Log in

Quantification and toxicokinetics of paraquat in mouse plasma and lung tissues by internal standard surface-enhanced Raman spectroscopy

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

A Correction to this article was published on 02 February 2022

This article has been updated

Abstract

Paraquat is a quaternary ammonium herbicide with an excellent herbicidal effect but is highly toxic to human and animals. Although prohibited by many countries, paraquat intoxication occurred occasionally and caused severe consequences. Rapid and accurate determination of paraquat concentration in intoxication samples is urgently needed in the clinic to promptly evaluate the prognosis of poisoning patients. Here we report an internal standard surface-enhanced Raman spectroscopy (IS-SERS) quantification method on paraquat in mouse plasma and lung tissues for the first time. One measurement per sample was fulfilled within 10 s via this IS-SERS method. Paraquat had good linearity in the range of 1 ~ 500 μg/L (plasma sample) and 1 ~ 100 μg/g (lung sample), with the LOD and LOQ of 0.5 μg/L and 0.1 μg/g (plasma sample), and 5 μg/L and 1 μg/g (lung sample), respectively. This IS-SERS method was validated according to the international guidelines and applied to a quantitative determination and the toxicokinetics on paraquat in mouse plasma and lung tissues. The results indicated that paraquat had a fast absorption rate and a slow elimination rate in mouse plasma and lung tissues. Paraquat was prone to accumulate in target organs after entering the blood. It also proved its good practical applicability in one clinical intoxication sample. Meanwhile, we unveiled an underestimation of free paraquat amount towards common biological sample pretreatment, a certain amount of paraquat bound to components with molecular weight less than 30 kDa in the plasma; we hope it could provide some interesting information for possible clinic treatment.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Canada)

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Change history

References

  1. Dinis-Oliveira RJ, Duarte JA, Sánchez-Navarro A, Remião F, Bastos ML, Carvalho F. Paraquat poisonings: mechanisms of lung toxicity, clinical features, and treatment. Crit Rev Toxicol. 2008;38(1):13–71.

    Article  CAS  Google Scholar 

  2. Sun B, Chen YG. Advances in the mechanism of paraquat-induced pulmonary injury. Eur Rev Med Pharmacol Sci. 2016;20(8):1597–602.

    CAS  PubMed  Google Scholar 

  3. Cha ES, Chang SS, Gunnell D, Eddleston M, Khang YH, Lee WJ. Impact of paraquat regulation on suicide in South Korea. Int J Epidemiol. 2016;45(2):470–9.

    Article  Google Scholar 

  4. Zyoud SH. Investigating global trends in paraquat intoxication research from 1962 to 2015 using bibliometric analysis. Am J Ind Med. 2018;61(6):462–70.

    Article  Google Scholar 

  5. Shi Y, Bai Y, Zou Y, Cai B, Liu F, Fu P, et al. The value of plasma paraquat concentration in predicting therapeutic effects of hemoperfusion in patients with acute paraquat poisoning. PLoS One. 2012;7(7):e40911.

    Article  CAS  Google Scholar 

  6. Liu XW, Ma T, Li LL, Qu B, Liu Z. Predictive values of urine paraquat concentration, dose of poison, arterial blood lactate and APACHE II score in the prognosis of patients with acute paraquat poisoning. Exp Ther Med. 2017;14(1):79–86.

    Article  CAS  Google Scholar 

  7. Koo JR, Yoon JW, Han SJ, Choi MJ, Park II, Lee YK, et al. Rapid analysis of plasma paraquat using sodium dithionite as a predictor of outcome in acute paraquat poisoning. Am J Med Sci. 2009;338(5):373–7.

    Article  Google Scholar 

  8. Koivunen ME, Gee SJ, Park EK, Lee K, Schenker MB, Hammock BD. Application of an enzyme-linked immunosorbent assay for the analysis of paraquat in human-exposure samples. Arch Environ Contam Toxicol. 2005;48(2):184–90.

    Article  CAS  Google Scholar 

  9. Yuan G, Li R, Zhao Q, Kong X, Wang Y, Wang X, et al. Simultaneous determination of paraquat and diquat in human plasma by HPLC-DAD: its application in acute poisoning patients induced by these two herbicides. J Clin Lab Anal. 2021;35(3):e23669.

    Article  CAS  Google Scholar 

  10. Ma J, Sun F, Chen B, Tu X, Peng X, Wen C, et al. Tissue metabolic changes for effects of pirfenidone in rats of acute paraquat poisoning by GC-MS. Toxicol Ind Health. 2017;33(12):887–900.

    Article  CAS  Google Scholar 

  11. Wen C, Lin F, Huang B, Zhang Z, Wang X, Ma J, et al. Metabolomics analysis in acute paraquat poisoning patients based on UPLC-Q-TOF-MS and machine learning approach. Chem Res Toxicol. 2019;32(4):629–37.

    Article  CAS  Google Scholar 

  12. Tsao YC, Lai YC, Liu HC, Liu RH, Lin DL. Simultaneous determination and quantitation of paraquat, diquat, glufosinate and glyphosate in postmortem blood and urine by LC-MS-MS. J Anal Toxicol. 2016;40(6):427–36.

    Article  CAS  Google Scholar 

  13. Ma J, Li H, Zhang J, Yan Y, Ye Q, Shao B. Determination of paraquat in serum by ultra performance liquid chromatography tandem mass spectrometry and toxicokinetics of paraquat in rat. J Hygiene Res. 2018;47(6):993–7.

    Google Scholar 

  14. Botta R, Eiamchai P, Horprathum M, Limwichean S, Chananonnawathorn C, Patthanasettakul V, et al. 3D structured laser engraves decorated with gold nanoparticle SERS chips for paraquat herbicide detection in environments. Sens Actuators B Chem. 2020;304(2):127327.1-127327.12.

    Google Scholar 

  15. Luo H, Wang X, Huang Y, Lai K, Rasco BA, Fan Y. Rapid and sensitive surface-enhanced Raman spectroscopy (SERS) method combined with gold nanoparticles for determination of paraquat in apple juice. J Sci Food Agric. 2018;98(10):3892–8.

    Article  CAS  Google Scholar 

  16. Zhu Y, Wu J, Gao H, Liu G, Tian Z, Feng J, et al. Rapid on-site detection of paraquat in biologic fluids by iodide-facilitated pinhole shell-isolated nanoparticle-enhanced Raman spectroscopy. RSC Adv. 2016;10:59919–26.

    Article  Google Scholar 

  17. Frens G. Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nat Phys Sci. 1973;241(105):20–2.

    Article  CAS  Google Scholar 

  18. European Medicines Agency. Guideline on bioanalytical method validation. http://www.ema.europa.eu/docs/en_GB/document_library/Scientific_guideline/2011/08/WC500109686.pdf (Accessed Aug 2019).

  19. Haiss W, Thanh NT, Aveyard J, Fernig DG. Determination of size and concentration of gold nanoparticles from UV-vis spectra. Anal Chem. 2007;79(11):4215–21.

    Article  CAS  Google Scholar 

  20. Zhou X, Hu Z, Yang D, **e S, Jiang Z, Niessner R, et al. Bacteria detection: from powerful SERS to its advanced compatible techniques. Adv Sci (Weinh). 2020;7(23):2001739.

    Article  CAS  Google Scholar 

  21. Fateixa S, Raposo M, Nogueira HIS, Trindade T. A general strategy to prepare SERS active filter membranes for extraction and detection of pesticides in water. Talanta. 2018;182:558–66.

    Article  CAS  Google Scholar 

  22. Koh EH, Mun C, Kim C, Park SG, Choi EJ, Kim SH, et al. M13 Bacteriophage/silver nanowire surface-enhanced Raman scattering sensor for sensitive and selective pesticide detection. ACS Appl Mater Interfaces. 2018;10(12):10388–97.

    Article  CAS  Google Scholar 

  23. Fornasaro S, Alsamad F, Baia M, Batista de Carvalho LAE, Beleites C, Byrne H, et al. Surface enhanced Raman spectroscopy for quantitative analysis: results of a large-scale European multi-instrument interlaboratory study. Anal Chem. 2020;92(5):4053–64.

    Article  CAS  Google Scholar 

  24. Liu H, Yang Z, Meng L, Sun Y, Wang J, Yang L, et al. Three-dimensional and time-ordered surface-enhanced Raman scattering hotspot matrix. J Am Chem Soc. 2014;136(14):5332–41.

    Article  CAS  Google Scholar 

  25. Li M, Wang JY, Chen QQ, Lin LH, Radjenovic P, Zhang H, et al. Background-free quantitative surface enhanced Raman spectroscopy analysis using core-shell nanoparticles with an inherent internal standard. Anal Chem. 2019;91(23):15025–31.

    Article  CAS  Google Scholar 

  26. Wang Y, Ma S, Yu H, Liu Y, Gao J, Yang L, et al. Effect of TiO2 arrays on surface enhanced Raman scattering (SERS) performance for Ag/TiO2 substrates. Nanotechnology. 2021;32(7):075708.

    Article  CAS  Google Scholar 

  27. Guo Z, Barimah AO, Guo C, Agyekum AA, Annavaram V, El-Seedi HR, et al. Chemometrics coupled 4-aminothiophenol labelled Ag-Au alloy SERS off-signal nanosensor for quantitative detection of mercury in black tea. Spectrochim Acta A Mol Biomol Spectrosc. 2020;242:118747.

    Article  CAS  Google Scholar 

  28. Lee KM, Yarbrough D, Kozman MM, Herrman TJ, Park J, Wang R, et al. A rapid and convenient screening method for detection of restricted monensin, decoquinate, and lasalocid in animal feed by applying SERS and chemometrics. Food Chem Toxicol. 2020;144:111633.

    Article  CAS  Google Scholar 

  29. Lin S, Lin X, Han S, Liu Y, Hasi W, Wang L. Flexible fabrication of a paper-fluidic SERS sensor coated with a monolayer of core-shell nanospheres for reliable quantitative SERS measurements. Anal Chim Acta. 2020;1108:167–76.

    Article  CAS  Google Scholar 

  30. Gao P, Weaver MJ. Metal-adsorbate vibrational frequencies as a probe of surface bonding: halides and pseudohalides at gold electrodes. J Phys Chem B. 1986;90(17):4057–63.

    Article  CAS  Google Scholar 

  31. Liu S, Lin L, Sun HB. Opto-thermophoretic manipulation. ACS Nano. 2021;15(4):5925–43.

    Article  CAS  Google Scholar 

  32. Subaihi A, Muhamadali H, Mutter ST, Blanch E, Ellis DI, Goodacre R. Quantitative detection of codeine in human plasma using surface-enhanced Raman scattering via adaptation of the isotopic labelling principle. Analyst. 2017;142(7):1099–105.

    Article  CAS  Google Scholar 

  33. Fang H, Zhang X, Zhang S, Liu L, Zhao Y, Xu H. Ultrasensitive and quantitative detection of paraquat on fruits skins via surface-enhanced Raman spectroscopy. Sens Actuators B Chem. 2015;213:452–6.

    Article  CAS  Google Scholar 

  34. Lopez-Ramirez MR, Guerrini L, Garcia-Ramos JV, Sanchez-Cortes S. Vibrational analysis of herbicide diquat: a normal Raman and SERS study on Ag nanoparticles. Vib Spectrosc. 2008;48(1):58–64.

    Article  CAS  Google Scholar 

  35. Chen H, Lin M, Wang C, Chang Y, Gwo S. Large-scale hot spot engineering for quantitative SERS at the single-molecule scale. J Am Chem Soc. 2015;137(42):13698–705.

    Article  CAS  Google Scholar 

  36. Yoon SC. Clinical outcome of paraquat poisoning. Korean J Intern Med. 2009;24(2):93–4.

    Article  CAS  Google Scholar 

  37. Qian J, Wu C, Wu D, Li L, Li Q, Deng T, et al. Anthrahydroquinone-2-6-disulfonate is a novel, powerful antidote for paraquat poisoning. Sci Rep. 2021;11(1):20159.

    Article  CAS  Google Scholar 

  38. Hong G, Hu L, Tang Y, Zhang T, Kang X, Zhao G, et al. Prognosis and survival analysis of paraquat poisoned patients based on improved HPLC-UV method. J Pharmacol Toxicol Methods. 2016;80:75–81.

    Article  CAS  Google Scholar 

  39. Lu H, Yu J, Wu L, **ng J, Wang J, Huang P, et al. Optimized ultra performance liquid chromatography tandem high resolution mass spectrometry method for the quantification of paraquat in plasma and urine. J Chromatogr B Analyt Technol Biomed Life Sci. 2016;1027:96–102.

    Article  CAS  Google Scholar 

  40. Ho YT, Azman N’, Loh FWY, Ong GKT, Engudar G, Kriz SA, et al. Protein corona formed from different blood plasma proteins affects the colloidal stability of nanoparticles differently. Bioconjug Chem. 2018;29(11):3923–34.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank Dr. Zhengsheng Mao in the Department of Forensic Sciences, School of Basic Medical Science, Nan**g Medical University, Jiangsu, China, for helpful experimental comparison.

Funding

This research was supported by the National Key Research and Development Program of China (No. 2018YFC1602600) and the National Natural Science Foundation of China (82072158).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Hao Sun or Lei Guo.

Ethics declarations

Ethics approval

The animal experiment was approved by the Institutional Animal Care and Use Committee of Nan**g Medical University (Jiangsu, China) with a permit number: IACUC-1905044. A clinical intoxication plasma sample was obtained from the Fifth Medical Center of Chinese PLA General Hospital, and the sample was provided with written informed consent and institutional review board and ethical approval (approval number: KY-2021-12-34-1).

Conflict of interest

The authors declare no competing interests.

Source of biological material

Male C57BL/6 J mice (8–9 weeks) were purchased from Model Animal Research Center of Nan**g University. A clinical intoxication plasma sample was provided by the Fifth Medical Center of Chinese PLA General Hospital.

Statement on animal welfare

All experiments were carried out in strict accordance with the recommendations in the Guide for the Care and Use of Laboratory Animals of Nan**g Medical University. Male C57BL/6 J mice (8–9 weeks) were kept in plastic cages with free access to water and standard diet. Mice were maintained in a temperature-controlled room (23 ± 2 °C) with a 12-h light–dark cycle and relative humidity of 50 ± 10%. They were acclimatized for at least 1 week prior to the experiment.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

The original online version of this article was revised: Unfortunately, there were some errors in table 1 and table 2 of this manuscript.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 524 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Qin, L., Zhang, X., Wu, J. et al. Quantification and toxicokinetics of paraquat in mouse plasma and lung tissues by internal standard surface-enhanced Raman spectroscopy. Anal Bioanal Chem 414, 2371–2383 (2022). https://doi.org/10.1007/s00216-022-03875-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-022-03875-1

Keywords

Navigation