QUANTIFY THE AMOUNT OF CHLORPYRIFOS IN URINE AND BLOOD SAMPLES USING A THIN-LAYER CHROMATOGRAPHY IMAGING SYSTEM COUPLED TO A VORTEX-ASSISTED DISPERSIVE LIQUID-LIQUID MICROEXTRACTION METHOD
DOI:
https://doi.org/10.48165/jfmt.2024.41.2.9Keywords:
ultraviolet, chlorpyrifosAbstract
Consumption of pesticides poses serious health concerns and a need for reliable and effective detection techniques. Chlorpyrifos has been linked to numerous poisoning incidents, including accidental, suicide, and homicidal ones in India. The impact of chlorpyrifos on human health is influenced by several variables, including the duration, volume, and frequency of exposure, the person’s health, and specific environmental circumstances. Due to their lethal toxicity, forensic toxicology laboratories frequently encounter cases of pesticide poisoning. Herein, a method utilizing VA-DLLME method in conjunction with a TLC image analysis system is presented to detect the presence of chlorpyrifos, an organophosphorus pesticide, in blood. Following the VA DLLME method, a TLC plate was spotted with 20µl of the sample(chlorpyrifos), and this plate was developed by using a mobile phase (ethyl acetate and cyclohexane ,9:1v/v). The developed plate was next imaged under the ultraviolet chamber at 254 nm, and the image was further analyzed by using the free software ImageJ to quantify the spots on the thin layer chromatography plate. The approach was discovered to be linear in the 0.5–10 µg/ spot range under ideal circumstances, with a correlation coefficient of 0.9917 for blood samples and 2-16 µg/spot with a correlation coefficient of 0.9932 for urine, respectively. LOD and LOQ for blood was found 0.93 and 13.96 µg/spot and 0.089 and 14.25 µg/spot for urine respectively. The technique can be frequently used in laboratories with limited resources to determine the presence of chlorpyrifos in biological samples (such as blood and urine) without the need for expensive, high end instruments.
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References
Jain B, Jain R, Jaiswal PK, Zughaibi T, Sharma T, Kabir A, Singh R, Sharma S. A non-instrumental green analytical method based on surfactant-assisted dispersive liquid–liquid microextraction–thin-layer chromatography–smartphone-based digital image colorimetry (SA-DLLME-TLC-SDIC) for determining favipiravir in biological samples. Molecules. 2023;5;28 2-529.
Chen D, Jiao Y, Jia H, Guo Y, Sun X, Wang X, Xu J. Acetylcholinesterase biosensor for chlorpyrifos detection based on multi-walled carbon nanotubes SnO2-chitosan nanocomposite modified screen printed electrode. International Journal of Electrochemical Science.2015;10:10491-501.
Narendra M, Kavitha G, Kiranmai AH, Rao NR, Varadacharyulu NC. Chronic exposure to pyrethroid based allethrin and prallethrin mosquito repellents alters plasma biochemical profile. Chemosphere. 2008; 1:73:360-4.
Kolaczinski JH, Curtis CF. Chronic illness as a result of low-level exposure to synthetic pyrethroid insecticides: a review of the debate. Food and chemical toxicology. 2004; 1: 42:697-706.
Regueiro J, Llompart M, Garcia-Jares C, Cela R. Development of a high-throughput method for the determination of organochlorinated compounds, nitromusks and pyrethroid insecticides in indoor dust. Journal of Chromatography A. 2007;1174:112-24.
Vázquez PP, Mughari AR, Galera MM. Solid-phase microextraction (SPME) for the determination of pyrethroids in cucumber and watermelon using liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection. Analytica chimica acta. 2008;607:74-82.
Gilbert-López B, Garcia-Reyes JF, Molina-Díaz A. Sample treatment and determination of pesticide residues in fatty vegetable matrices: A review. Talanta. 2009;79:109-28.
Akkad R, Schwack W. Determination of organophosphorus and carbamate insecticides in fresh fruits and vegetables by high-performance thin layer chromatography-multienzyme inhibition assay. Journal of AOAC International. 2012;1;95:1371-7.
Li A, Liu X, Kong J, Huang R, Wu C. Chemiluminescence determination of organophosphorus pesticides chlorpyrifos in vegetable. Analytical letters. 2008;16;41:1375-86.
Alam MK. Determination of cypermethrin, chlorpyrifos and diazinon residues in tomato and reduction of cypermethrin residues in tomato using rice bran. World.
;1:30-5.
Barkat AK, Ahmad Z, Sher AK, Zahoor U. Monitoring pesticide residues in fruits and vegetables grown in Khyber Pakhtoonkhwa. International Journal of Green and Herbal Chemistry. 2012;3:302-13.
Chauhan V, Tomar S, Saini Y, Tripathi RM. Method development for determination of residual Chlorpyrifos in the grapes by Tlc-fid. Egyptian Journal of Forensic Sciences. 2017;7:1-7.
Pujeri US, Pujar AS, Hiremath SC, Pujari KG, Yadawe MS. Analysis of pesticide residues in vegetables in Vijayapur, Karnataka India. World J Pharm Pharm Sci. 2015;164:1743-50.
Bhushan C, Bhardwaj A, Misra SS. State of Pesticide Regulations in India, Centre for Science and Environment, New Delhi 2 STATE OF PESTICIDE REGULATIONS IN INDIA Page 3 3 The Indian Parliament sets up the Joint Parliamentary Committees (JPC) only on critical issues of public in-terest. Only five such committees have been formed in the history of independent India. The JPC formed on Pesticide Residues in and Safety Standards for Soft Drinks, Fruit Juices and Other Beverages, in. 2003.
Jiménez-López J, Llorent-Martínez EJ, Ortega Barrales P, Ruiz-Medina A. Analysis of neonicotinoid pesticides in the agri-food sector: a critical assessment of the state of the art. Applied Spectroscopy Reviews. 2020;1355:613-46.
Xiao Y, Zhang H. Homogeneous ionic liquid microextraction of the active constituents from fruits of Schisandra chinensis and Schisandra sphenanthera. Analytica chimica acta. 2012;712:78-84.
Breadmore MC. Ionic liquid-based liquid phase microextraction with direct injection for capillary electrophoresis. Journal of Chromatography A. 2011;1218:1347-52.
Anastassiades M, Lehotay SJ, Štajnbaher D, Schenck FJ. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC international. 2003; 1;86:412-31.
Fritz JS, Macka M. Solid-phase trapping of solutes for further chromatographic or electrophoretic analysis. Journal of Chromatography A. 2000;902:137- 66.
Behbahani M, Hassanlou PG, Amini MM, Omidi F, Esrafili A, Farzadkia M, Bagheri A. Application of solvent-assisted dispersive solid phase extraction as a new, fast, simple and reliable preconcentration and trace detection of lead and cadmium ions in fruit and water samples. Food chemistry. 2015;187:82-8.
Rezaee M, Assadi Y, Hosseini MR, Aghaee E, Ahmadi F, Berijani S. Determination of organic compounds in water using dispersive liquid–liquid microextraction. Journal of Chromatography a. 2006;1116:1-9.
Jamali MR, Firouzjah A, Rahnama R. Solvent assisted dispersive solid phase extraction. Talanta. 2013;116:454-9.
Zhang Y, Lee HK. Low-density solvent-based vortex assisted surfactant-enhanced-emulsification liquid– liquid microextraction combined with gas chromatography–mass spectrometry for the fast determination of phthalate esters in bottled water. Journal of Chromatography A. 2013;1274:28-35.
Barata C, Solayan A, Porte C. Role of B-esterases in assessing toxicity of organophosphorus (chlorpyrifos, malathion) and carbamate (carbofuran) pesticides to Daphnia magna. Aquatic toxicology. 2004;66:125-39.
Jain R, Singh R, Sudhaker S, Barik AK, Kumar S. Coupling microextraction with thin layer chromatography–Image processing analysis: A new analytical platform for drug analysis. Toxicology and Forensic Medicine Open Journal. 2017;2:17-25.
Jain R, Kumari A, Khatri I. Simple and rapid analysis of acetaminophen in human autopsy samples by vortex assisted dispersive liquid–liquid microextraction thin layer chromatography image analysis. Separation Science Plus. 2021;4:92-100.
Jain R, Tripathi RM, Negi A, Singh SP. A simple, cost-effective and rapid method for simultaneous determination of Strychnos nux-vomica alkaloids in blood and Ayurvedic medicines based on ultrasound assisted dispersive liquid–liquid microextraction–thin layer chromatography-image analysis. Journal of Chromatographic Science. 2020;58:477-84.
Meisen I, Wisholzer S, Soltwisch J, Dreisewerd K, Mormann M, Müthing J, Karch H, Friedrich AW. Normal silica gel and reversed phase thin-layer chromatography coupled with UV spectroscopy and IR-MALDI-o-TOF-MS for the detection of tetracycline antibiotics. Analytical and bioanalytical chemistry. 2010;398:2821-31.
Parys W, Pyka-Paj¹k A. TLC–Densitometry for Determination of Omeprazole in Simple and Combined Pharmaceutical Preparations. Pharmaceuticals. 2022;15:1016.
Domínguez C, Jover E, Garde F, Bayona JM, Erra P. Characterization of supercritical fluid extracts from raw wool by TLC FID and GC MS. Journal of the American Oil Chemists’ Society. 2003;80:717-24.
Nakamura K, Suzuki Y, Goto-Inoue N, Yoshida-Noro C, Suzuki A. Structural characterization of neutral
glycosphingolipids by thin-layer chromatography coupled to matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight MS/MS. Analytical chemistry. 2006;78:5736-43.
Deshpande SS, Kar KK, Walker J, Pressler J, Su W. An experimental and computational investigation of vortex formation in an unbaffled stirred tank. Chemical Engineering Science. 2017;168:495-506.
Akkaya E, Bozyiðit GD, Bakirdere S. Simultaneous determination of 4-tert-octylphenol, chlorpyrifos ethyl and penconazole by GC–MS after sensitive and selective preconcentration with stearic acid coated magnetic nanoparticles. Microchemical Journal. 2019;146:1190-4.
Gao N, Guo X, Zhang K, Hu D. High-Performance Liquid Chromatography and Gas Chromatography— Mass Spectrometry Methods for the Determination of Imidacloprid, Chlorpyrifos, and Bifenthrin Residues in Tea Leaves. Instrumentation Science & Technology. 2014;4;42:267-77.
Liu L, Yang M, He M, Liu T, Chen F, Li Y, Feng X, Zhang Y, Zhang F. Magnetic solid phase extraction sorbents using methyl-parathion and quinalphos dual template imprinted polymers coupled with GC-MS for class-selective extraction of twelve organophosphorus pesticides. Microchimica Acta. 2020;187:1-2.sss
Moinfar S, Khodayari A, Abdulrahman SS, Aghaei A, Sohrabnezhad S, Jamil LA. Development of a SPE/ GC–MS method for the determination of organophosphorus pesticides in food samples using syringe filters packed by GNP/MIL-101 (Cr) nanocomposite. Food Chemistry. 2022;371:130997.
Alam S, Srivastava N, Iqbal N, Saini MK, Kumar J. Magnetic solid-phase extraction (MSPE) using magnetite-based core-shell nanoparticles with silica network (SiO2) coupled with GC-MS/MS analysis for determination of multiclass pesticides in water. Journal of AOAC International. 2021;1;104:633-44.
glycosphingolipids by thin-layer chromatography coupled to matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight MS/MS. Analytical chemistry. 2006;78:5736-43.
Deshpande SS, Kar KK, Walker J, Pressler J, Su W. An experimental and computational investigation of vortex formation in an unbaffled stirred tank. Chemical Engineering Science. 2017;168:495-506.
Akkaya E, Bozyiðit GD, Bakirdere S. Simultaneous determination of 4-tert-octylphenol, chlorpyrifos ethyl and penconazole by GC–MS after sensitive and selective preconcentration with stearic acid coated magnetic nanoparticles. Microchemical Journal. 2019;146:1190-4.
Gao N, Guo X, Zhang K, Hu D. High-Performance Liquid Chromatography and Gas Chromatography— Mass Spectrometry Methods for the Determination of Imidacloprid, Chlorpyrifos, and Bifenthrin Residues in Tea Leaves. Instrumentation Science & Technology. 2014;4;42:267-77.
Liu L, Yang M, He M, Liu T, Chen F, Li Y, Feng X, Zhang Y, Zhang F. Magnetic solid phase extraction sorbents using methyl-parathion and quinalphos dual template imprinted polymers coupled with GC-MS for class-selective extraction of twelve organophosphorus pesticides. Microchimica Acta. 2020;187:1-2.sss
Moinfar S, Khodayari A, Abdulrahman SS, Aghaei A, Sohrabnezhad S, Jamil LA. Development of a SPE/ GC–MS method for the determination of organophosphorus pesticides in food samples using syringe filters packed by GNP/MIL-101 (Cr) nanocomposite. Food Chemistry. 2022;371:130997.
Alam S, Srivastava N, Iqbal N, Saini MK, Kumar J. Magnetic solid-phase extraction (MSPE) using magnetite-based core-shell nanoparticles with silica network (SiO2) coupled with GC-MS/MS analysis for determination of multiclass pesticides in water. Journal of AOAC International. 2021;1;104:633-44.
