At present, the detection of chlorothalonil is generally based on chromatography and immunoassay; both of which are time-consuming and costly. In this study, Surface-enhanced Raman Spectroscopy (SERS) has been successfully utilized in the detection of chlorothalonil coupled with photochemistry and meanwhile, gold nanoparticles were prepared to enhance the Raman signal. Two Raman peaks (2246 cm− 1 and 2140 cm− 1) of chlorothalonil were appeared after ultraviolet (UV) irradiation compared to the original solution. Chlorothalonil generated excited and weakened C≡N bonds in its structure by absorbing UV energy, thus leading to two kinds of corresponding peaks. These two kinds of peaks were both selected as analytical peaks in chlorothalonil detection. Different light sources and solvents were made different contributions to the final spectra. Chlorothalonil methanol solution under 302 nm wavelength irradiation was performed the best. The 2246 cm− 1 sharp peak represented to the normal C≡N bond appeared at first, which overall trend was significantly increased followed by a gradual decrease. The 2140 cm− 1 broad peak represented to the weakened C≡N bond appeared later, which overall trend was increased as the irradiation time passing by and then kept stable. Natural bond orbital (NBO) analysis indicates that the downshift of C≡N bond from 2246 cm− 1 to 2140 cm− 1 is due to the increase of electronic populations of π* orbital of C≡N bond transited from π orbital excited by UV irradiation. The positively charged C≡N bond had more chance to approach negatively charged gold nanoparticles. The detection limit of chlorothalonil was as low as 0.1 ppm in the standard solution. Orange peels spiked with chlorothalonil oil were also detected in this paper to confirm the practical operability of this method. The SERS method may be further developed as a rapid detection of pesticides that contains a triple bond by utilizing photochemistry.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Price includes VAT (USA)
Tax calculation will be finalised during checkout.
Abdalla AA, Afify AS, Hasaan IE, Mohamed A (2018) Studying the effect of household-type treatment and processing on the residues of ethion and profenofos pesticides and on the contents of capsaicinoids in green chili pepper using GC-MS/MS and HPLC. Food Anal Meth 11(2):382–393. https://doi.org/10.1007/s12161-017-1009-9
Amelin VG, Bol’shakov DS, Andoralov AM (2018) Screening and determination of pesticides from various classes in natural water without sample preparation by ultra HPLC–high-resolution quadrupole time-of-flight mass spectrometry. J Anal Chem 73(3):257–265. https://doi.org/10.1134/S1061934818030024
Bolat G, Abaci S, Vural T, Bozdogan B, Denkbas EB (2018) Sensitive electrochemical detection of fenitrothion pesticide based on self-assembled peptide-nanotubes modified disposable pencil graphite electrode. J Electroanal Chem 809:88–95. https://doi.org/10.1016/j.jelechem.2017.12.060
Caux PY, Kent RA, Fan GT, Stephenson GL (1996) Environmental fate and effects of chlorothalonil: a canadian perspective. Crit Rev Environ Sci Technol 26(1):45–93. https://doi.org/10.1080/10643389609388486
Chaves A, Shea D, Danehower D (2008) Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS. Chemosphere 71(4):629–638. https://doi.org/10.1016/j.chemosphere.2007.11.015
Dhas DA, Joe IH, Roy SDD, Freeda TH (2010) DFT computations and spectroscopic analysis of a pesticide: chlorothalonil. Spectroc Acta Pt A 77(1):36–44. https://doi.org/10.1016/j.saa.2010.04.020
Du PF, Jin MJ, Zhang C, Chen G, Cui XY, Zhang YD, Zhang YX, Zou P, Jiang ZJ, Cao XL, She YX, Jin F, Wang J (2018) Highly sensitive detection of triazophos pesticide using a novel bio-bar-code amplification competitive immunoassay in a micro well plate-based platform. Sens Actuator B 256:457–464. https://doi.org/10.1016/j.snb.2017.10.075
Fang H, Zhang X, Zhang SJ, Liu L, Zhao YM, Xu HJ (2015) Ultrasensitive and quantitative detection of paraquat on fruits skins via surface-enhanced Raman spectroscopy. Sens Actuator B 213:452–456. https://doi.org/10.1016/j.snb.2015.02.121
Harshit D, Charmy K, Nrupesh P (2017) Organophosphorus pesticides determination by novel HPLC and spectrophotometric method. Food Chem 230:448–453. https://doi.org/10.1016/j.foodchem.2017.03.083
Hu GS, Han DF, Jia GQ, Chen T, Feng ZC, Li C (2009) Coadsorption of trimethyl phosphine and thiocyanate on colloidal silver: a SERS study combined with theoretical calculations. J Raman Spectrosc 40(4):387–393. https://doi.org/10.1002/jrs.2137
Jung D, Jeon K, Yeo J, Hussain S, Pang Y (2017) Multifaceted adsorption of alpha-cyano-4-hydroxycinnamic acid on silver colloidal and island surfaces. Appl Surf Sci 425:63–68. https://doi.org/10.1016/j.apsusc.2017.06.276
Khan MM, Cho MH (2018) Positively charged gold nanoparticles for hydrogen peroxide detection. BioNanoScience 8(2):537–543. https://doi.org/10.1007/s12668-018-0503-x
Lee PC, Meisel D (1982) Adsorption and surface-enhanced Raman of dyes on silver and gold sols. J Phys Chem 86(17):3391–3395. https://doi.org/10.1021/j100214a025
Liu YD, Zhang YX, Wang HY, Ye B (2016) Detection of pesticides on navel orange skin by surface-enhanced Raman spectroscopy coupled with Ag nanostructures. Int J Agric Biol Eng 9(2):179–185. https://doi.org/10.3965/j.ijabe.20160902.1960
Mi S, Ji L, Yu H, Guo Y, Cheng Y, Yang F, Yao W, Xie Y (2021) Zero-background surface-enhanced Raman scattering detection of cymoxanil based on the change of the cyano group after ultraviolet irradiation. J Agric Food Chem 69(1):520–527. https://doi.org/10.1021/acs.jafc.0c06231
Sheng E, Lu Y, Tan Y, Xiao Y, Li Z, Dai Z (2020) Ratiometric fluorescent quantum dot-based biosensor for chlorothalonil detection via an inner-filter effect. Anal Chem 92(6):4364–4370. https://doi.org/10.1021/acs.analchem.9b05199
Sherrard RM, Murray-Gulde CL, Rodgers JH, Shah YT (2003) Comparative toxicity of chlorothalonil: ceriodaphnia dubia and pimephales promelas. Ecotox Environ Saf 56(3):327–333. https://doi.org/10.1016/s0147-6513(02)00073-8
Wang C, Li XM, Peng T, Wang ZH, Wen K, Jiang HY (2017) Latex bead and colloidal gold applied in a multiplex immunochromatographic assay for high-throughput detection of three classes of antibiotic residues in milk. Food Control 77:1–7. https://doi.org/10.1016/j.foodcont.2017.01.016
Wu YX, Liang P, Dong QM, Bai Y, Yu Z, Huang J, Zhong Y, Dai YC, Ni DJ, Shu HB, Pittman CU (2017) Design of a silver nanoparticle for sensitive surface enhanced Raman spectroscopy detection of carmine dye. Food Chem 237:974–980. https://doi.org/10.1016/j.foodchem.2017.06.057
Xie YF, Hu Q, Zhao MY, Cheng YL, Guo YH, Qian H, Yao WR (2018) Simultaneous determination of erythromycin, tetracycline, and chloramphenicol residue in raw milk by molecularly imprinted polymer mixed with solid-phase extraction. Food Anal Methods 11(2):374–381. https://doi.org/10.1007/s12161-017-1008-x
Xu ML, Gao Y, Han XX, Zhao B (2017) Detection of pesticide residues in food using surface-enhanced raman spectroscopy: a review. J Agric Food Chem 65(32):6719–6726. https://doi.org/10.1021/acs.jafc.7b02504
Xu XH, Liu XM, Zhang L, Mu Y, Zhu XY, Fang JY, Li SP, Jiang JD (2018) Bioaugmentation of chlorothalonil-contaminated soil with hydrolytically or reductively dehalogenating strain and its effect on soil microbial community. J Hazard Mater 351:240–249. https://doi.org/10.1016/j.jhazmat.2018.03.002
Yu H, Zhong Q, Xie Y, Guo Y, Cheng Y, Yao W (2020) Kinetic study on the generation of furosine and pyrraline in a Maillard reaction model system of d-glucose and l-lysine. Food Chem 317:126458. https://doi.org/10.1016/j.foodchem.2020.126458
Zhang Y, Liu JY, Ahn JW, Xiao TH, Li ZY, Qin D (2017) Observing the overgrowth of a second metal on silver cubic seeds in solution by surface-enhanced raman scattering. ACS Nano 11(5):5080–5086. https://doi.org/10.1021/acsnano.7b01924
Zhang H, Zhang W, Gao X, Man P, Sun Y, Liu C, Li Z, Xu Y, Man B, Yang C (2019) Formation of the AuNPs/GO@MoS2/AuNPs nanostructures for the SERS application. Sens. Actuators B 282:809–817. https://doi.org/10.1016/j.snb.2018.10.095
The following funding sources are gratefully acknowledged: National Key R&D Program of China (2018YFC1602300), National Nature Science Foundation of China (32001627), Science and Technology Project of Market Supervision Administration of Jiangsu Province (KJ204132), Key R&D Program of Jiangsu Province (BE2019362), the Fundamental Research Funds for the Central Universities (JUSRP11904 and JUSRP321014), National first-class discipline program of Food Science and Technology (JUFSTR20180509). The first author would like to thank the financial support from High-level Innovation and Entrepreneurship Talents Introduction Program of Jiangsu Province (Su Talent Office  No. 20).
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Yu, H., Xu, L., Yang, F. et al. Rapid Surface-Enhanced Raman Spectroscopy Detection of Chlorothalonil in Standard Solution and Orange Peels with Pretreatment of Ultraviolet Irradiation. Bull Environ Contam Toxicol 107, 221–227 (2021). https://doi.org/10.1007/s00128-021-03258-9
- UV irradiation
- C≡N bond
- Orange peels