Skip to main content
Log in

Colorimetric detection of glutathione by an anionic pyridylazo dye-based Cu2+ complex in the presence of a cationic polyelectrolyte

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

The colorimetric sensing system for glutathione (GSH) was constructed by the mixture of three components, an anionic dye 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol (BrPAPS), a cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC), and Cu2+ in an aqueous solution. BrPAPS was complexed with Cu2+ in a 2:1 molar ratio via the electrostatic interaction with PDADMAC (BrPAPS2-Cu2+-PDADMAC). The addition of GSH to the complex caused a hypsochromic shift with a distinct colorimetric response from red to yellow since the regeneration of the original BrPAPS through the interaction between GSH and Cu2+ in a 1:1 stoichiometry. BrPAPS2-Cu2+-PDADMAC allowed the selective recognition of GSH over other amino acids and the detection suffer little interference from them. Hence, BrPAPS2-Cu2+-PDADMAC provides efficient colorimetric sensing of GSH with high selectivity and sensitivity in pure aqueous media.

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Scheme 2
Fig. 6
Fig. 7

Similar content being viewed by others

Data availability

Not applicable.

References

  1. Cooper, A.J.: Biochemistry of sulfur-containing amino acids. Annu. Rev. Biochem. 52, 187–222 (1983)

    Article  CAS  PubMed  Google Scholar 

  2. Dalton, T.P., Shertzer, H.G., Puga, A.: Annu. Rev. Pharmacol. Toxicol. 39, 67–101 (1999)

    Article  CAS  PubMed  Google Scholar 

  3. Meister, A., Anderson, M.E.: Glutathione. Ann. Rev. Biochem. 52, 711–760 (1983)

    Article  CAS  PubMed  Google Scholar 

  4. Townsend, D.M., Tew, K.D., Tapiero, H.: The importance of glutathione inhuman disease. Biomed. Pharmacother. 57, 145–155 (2003)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Shi, C., Liu, J., Wu, F., Yew, D.T.: Ginkgo biloba extract in Alzheimer’s disease: From action mechanisms to medical practice. Int. J. Mol. Sci. 11, 107–123 (2010)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Li, S., Tan, H.Y., Wang, N., Zhang, Z.J., Lao, L., Wong, C.W., Feng, Y.: The role of oxidative stress and antioxidants in liver diseases. Int. J. Mol. Sci. 16, 26087–26124 (2015)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. Harfield, J.C., Batchelor-McAuley, C., Compton, R.G.: Electrochemical determination of glutathione: A review. Analyst. 137, 2285–2296 (2012)

    Article  CAS  PubMed  Google Scholar 

  8. Wei, L., Song, Y., Liu, P., Kang, X.: Polystyrene nanofibers capped with copper nanoparticles for selective extraction of glutathione prior to its determination by HPLC. Microchim. Acta. 185, 321–328 (2018)

    Article  Google Scholar 

  9. Yu, J., Li, C., Shen, S., Liu, X., Peng, Y., Zheng, J.: Mass spectrometry based detection of glutathione with sensitivity for single-cell analysis. Rapid Commun. Mass. Spectrom. 29, 681–689 (2015)

    Article  CAS  PubMed  Google Scholar 

  10. Hou, X., Guo, X., Chen, B., Liu, C., Gao, F., Zhao, J., Wang, J.: Rhodamine-based fluorescent probe for highly selective detection of glutathione over cysteine and homocysteine. Sens. and Actuators B: Chem. 209, 838–845 (2015)

    Article  CAS  Google Scholar 

  11. Liu, X.L., Niu, L.Y., Chen, Y.Z., Zheng, M.L., Yang, Y., Yang, Q.Z.: A mitochondria targeting fluorescent probe for the selective detection of glutathione in living cells. Org. Biomol. Chem. 15, 1072–1075 (2017)

    Article  CAS  PubMed  Google Scholar 

  12. Lee, S., Li, J., Zhou, X., Yin, J., Yoon, J.: Recent progress on the development of glutathione (GSH) selective fluorescent and colorimetric probes. Coordin Chem. Rev. 366, 29–68 (2018)

    Article  CAS  Google Scholar 

  13. Jangi, S.R.H., Akhond, M., Absalan, G.: A novel selective and sensitive multinanozyme colorimetric method for glutathione detection by using an indamine polymer. Anal. Chim. Acta. 1127, 1–8 (2020)

    Article  Google Scholar 

  14. Jiang, C., Zhang, C., Song, J., Ji, X., Wang, W.: Cytidine-gold nanoclusters as peroxidase mimetic for colorimetric detection of glutathione (GSH), glutathione disulfide (GSSG) and glutathione reductase (GR). Spectrochim. Acta Pt A: Mol. Spectrosc. 250, 119316 (2021)

    Article  CAS  Google Scholar 

  15. Wu, J., Kwon, B., Liu, W., Anslyn, E.V., Wang, P., Kim, J.S.: Chromogenic/fluorogenic ensemble chemosensing systems. Chem. Rev. 115, 7893–7943 (2015)

    Article  CAS  PubMed  Google Scholar 

  16. Nguyen, B.T., Anslyn, E.V.: Indicator–displacement assays. Coord. Chem. Rev. 250, 3118–3127 (2006)

    Article  CAS  Google Scholar 

  17. Inoue, K., Aikawa, S., Fukushima, Y.: Colorimetric detection of oxalate in aqueous solution by a pyrogallol red-based Cu2+ complex. Luminescence. 33, 277–281 (2018)

    Article  CAS  PubMed  Google Scholar 

  18. Inoue, K., Aikawa, S., Fukushima, Y.: Colorimetric detection of pyrophosphate in aqueous solution by pyrogallol red-based Zn2+ complex in the presence of poly(diallyldimethylammonium chloride), Polym. Bull. 76, 1641–1649 (2018)

    Google Scholar 

  19. Inoue, K., Aikawa, S., Fukushima, Y.: Colorimetric chemosensor based on a carminic acid and Pb2+ complex for selective detection of cysteine over homocysteine and glutathione in aqueous solution. J. Incl. Phenom. Macrocycl. Chem. 90, 105–110 (2017)

    Article  Google Scholar 

  20. Nagae, T., Aikawa, S., Inoue, K., Fukushima, Y.: Colorimetric detection of histidine in aqueous solution by Ni2+ complex of a thiazolylazo dye based on indicator displacement mechanism. Tetrahedron Lett. 59, 3988–3993 (2018)

    Article  CAS  Google Scholar 

  21. Fukushima, Y., Aikawa, S.: Colorimetric chemosensor based on a Ni2+ complex of a pyridylazo dye for detection of citrate in aqueous solution. Tetrahedron Lett. 61, 151681 (2020)

    Article  CAS  Google Scholar 

  22. Fukushima, Y., Aikawa, S.: Colorimetric detection of iodide ion by a nuclear fast red-based Hg2+ complex in aqueous media. Tetrahedron Lett. 62, 152877 (2021)

    Article  Google Scholar 

  23. Fukushima, Y., Aikawa, S.: Colorimetric detection of homocysteine by a pyridylazo dye-based Cu2+ complex via indicator displacement mechanism. Anal. Biochem. 621, 114185 (2021)

    Article  CAS  PubMed  Google Scholar 

  24. Fukushima, Y., Aikawa, S.: Colorimetric sensing of histamine in aqueous solution by a system composed of alzarin complexone and Ni2+ complex via indicator displacement approach. Tetrahedron Lett. 72, 153088 (2021)

    Article  CAS  Google Scholar 

  25. Shimizu, M., Aikawa, S., Fukushima, Y.: Colorimetric detection of ATP by a chlorophosphonazo III-based Mg2+ complex in aqueous solution via indicator displacement approach. J. Fluoresc. 33, 255–260 (2023)

    Article  CAS  PubMed  Google Scholar 

  26. Kim, M.S., Jung, J.M., Kang, J.H., Ahn, H.M., Kim, P.-G., Kim, C.: A new indazole-based colorimetric chemosensor for sequential detection of Cu2+ and GSH in aqueous solution. Tetrahedron. 73, 4750–4757 (2017)

    Article  CAS  Google Scholar 

  27. You, G.R., Jang, H.J., Jo, T.G., Kim, C.: A novel displacement-type colorimetric chemosensor for the detection of Cu2+ and GSH in aqueous solution. RSC Adv. 6, 74400–74408 (2016)

    Article  CAS  Google Scholar 

  28. Horiguchi, D., Saito, M., Noda, K., Kina, K.: Water soluble pyridylazoaminophenols and pyridylazoaminobenzoic acids as highly sensitive photometric reagents for zinc, uranium, cobalt and nickel. Anal. Sci. 1, 461–465 (1985)

    Article  CAS  Google Scholar 

  29. Shijo, Y., Sakai, K.: Spectrophotometric and analogue derivative spectrophotometric determination of chromium(III) with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino) phenol. Bull. Chem. Soc. Jpn. 59, 1455–1458 (1986)

    Article  CAS  Google Scholar 

  30. Inoue, K., Aikawa, S., Sakamaki, M., Fukushima, Y.: Colorimetric Co2+ sensor based on an anionic pyridylazo dye and a cationic polyelectrolyte in aqueous solution. Polym. Int. 67, 1589–1594 (2018)

    Article  CAS  Google Scholar 

  31. Job, P.: Formation and stability of inorganic complexes in solution. Ann. Chim. 9, 113–203 (1928)

    CAS  Google Scholar 

  32. Grynkiewicz, G., Poenie, M., Tsien, R.Y.: A new generation of Ca2+ indicators with greatly improved fluorescence properties. J. Biol. Chem. 260, 3440–3450 (1985)

    Article  CAS  PubMed  Google Scholar 

  33. Michelet, F., Gueguen, R., Leroy, P., Wellman, M., Nicolas, A., Siest, G.: Blood and plasma glutathione measured in healthy subjects by HPLC: Relation to sex, aging, biological variables, and life habits. Clin. Chem. 41, 1509–1517 (1995)

    Article  CAS  PubMed  Google Scholar 

  34. Jia, H., Yang, M., Meng, Q., He, G., Wang, Y., Hu, Z., Zhang, R., Zhang, Z.: Synthesis and application of an aldazine-based fluorescence chemosensor for the sequential detection of Cu2+ and biological thiols in aqueous solution and living cells. Sensors. 16, 79–92 (2016)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  35. Hu, Y., Heo, C.H., Kim, G., Jun, E.J., Yin, J., Kim, H.M., Yoon, J.: One-photon and two-photon sensing of biothiols using a bis-pyrene-Cu(II) ensemble and its application to image GSH in the cells and tissues. Anal. Chem. 87, 3308–3313 (2015)

    Article  CAS  PubMed  Google Scholar 

  36. Yang, Y.-L., Zhang, F.-M., Wang, Y.-W., Zhang, B.-X., Fang, R., Fang, J.-G., Peng, Y.: An iminocoumarin sulfonamide based turn-on fluorescent probe for the detection of biothiols in aqueous solution. Chem. Asian J. 10, 422–426 (2015)

    Article  CAS  PubMed  Google Scholar 

  37. Li, S., Cao, D., Meng, X., Hu, Z., Li, Z., Yuan, C., Zhou, T., Han, X., Ma, W.: A novel fluorescent sensor for specific recognition of GSH based on the copper complex and its bioimaging in living cells. Bioorg. Chem. 100, 103923 (2020)

    Article  CAS  PubMed  Google Scholar 

Download references

Funding

Not applicable.

Author information

Authors and Affiliations

Authors

Contributions

MS: and YK: performed absorption measurements. SA: prepared all figures. YF: wrote the main manuscript and supervised the study. All authors reviewed the manuscript.

Corresponding author

Correspondence to Yasumasa Fukushima.

Ethics declarations

Conflict of interest

The authors declare they have no competing interests.

Ethical approval

Not applicable.

Consent to participate

Not applicable.

Consent for publication

The authors agreed for the article publication.

Additional information

Publisher’s Note

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

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 124.2 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shimizu, M., Koizumi, Y., Aikawa, S. et al. Colorimetric detection of glutathione by an anionic pyridylazo dye-based Cu2+ complex in the presence of a cationic polyelectrolyte. J Incl Phenom Macrocycl Chem 103, 123–129 (2023). https://doi.org/10.1007/s10847-023-01183-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-023-01183-4

Keywords

Navigation