Combining gold nanoparticle-based headspace single-drop microextraction and a paper-based colorimetric assay for selenium determination

  • Neda Bagheri
  • Mohammad SarajiEmail author
Research Paper


A novel method combining headspace single-drop microextraction with a paper-based colorimetric assay was developed. Headspace single-drop microextraction using a microdrop containing unmodified gold nanoparticles (AuNPs) as both the extractant and the colorimetric probe was used for the sensitive and selective determination of Se(IV). The method relies on the color change of the microdrop solution caused by the adsorption of in situ-generated hydrogen selenide on the surface of AuNPs. Following extraction, the microdrop was spotted onto cellulose paper, and scanometric-assisted digital image analysis was used for selenium quantification. The analytical variables affecting the method sensitivity, including the drop volume, the concentrations of KBH4, HCl, and AuNP solutions, and the extraction time, were studied. Under the optimal conditions, a linear correlation between the colorimetric signal and Se(IV) concentration in the range from 15–100 μg L−1 with a limit of quantification of 12 μg L−1 was achieved. The repeatability of the method was studied by the calculation of intraday and interday precision for the standard solutions at concentrations of 20 and 70 μg L-1. The batch-to-batch reproducibility of the AuNPs synthesized under the same conditions was also assessed. The relative standard deviations were less than 7%. The method provided satisfactory results for the determination of selenium in real samples.


Headspace single-drop microextraction Hydride generation Gold nanoparticles Paper-based colorimetric assay Scanometric detection Selenium 



We acknowledge financial support for this study from the Research Council of Isfahan University of Technology and the Center of Excellence in Sensor and Green Chemistry.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

216_2019_2106_MOESM1_ESM.pdf (121 kb)
ESM 1 (PDF 121 kb)


  1. 1.
    World Health Organization. Guidelines for drinking-water quality, fourth ed: incorporating first addendum. 2017.Google Scholar
  2. 2.
    Schloske L, Waldner H, Marx F. Optimisation of sample pre-treatment in the HG-AAS selenium analysis. Anal. Bioanal. Chem. 2002;372(5-6):700–4.CrossRefGoogle Scholar
  3. 3.
    Kratzer J, Dědina J. Arsine and selenium hydride trapping in a novel quartz device for atomic-absorption spectrometry. Anal. Bioanal. Chem. 2007;388(4):793–800.CrossRefGoogle Scholar
  4. 4.
    Liang J, Wang Q, Huang B. Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO2 photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry. Anal. Bioanal. Chem. 2005;381(2):366–72.CrossRefGoogle Scholar
  5. 5.
    Tyburska A, Jankowski K, Rodzik A. Determination of arsenic and selenium by hydride generation and headspace solid phase microextraction coupled with optical emission spectrometry. Spectrochim. Acta, Part B. 2011;66:517–21.CrossRefGoogle Scholar
  6. 6.
    Mester Z, Sturgeon RE, Lam JW. Sampling and determination of metal hydrides by solid phase microextraction thermal desorption inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom. 2000;15:1461–5.CrossRefGoogle Scholar
  7. 7.
    Fragueiro S, Lavilla I, Bendicho C. Hydride generation-headspace single-drop microextraction-electrothermal atomic absorption spectrometry method for determination of selenium in waters after photoassisted prereduction. Talanta. 2006;68:1096–101.CrossRefGoogle Scholar
  8. 8.
    Ullah N, Mansha M, Khan I, Qurashi A. Nanomaterial-based optical chemical sensors for the detection of heavy metals in water: eecent advances and challenges. Trends Anal. Chem. 2018;100:155–66.CrossRefGoogle Scholar
  9. 9.
    Xu F, Hu J, Zhang J, Hou X, Jiang X. Nanomaterials in speciation analysis of mercury, arsenic, selenium, and chromium by analytical atomic/molecular spectrometry. Appl. Spectrosc. Rev. 2017;53:333–48.CrossRefGoogle Scholar
  10. 10.
    Huang S, Jin Y, Cao G, Tian Y, Xu K, Hou X. A silver nanoparticle-based colorimetric assay of trace selenium with hydride generation for sample introduction. Microchem. J. 2018;141:258–63.CrossRefGoogle Scholar
  11. 11.
    Piriya VSA, Joseph P, Daniel SCGK, Lakshmanan S, Kinoshita T, Muthusamy S. Colorimetric sensors for rapid detection of various analytes. Mater. Sci. Eng. C. 2017;78:1231–45.CrossRefGoogle Scholar
  12. 12.
    Sabela M, Balme S, Bechelany M, Janot JM, Bisetty KA. Review of gold and silver nanoparticle-based colorimetric sensing assays. Adv. Eng. Mater. 2017;19:1700270.CrossRefGoogle Scholar
  13. 13.
    Wang P, Lin Z, Su X, Tang Z. Application of Au based nanomaterials in analytical science. Nano Today. 2017;12:64–97.CrossRefGoogle Scholar
  14. 14.
    Yuan Z, Hu CC, Chang HT, Lu C. Gold nanoparticles as sensitive optical probes. Analyst. 2016;141:1611–26.CrossRefGoogle Scholar
  15. 15.
    Zhang Y, McKelvie ID, Cattrall RW, Kolev SD. Colorimetric detection based on localised surface plasmon resonance of gold nanoparticles: Merits, inherent shortcomings and future prospects. Talanta. 2016;152:410–22.CrossRefGoogle Scholar
  16. 16.
    Elahi N, Kamali M, Baghersad MH. Recent biomedical applications of gold nanoparticles: a review. Talanta. 2018;184:537–56.CrossRefGoogle Scholar
  17. 17.
    Abbasi-Ahd A, Shokoufi N, Kargosha K. Headspace single-drop microextraction coupled to microchip-photothermal lens microscopy for highly sensitive determination of captopril in human serum and pharmaceuticals. Microchim. Acta. 2017;184:2403–9.CrossRefGoogle Scholar
  18. 18.
    Tolessa T, Tan ZQ, Yin YG, Liu JF. Single-drop gold nanoparticles for headspace microextraction and colorimetric assay of mercury (II) in environmental waters. Talanta. 2018;176:77–84.CrossRefGoogle Scholar
  19. 19.
    Costas-Mora I, Romero V, Pena-Pereira F, Lavilla I, Bendicho C. Quantum dot-based headspace single-drop microextraction technique for optical sensing of volatile species. Anal. Chem. 2011;83:2388–93.CrossRefGoogle Scholar
  20. 20.
    Akyazi T, Basabe-Desmonts L, Benito-Lopez F. Review on microfluidic paper-based analytical devices towards commercialisation. Anal. Chim. Acta. 2018;1001:1–17.CrossRefGoogle Scholar
  21. 21.
    Bagheri N, Cinti S, Caratelli V, Massoud R, Saraji M, Moscone D, et al. A 96-well wax printed Prussian Blue paper for the visual determination of cholinesterase activity in human serum. Biosens. Bioelectron. 2019;134:97–102.CrossRefGoogle Scholar
  22. 22.
    Huang K, Xu K, Zhu W, Yang L, Hou X, Zheng C. Hydride generation for headspace solid-phase extraction with CdTe quantum dots immobilized on paper for sensitive visual detection of selenium. Anal. Chem. 2016;88:789–95.CrossRefGoogle Scholar
  23. 23.
    Saraji M, Bagheri N. Paper-based headspace extraction combined with digital image analysis for trace determination of cyanide in water samples. Sens. Actuators B. 2018;270:28–34.CrossRefGoogle Scholar
  24. 24.
    Cao G, Xu F, Wang S, Xu K, Hou X, Wu P. Gold nanoparticle-based colorimetric assay for selenium detection via hydride generation. Anal. Chem. 2017;89:4695–700.CrossRefGoogle Scholar
  25. 25.
    Sigrist M, Brusa L, Campagnoli D, Beldomenico H. Determination of selenium in selected food samples from Argentina and estimation of their contribution to the Se dietary intake. Food Chem. 2012;134:1932–7.CrossRefGoogle Scholar
  26. 26.
    Mackey E-SMA. Chemosensitization of cancer cells via gold nanoparticle-induced cell cycle regulation. Photochem Photobiol. 2014;90:306–12.CrossRefGoogle Scholar
  27. 27.
    National Institute for Occupational Safety and Health. Hydrogen selenide. Accessed Jun 2019.
  28. 28.
    Nuttall KL, Allen FS. Kinetics of the reaction between hydrogen selenide ion and oxygen. Inorg. Chim. Acta. 1984;91:243–6.CrossRefGoogle Scholar
  29. 29.
    Revanasiddappa HD. Kumar TNK. A facile spectrophotometric method for the determination of selenium. Anal. Sci. 2001;17:1309–12.CrossRefGoogle Scholar
  30. 30.
    Revanasiddappa HD, Kiran Kumar TN. Spectrophotometric determination of selenium by use of thionin. Anal. Bioanal. Chem. 2002;374:1121–4.CrossRefGoogle Scholar
  31. 31.
    Kartal Ş, Oymak T, Tokalıoǧlu Ş. Spectrophotometric determination of selenium(IV) with 4-methyl-o-phenylenediamine based on piazselenol formation. J. Anal. Chem. 2010;65:1221–7.CrossRefGoogle Scholar
  32. 32.
    Chen YH, Zhang YN, Tian FS. Determination of selenium via the fluorescence quenching effect of selenium on hemoglobin-catalyzed peroxidative reaction. Luminescence. 2015;30:263–8.CrossRefGoogle Scholar
  33. 33.
    Liang S, Chen J, Pierce DT, Zhao JX. A turn-on fluorescent nanoprobe for selective determination of selenium(IV). ACS Appl. Mater. Interfaces. 2013;5:5165–73.CrossRefGoogle Scholar
  34. 34.
    Feng G, Dai Y, Jin H, Xue P, Huan Y, Shan H, et al. A highly selective fluorescent probe for the determination of Se(IV) in multivitamin tablets. Sens. Actuators B. 2014;193:592–8.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryIsfahan University of TechnologyIsfahanIran

Personalised recommendations