Chemiluminescence Detection of Chlorpyrifos via Luminol-H2O2-Ferricyanide System using Microcontroller-based Photometer
Angelo Gabriel E. Buenaventura1,2 and Allan Christopher C. Yago1,2*
1Institute of Chemistry, University of the Philippines Diliman, Quezon City 1101 Philippines
2Natural Sciences Research Institute, University of the Philippines Diliman,
Quezon City 1101 Philippines
*Corresponding author: This email address is being protected from spambots. You need JavaScript enabled to view it.
ABSTRACT
A low-cost photometer for chemiluminescence (CL) detection of chlorpyrifos (CPF) was constructed based on Arduino microcontroller, Si photodiode, and operational amplifier. The CPF detection via CL is based on the decrease in light intensity of the sensing solution (luminol-H2O2-Fe(CN)63–-CPF) as compared to the blank solution (luminol-H2O2 Fe(CN)63–). The decrease in light intensity is due to the known reaction of organophosphates with H2O2 and luminol, thereby consuming the reactants for CL reaction. The change in response (ΔICL) was determined by the difference between the response of the blank solution (IB) and the sensing solution (Iss). Different parameters for both blank and sensing solutions were optimized. A linearly decreasing response with increasing CPF concentration was found between 0.7 ppm and 2.45 ppm CPF (2.00–7.00 μM CPF), with a limit of detection (LOD) of 0.663 ppm (1.89 μM). The system was shown to be selective mainly toward organophosphate pesticides as non-organophosphate herbicides – such as 2,4-dichlorophenoxyacetic acid (2,4-D) and atrazine – did not show significant changes in response as compared to blank solution.
INTRODUCTION
Organophosphates are a class of insecticides that primarily act by irreversibly inhibiting acetylcholinesterase (AChE), the enzyme responsible for acetylcholine hydrolysis (Lukaszewicz-Hussain 2010). Irreversible inhibition of AChE can lead to build-up of the neurotransmitter acetylcholine, which interferes with muscular response and produce serious symptoms in vital organs (Mulchandani et al. 2001). Despite the toxicity of organophosphates, certain organophosphates are still allowed to be used in many countries. Chlorpyrifos (CPF), an organophosphate insecticide, is widely used in agriculture and household applications. CPF and its derivative methyl-chlorpyrifos are the main active ingredients in insecticide formulations widely used to control insect and arthropod pests on agricultural crops such as grains, cotton, nuts, and fruits. Urban applications of CPF include controlling pests on lawn and ornamental plants (Mauriz et al. 2006). Due to the wide usage of CPF, point-source and agricultural discharges of CPF became responsible for aquatic life toxicity . . . . . read more
REFERENCES
ARMENTA S, QUINTÁS G, GARRIGUES S, DE LA GUARDIA M. 2005. A validated and fast procedure for FTIR determination of Cypermethrin and Chlorpyrifos. Talanta 67(3): 634–639. doi: http://dx.doi.org/10.1016/j.talanta.2005.03.008
DODEIGNE C, THUNUS L, LEJEUNE R. 2000. Chemiluminescence as diagnostic tool. A review. Talanta 51(3): 415–439. doi: http://dx.doi.org/10.1016/S0039-9140(99)00294-5
DU J, LI Y, LU J. 2001a. Flow injection chemiluminescence determination of polyhydroxy phenols using luminol–ferricyanide/ferrocyanide system. Talanta 55(6): 1055–58. doi: https://doi.org/10.1016/S0039-9140(01)00452-0
DU J, LI Y, LU J. 2001b. Flow Injection Chemiluminescence Determination of Rutin based on its enhancing effect on the Luminol-Ferricyanide/Ferrocyanide system. Analytical Letters 34(10): 1741–48. doi:10.1081/AL-100105357
DU J, LI Y, LU J. 2002. Flow injection chemiluminescence determination of captopril based on its enhancing effect on the luminol–ferricyanide/ferrocyanide reaction. Luminescence 17(3): 165–167. doi:10.1002/bio.685
[EC] EU Commission. 2014. Commission Regulation (EU) 2016/60. Official Journal of the European Union 12(4): 3640. doi:10.2903/j.efsa.2014.3640
GÁMIZ-GRACIA L, GARCÍA-CAMPAÑA AM, SOTO-CHINCHILLA JJ, HUERTAS-PÉREZ JF, GONZÁLEZ-CASADO A. 2005. Analysis of pesticides by chemiluminescence detection in the liquid phase. TrAC Trends in Analytical Chemistry 24(11): 927-942. doi: http://dx.doi.org/10.1016/j.trac.2005.05.009
GIRDHAR KK, JAIN DVS. 1965. Kinetics of the decomposition of hydrogen peroxide in presence of ferricyanide. Journal of Inorganic and Nuclear Chemistry 27(12): 2653–57. doi: http://dx.doi.org/10.1016/0022-1902(65)80169-5
GUARDINO X, OBIOLS J, ROSELL MG, FARRAN A, SERRA C. 1998. Determination of chlorpyrifos in air, leaves and soil from a greenhouse by gas-chromatography with nitrogen-phosphorus detection, high-performance liquid chromatography and capillary electrophoresis. Journal of Chromatography A 823(1–2): 91–96. doi: http://dx.doi.org/10.1016/S0021-9673(98)00272-6
HU H, LIU X, JIANG F, YAO X, CUI X. 2010. A novel chemiluminescence assay of organophosphorous pesticide quinalphos residue in vegetable with luminol detection. Chemistry Central Journal 4(1): 13. doi:10.1186/1752-153X-4-13
KAVIYARASAN K, ANANDAN S, MANGALARAJA RV, SIVASANKAR T, ASHOKKUMAR M. 2016. Sonochemical synthesis of Cu2O nanocubes for enhanced chemiluminescence applications. Ultrasonics Sonochemistry 29: 388–393. doi: http://dx.doi.org/10.1016/j.ultsonch.2015.10.018
KHAN P, IDREES D, MOXLEY MA, CORBETT JA, AHMAD F, VON FIGURA G, SLY WS, WAHEED A, HASSAN MI. 2014. Luminol-based Chemiluminescent Signals: Clinical and Non-clinical Application and Future Uses. Applied Biochemistry and Biotechnology 173(2): 333–355. doi:10.1007/s12010-014-0850-1
KUBÍNOVÁ Š, ŠLÉGR J. 2015. ChemDuino: Adapting Arduino for Low-Cost Chemical Measurements in Lecture and Laboratory. Journal of Chemical Education 92(10): 1751–53. doi:10.1021/ed5008102
KUSWANDI B, FIKRIYAH CI, GANI AA. 2008. An optical fiber biosensor for chlorpyrifos using a single sol-gel film containing acetylcholinesterase and bromothymol blue. Talanta 74(4): 613–618. doi: http://dx.doi.org/10.1016/j.talanta.2007.06.042
LI A, LIU X, KONG J, HUANG R, WU C. 2008. Chemiluminescence Determination of Organophosphorus Pesticides Chlorpyrifos in Vegetable. Analytical Letters 41(8): 1375–86. doi:10.1080/00032710802119228
LI Y, YOU X, SHI X. 2017. Enhanced Chemiluminescence Determination of Hydrogen Peroxide in Milk Sample Using Metal-organic Framework Fe-MIL-88NH2 as Peroxidase Mimetic. Food Analytical Methods 10(3): 626–633. doi:10.1007/s12161-016-0617-0
LI YC, MELENBRINK EL, CORDONIER GJ, BOGGS C, KHAN A, ISAAC MK, NKHONJERA LK, BAHATI D, BILLINGE SJ, HAILE SM, KREUTER RA, CRABLE RM, MALLOUK TE. 2018. An Easily Fabricated Low-Cost Potentiostat Coupled with User-Friendly Software for Introducing Students to Electrochemical Reactions and Electroanalytical Techniques. Journal of Chemical Education 95(9): 1658–61. doi:10.1021/acs.jchemed.8b00340
LIU H, ZHANG L, ZHOU J, HAO Y, HE P, FANG Y. 2005. Flow injection chemiluminescence determination of dobutamine hydrochloride injection using luminol–ferricyanide/ferrocyanide system. Analytica Chimica Acta 541(1): 123–127. doi: https://doi.org/10.1016/j.aca.2004.11.071
LIU M, LIN Z, LIN J-M. 2010. A review on applications of chemiluminescence detection in food analysis. Analytica Chimica Acta 670(1–2): 1–10. doi: http://dx.doi.org/10.1016/j.aca.2010.04.039
LIU T, XU M, YIN H, AI S, QU X, ZONG S. 2011. A glassy carbon electrode modified with graphene and tyrosinase immobilized on platinum nanoparticles for sensing organophosphorus pesticides. Microchimica Acta 175(1): 129. doi:10.1007/s00604-011-0665-5
LUKASZEWICZ-HUSSAIN A. 2010. Role of oxidative stress in organophosphate insecticide toxicity – Short review. Pesticide Biochemistry and Physiology 98(2): 145–150. doi: http://dx.doi.org/10.1016/j.pestbp.2010.07.006
MARTÍNEZ GALERA M, MARTÍNEZ VIDAL JL, FRENICH AG. 1994. Simultaneous Determination of Atrazine and Chlorpyrifos in Pesticide Formulations, in Soils and Waters by Derivative Spectrophotometry and Ratio Spectra Derivative. Analytical Letters 27(4): 807–818. doi:10.1080/00032719408000273
MAURIZ E, CALLE A, LECHUGA LM, QUINTANA J, MONTOYA A, MANCLÚS JJ. 2006. Real-time detection of chlorpyrifos at part per trillion levels in ground, surface and drinking water samples by a portable surface plasmon resonance immunosensor. Analytica Chimica Acta 561(1–2): 40–47. doi: http://dx.doi.org/10.1016/j.aca.2005.12.069
MERÉNYI G, LIND J, ERIKSEN TE. 1990. Luminol chemiluminescence: Chemistry, excitation, emitter. Journal of Bioluminescence and Chemiluminescence 5(1): 53–56. doi:10.1002/bio.1170050111
MULCHANDANI A, CHEN W, MULCHANDANI P, WANG J, ROGERS KR. 2001. Biosensors for direct determination of organophosphate pesticides. Biosensors and Bioelectronics 16(4–5): 225–230. doi: http://dx.doi.org/10.1016/S0956-5663(01)00126-9
OLIVA J, NAVARRO S, BARBA A, NAVARRO G. 1999. Determination of chlorpyrifos, penconazole, fenarimol, vinclozolin and metalaxyl in grapes, must and wine by on-line microextraction and gas chromatography. Journal of Chromatography A 833(1): 43–51. doi: http://dx.doi.org/10.1016/S0021-9673(98)00860-7
PARK J-M, JUNG H-W, CHANG YW, KIM H-S, KANG M-J, PYUN J-C. 2015. Chemiluminescence lateral flow immunoassay based on Pt nanoparticle with peroxidase activity. Analytica Chimica Acta 853: 360–367. doi: http://dx.doi.org/10.1016/j.aca.2014.10.011
ROBARDS K, WORSFOLD PJ. 1992. Analytical applications of liquid-phase chemiluminescence. Analytica Chimica Acta 266(2): 147–173. doi: http://dx.doi.org/10.1016/0003-2670(92)85040-D
SHEVLIN PB, NEUFELD HA. 1970. Mechanism of the ferricyanide-catalyzed chemiluminescence of luminol. The Journal of Organic Chemistry 35(7): 2178–82. doi:10.1021/jo00832a015
TUNÇELI A, BAĞ H, TÜRKER RA. 2001. Spectrophotometric determination of some pesticides in water samples after preconcentration with Saccharomyces cerevisiae immobilized on sepiolite. Fresenius' Journal of Analytical Chemistry 371(8): 1134–38. doi:10.1007/s002160101088
UYGUN ZO, DILGIN Y. 2013. A novel impedimetric sensor based on molecularly imprinted polypyrrole modified pencil graphite electrode for trace level determination of chlorpyrifos. Sensors and Actuators B: Chemical 188: 78–84. doi: http://dx.doi.org/10.1016/j.snb.2013.06.075
VISWANATHAN S, RADECKA H, RADECKI J. 2009. Electrochemical biosensor for pesticides based on acetylcholinesterase immobilized on polyaniline deposited on vertically assembled carbon nanotubes wrapped with ssDNA. Biosensors and Bioelectronics 24(9): 2772–77. doi: http://dx.doi.org/10.1016/j.bios.2009.01.044
YOTTER RA, WILSON DM. 2003. A review of photodetectors for sensing light-emitting reporters in biological systems. IEEE Sensors Journal 3(3): 288–303. doi:10.1109/JSEN.2003.814651
YU D, WANG P, ZHAO Y, FAN A. 2016. Iodophenol blue-enhanced luminol chemiluminescence and its application to hydrogen peroxide and glucose detection. Talanta 146: 655–661. doi: http://dx.doi.org/10.1016/j.talanta.2015.06.059
ZAMFIR L-G, ROTARIU L, BALA C. 2011. A novel, sensitive, reusable and low potential acetylcholinesterase biosensor for chlorpyrifos based on 1-butyl-3-methylimidazolium tetrafluoroborate/multiwalled carbon nanotubes gel. Biosensors and Bioelectronics 26(8): 3692–95. doi: http://dx.doi.org/10.1016/j.bios.2011.02.001