple flow injection system for non-enzymatic glucose
sensing based on an electrode modified with palladium nanoparticles-graphene nanoplatelets/mullti-walled carbon nanotubes. Electrochimica Acta, 320, 134621.
Sakai, K., & Matsumura, F. (1971). Degradation of certain organophosphate and carbamate insecticides by
human brain esterases. Toxicology and applied pharmacology, 19(4), 660-666.
Spittler, T. D., Marafioti, R. A., Helfman, G. W., & Morse, R. A. (1986). Determination of carbaryl in honeybees and
pollen by high-performance liquid chromatography. Journal of Chromatography A, 352, 439-443.
Stenersen, J. (2004). Chemical pesticides mode of action and toxicology. CRC press.
Supharoek, S. A., Ponhong, K., Siriangkhawut, W., & Grudpan, K. (2019). A new method for spectrophotometric
determination of carbaryl based on rubber tree bark peroxidase enzymatic reaction. Microchemical Journal, 144, 56-63.
Toader, A. M., Volanschi, E., Lazarescu, M. F., & Lazarescu, V. (2010). Redox behavior of hemin at p-GaAs (1 0 0)
electrode. Electrochimica acta, 56(2), 863-866.
Vytřas, K., Švancara, I., & Metelka, R. (2009). Carbon paste electrodes in electroanalytical chemistry. Journal of
the Serbian Chemical Society, 74(10), 1021-1033.
Wang, L., Yang, H., He, J., Zhang, Y., Yu, J., & Song, Y. (2016). Cu-hemin metal-organic-frameworks/chitosan-
reduced graphene oxide nanocomposites with peroxidase-like bioactivity for electrochemical sensing. Electrochimica Acta, 213, 691-697.
Wei, H., Sun, J. J., Wang, Y. M., Li, X., & Chen, G. N. (2008). Rapid hydrolysis and electrochemical detection of
trace carbofuran at a disposable heated screen-printed carbon electrode. Analyst, 133(11), 1619-1624.
Wong, A., Materon, E. M., & Sotomayor, M. D. P. T. (2014). Development of a biomimetic sensor modified with
hemin and graphene oxide for monitoring of carbofuran in food. Electrochimica Acta, 146, 830-837.
Yu, L., Xu, Q., Jin, D., Zhang, Q., Mao, A., Shu, Y., ... & Hu, X. (2016). Highly sensitive electrochemical
determination of sulfate in PM2. 5 based on the formation of heteropoly blue at poly-l-lysine-functionalized graphene modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide. Chemical Engineering Journal, 294, 122-131.
Zajkoska, S. P., Mulone, A., Hansal, W. E., Klement, U., Mann, R., & Kautek, W. (2018). Alkoxylated β-naphthol as
an additive for tin plating from chloride and methane sulfonic acid electrolytes. Coatings, 8(2), 79.
based adsorbents for remediation of noxious pollutants from wastewater. Environment international, 127, 160-180.
Cao, H., Sun, X., Zhang, Y., Hu, C., & Jia, N. (2012). Electrochemical sensing based on hemin-ordered
mesoporous carbon nanocomposites for hydrogen peroxide. Analytical Methods, 4(8), 2412-2416.
Cheng, L., Yan, K., & Zhang, J. (2016). Integration of graphene-hemin hybrid materials in an electroenzymatic
system for degradation of diclofenac. Electrochimica Acta, 190, 980-987.
Dogheim, S. M., El-Marsafy, A. M., Salama, E. Y., Gadalla, S. A., & Nabil, Y. M. (2002). Monitoring of pesticide
residues in Egyptian fruits and vegetables during 1997. Food Additives & Contaminants, 19(11),
1015-1027.
Ensafi, A. A., Nasr-Esfahani, P., & Rezaei, B. (2018). Metronidazole determination with an extremely sensitive and
selective electrochemical sensor based on graphene nanoplatelets and molecularly imprinted polymers on graphene quantum dots. Sensors and Actuators B: Chemical, 270, 192-199.
Fan, Y., Lai, K., Rasco, B. A., & Huang, Y. (2015). Determination of carbaryl pesticide in Fuji apples using surface-
enhanced Raman spectroscopy coupled with multivariate analysis. LWT-Food Science and Technology, 60(1), 352-357.
Grenoble, D. C., & Drickamer, H. G. (1968). The effect of pressure on the oxidation state of iron. 3. Hemin and
hematin. Proceedings of the National Academy of Sciences of the United States of America, 61(4), 1177.
Hashemi, P., Karimian, N., Khoshsafar, H., Arduini, F., Mesri, M., Afkhami, A., & Bagheri, H. (2019). Reduced
graphene oxide decorated on Cu/CuO-Ag nanocomposite as a high-performance material for the construction of a non-enzymatic sensor: Application to the determination of carbaryl and fenamiphos pesticides. Materials Science and Engineering: C, 102, 764-772.
Hulanicki, A., Glab, S., & Ingman, F. O. L. K. E. (1991). Chemical sensors: definitions and classification. Pure and
Applied Chemistry, 63(9), 1247-1250.
Moraes, F. C., Mascaro, L. H., Machado, S. A., & Brett, C. M. (2009). Direct electrochemical determination of
carbaryl using a multi-walled carbon nanotube/cobalt phthalocyanine modified electrode. Talanta, 79(5), 1406-1411.
Murillo Pulgarín, J. A., García Bermejo, L. F., & Carrasquero Durán, A. (2018). Simultaneous chemiluminescent
determination of carbaryl and 1-naphthol in soils using a flow-injection system. International Journal of Environmental Analytical Chemistry, 98(2), 111-123
Oh-Shin, Y. S., Ko, M., & Shin, H. S. (1997). Simultaneous quantification of insecticides including carbaryl in
drinking water by gas chromatography using dual electron-capture and nitrogen–phosphorus detection. Journal of Chromatography A, 769(2), 285-291.
Promsuwan, K., Kachatong, N., & Limbut, W. (2019). Simple flow injection system for non-enzymatic glucose
sensing based on an electrode modified with palladium nanoparticles-graphene nanoplatelets/mullti-walled carbon nanotubes. Electrochimica Acta, 320, 134621.
Sakai, K., & Matsumura, F. (1971). Degradation of certain organophosphate and carbamate insecticides by
human brain esterases. Toxicology and applied pharmacology, 19(4), 660-666.
Spittler, T. D., Marafioti, R. A., Helfman, G. W., & Morse, R. A. (1986). Determination of carbaryl in honeybees and
pollen by high-performance liquid chromatography. Journal of Chromatography A, 352, 439-443.
Stenersen, J. (2004). Chemical pesticides mode of action and toxicology. CRC press.
Supharoek, S. A., Ponhong, K., Siriangkhawut, W., & Grudpan, K. (2019). A new method for spectrophotometric
determination of carbaryl based on rubber tree bark peroxidase enzymatic reaction. Microchemical Journal, 144, 56-63.
Toader, A. M., Volanschi, E., Lazarescu, M. F., & Lazarescu, V. (2010). Redox behavior of hemin at p-GaAs (1 0 0)
electrode. Electrochimica acta, 56(2), 863-866.
Vytřas, K., Švancara, I., & Metelka, R. (2009). Carbon paste electrodes in electroanalytical chemistry. Journal of
the Serbian Chemical Society, 74(10), 1021-1033.
Wang, L., Yang, H., He, J., Zhang, Y., Yu, J., & Song, Y. (2016). Cu-hemin metal-organic-frameworks/chitosan-
reduced graphene oxide nanocomposites with peroxidase-like bioactivity for electrochemical sensing. Electrochimica Acta, 213, 691-697.
Wei, H., Sun, J. J., Wang, Y. M., Li, X., & Chen, G. N. (2008). Rapid hydrolysis and electrochemical detection of
trace carbofuran at a disposable heated screen-printed carbon electrode. Analyst, 133(11), 1619-1624.
Wong, A., Materon, E. M., & Sotomayor, M. D. P. T. (2014). Development of a biomimetic sensor modified with
hemin and graphene oxide for monitoring of carbofuran in food. Electrochimica Acta, 146, 830-837.
Yu, L., Xu, Q., Jin, D., Zhang, Q., Mao, A., Shu, Y., ... & Hu, X. (2016). Highly sensitive electrochemical
determination of sulfate in PM2. 5 based on the formation of heteropoly blue at poly-l-lysine-functionalized graphene modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide. Chemical Engineering Journal, 294, 122-131.
Zajkoska, S. P., Mulone, A., Hansal, W. E., Klement, U., Mann, R., & Kautek, W. (2018). Alkoxylated β-naphthol as
an additive for tin plating from chloride and methane sulfonic acid electrolytes. Coatings, 8(2), 79.
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2020-09-01
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