Fluorescent monitoring of copper ions release from the surface of functional materials using biocompatible chemosensor molecules

A.M. Eremenko; I.S. Petryk; N.P. Smirnova; A.P. Naumenko

doi:10.15407/hftp17.03.358

Authors

A.M. Eremenko Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
I.S. Petryk Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine https://orcid.org/0000-0001-5244-1519
N.P. Smirnova Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine
A.P. Naumenko Taras Shevchenko National University of Kyiv

DOI:

https://doi.org/10.15407/hftp17.03.358

Keywords:

fluorescence, acridine orange, copper ions, sodium dodecyl sulfate, Stern-Volmer function

Abstract

The use of organic dyes or biomolecules that fluoresce under the action of UV or visible light – fluorescent chemosensors – allows for high-precision quantitative assessment of the level of metal ions in water or biological fluids in living cells by quenching their fluorescence when interacting with transition metal ions, in particular Cu²⁺. The fluorescence of acridine orange (AO) when interacting with a metal ion is quenched in proportion to the number of interacting ions. according to the Stern-Volmer function. The dependence of the specific amount of copper ions released from the tissue surface into the aqueous solution of AO and sodium dodecyl sulfate (SDS), calculated from the AO fluorescence decay spectra, is nonlinear. Its shape indicates that both mechanisms of fluorescence quenching are present in the system: dynamic and static. It is shown that in the presence of SDS micelles at pH ~ 8, the efficiency of fluorescence quenching is significantly increased and no re-adsorption of copper ions on the surface of the fabric is observed, which allows such a determination to be carried out in situ, directly in biological environments. This method makes it possible to assess quantitatively the dynamics of desorption of metal ions that have bactericidal properties over time and determine the optimal time for using wound dressings (powders, hydrogels, textiles, films, and other systems with action based on the release of ions of copper and other heavy metals).

References

1. Lakowicz J.R. Principles of fluorescence spectroscopy. 3rd edn. (Springer, 2006). https://doi.org/10.1007/978-0-387-46312-4

2. Goyal A.K., Nigam A. Sensors for toxic metal ion detection in aquatic environment: current status and future perspectives. Discov. Appl. Sci. 2025. 7: 1405. https://doi.org/10.1007/s42452-025-07936-9

3. Rayati S., Akbari Jami M., Ghasemi J.B. A selective fluorescent sensor for Cu(II) ion based on porphyrins supported onto multiwall carbon nanotubes. Inorg. Chem. Commun. 2025. 180(1): 114998. https://doi.org/10.1016/j.inoche.2025.114998

4. Petrik I., Eremenko A., Naumenko A., Rudenko A. Effect of silver and copper nanoparticles on adsorption and fluorescence of tryptophan on the surface of bactericidal textile. Appl. Nanosci. 2020. 10: 2557. https://doi.org/10.1007/s13204-020-01315-z

5. Kr?mer R. Fluorescent Chemosensors for Cu2+ Ions: Fast, Selective, and Highly Sensitive. Angew. Chem. Int. Ed. 1998. 37(6): 772. https://doi.org/10.1002/(SICI)1521-3773(19980403)37:6<772::AID-ANIE772>3.3.CO;2-Q

6. Linder M.C., Hazegh-Azam M. Copper biochemistry and molecular biology. Am. J. Clin. Nutr. 1996. 63(5): 797S. https://doi.org/10.1093/ajcn/63.5.797

7. Turnlund J.R. Copper. In: Shils M.E., Shike M., Ross A.C., Caballero B., Cousins R.J., eds. Modern Nutrition in Health and Disease. 10th ed. (Philadelphia: Lippincott Williams & Wilkins, 2006).

8. Prohaska J.R. Copper. In: Erdman J.W., Macdonald I.A., Zeisel S.H., eds. Present Knowledge in Nutrition. 10th ed. (Ames: Wiley-Blackwell, 2012).

9. Prohaska J.R. Impact of copper limitation on expression and function of multicopper oxidases (ferroxidases). Adv. Nutr. 2011. 2(2): 89. https://doi.org/10.3945/an.110.000208

10. Hua X.M., Gersten J.I. Theory of energy transfer between molecules near solid state particles. J. Chem. Phys. 1985. 83(7): 3650. https://doi.org/10.1063/1.449120

11. Mukha Yu., Eremenko A., Smirnova N., Valakh M., Dzhagan V. Enhancement of absorption and fluorescence of rhodamine 6G molecules near gold nanoparticles in a SiO2 matrix. Him. Fiz. Tehnol. Poverhni. 2011. 2(3): 284.

12. Jain P.K., Lee K.S., El-Sayed I.H., El-Sayed M.A. Calculated absorption and scattering properties of gold nanoparticles of different shape and composition: Applications in biological imaging and biomedicine. J. Phys. Chem. B. 2006. 110(14): 7238. https://doi.org/10.1021/jp057170o

13. Eremenko A., Smirnova N., Mukha I., Naumenko A., Belyi N., Hayden S.C. Effect of gold nanoparticles on an aerosil surface on the fluorescence and Raman spectra of adsorbed tryptophan. Theor. Exp. Chem. 2012. 48(1): 54. https://doi.org/10.1007/s11237-012-9242-1

14. Petrik I.S., Eremenko A.M., Naumenko A.P., Rudenko A.V. Effect of silver and copper nanoparticles on adsorption and fluorescence of tryptophan on the surface of bactericidal textile. Appl. Nanosci. 2020. 10: 2557. https://doi.org/10.1007/s13204-020-01315-z

15. Eremenko A.M., Petrik I.S., Naumenko A.P. Concentration-dependent fluorescence of quercetin in aqueous solutions of ions and colloids of silver nanoparticles. In: Proceedings of the Ukrainian conference with international participation «Chemistry, physics and technology of surface». 2023. P. 125.

16. Malovytsia U., Zhytniakivska O., Yeltsov K., Vus K., Trusova V., Kirilova E., Gorbenko G. Fluorescent Detection of Heavy Metal Ions Using Benzanthrone Dye. East European Journal of Physics. 2025. 3: 523. https://doi.org/10.26565/2312-4334-2025-3-58

17. Luk C.K. Quenching of the emission of tryptophan, tyrosine, and serum albumins by cupric ion. Biopolymers. 1971. 10(7): 1229. https://doi.org/10.1002/bip.360100712

18. Liu S., Wang Y.-M., Han J. Fluorescent chemosensors for copper (II) ion: Structure, mechanism and application. J. Photochem. Photobiol., C. 2017. 32: 78. https://doi.org/10.1016/j.jphotochemrev.2017.06.002

19. Badran I., Riyaz N.S. The mechanism of fluorescence quenching of naphthalimide, A/C leak detector by copper(II). Chemistry. 2023. 17: 69. https://doi.org/10.1186/s13065-023-00987-2

20. De Santis G., Fabbrizzi L., Licchelli M., Mangano C., Sacchi D., Sardone N. A fluorescent chemosensor for the copper(II) ion. Inorg. Chim. Acta. 1997. 257(1): 69. https://doi.org/10.1016/S0020-1693(96)05452-7

21. Li P., Duan X., Chen Z., Liu Y., Xie T., Fang L., Li X., Yin M., Tang B. A near-infrared fluorescent probe for detecting copper(II) with high selectivity and sensitivity and its biological imaging applications. Chem. Commun. 2011. 47(27): 7755. https://doi.org/10.1039/c1cc11885d

22. Taki M., Iyoshi S., Ojida A., Hamachi I., Yamamoto Y. Development of Highly Sensitive Fluorescent Probes for Detection of Intracellular Copper(I) in Living Systems. J. Am. Chem. Soc. 2010. 132(17): 5938. https://doi.org/10.1021/ja100714p

23. Wu S.-P., Wang T.-H., Liu S.-R. A highly selective turn-on fluorescent chemosensor for copper (II) ion. Tetrahedron. 2010. 66(51): 9655. https://doi.org/10.1016/j.tet.2010.10.054

24. Nikolaev S.V., Pojar V.V., Dziubenko M.I., Nikolaev K.S. Effect of Silver NPs on the Fluorescence Intensity of Rhodamine 6G and Sulforhodamine 101. Radiophysics and electronics. 2016. 7(2): 53. [in Ukrainian]. https://doi.org/10.15407/rej2016.02.053

25. Zanker V.Z.Z. On the detection of defined reversible associates ("reversible polymers") of acridine orange through absorption and fluorescence measurements in aqueous solution. Phys. Chem. 1952. 199: 225. https://doi.org/10.1515/zpch-1952-19918

26. Wyn?Jones E., Gormally J. (editors). Aggregation Processes in Solution. (Amsterdam: Elsevier, 1983).

27. Schreiber J.P., Daune M.P. Fluorescence of complexes of acridine dye with synthetic polydeoxyribonucleotides: A physical model of frameshift mutation. J. Mol. Biol. 1974. 83(4): 487. https://doi.org/10.1016/0022-2836(74)90509-9

28. Guo X.-Q., Zhang Z.-L., Zhao Y.-B., Wangs D.-Y., Xu J.-G. DNA-Dye Fluorescence Enhancement Based on Shifting the Dimer-Monomer Equilibrium of Fluorescent Dye. Appl. Spectrosc. 1997. 51(7):1002. https://doi.org/10.1366/0003702971941386

29. Zimmermann F., Hossenfelder B., Panitz J.C., Wokaun A. SERRS study of acridine orange and its binding to DNA strands. J. Phys. Chem. 1994. 98(48): 12796. https://doi.org/10.1021/j100099a051

30. Falcone R.D., Correa N.M., Biasutti M.A., Silber J.J. Acid-Base and Aggregation Processes of Acridine Orange Base in n-Heptane/AOT/Water Reverse Micelles. Langmuir. 2002. 18(6): 2039. https://doi.org/10.1021/la011411b

31. Surovceva N.I., Smirnova N.P., Fesenko T.V., Gnatyuk Yu.I., Eremenko A.M., Pokrovsksy V.A. Spectroscopic and mass-spectrometric study of acridine orange photodegradation on the surface of mesoporous SiO2, TiO2/SiO2 and SiO2 films. J. Adv. Oxid. Technol. 2008. 11: 551. https://doi.org/10.1515/jaots-2008-0315

32. Davies D.B., Veselkov D.A., Kodintsev V.V., Evstigneev M.P., Veselkov A.N. 1H NMR investigation of the hetero-association of aromatic molecules in aqueous solution: factors involved in the stabilization of complexes of daunomycin and acridine drugs. Mol. Phys. 2000. 98(23): 1961. https://doi.org/10.1080/00268970009483399

33. Amado M., Ramos A.P., Silva E.R., Borisevitch I.E. Quenching of acridine orange fluorescence by salts in aqueous solutions: Effects of aggregation and charge transfer. J. Luminescence. 2016. 178: 288. https://doi.org/10.1016/j.jlumin.2016.06.006

34. Bandyopadhyay P., Ghosh A.K., Bandyopadhyay S. Brij-micelle and polyacrylic acid interaction investigated by Cu2+-induced pyrene fluorescence: Effect of brij-micelle structure. Chem. Phys. Lett. 2009. 476(4-6): 244. https://doi.org/10.1016/j.cplett.2009.06.023

35. Ghosh A.K., Samanta A., Bandyopadhyay P. Cu2+-Induced Micellar Charge Selective Fluorescence Response of Acridine Orange: Effect of Micellar Charge, pH, and Mechanism. J. Phys. Chem. B. 2011. 115(41): 11823. https://doi.org/10.1021/jp206644b

36. Ghosh A.K., Samanta A., Bandyopadhyay P. Anionic micelle-induced fluorescent sensor activity enhancement of acridine orange: Mechanism and pH effect. Chem. Phys. Lett. 2011. 507(1-3): 162. https://doi.org/10.1016/j.cplett.2011.03.053

37. Okazaki M., Toriyama K., Tomura S., Kodama T., Watanabe E. A Monolayer Complex of Cu2(OH)3C12H25SO4 Directly Precipitated from an Aqueous SDS Solution. Inorg. Chem. 2000. 39(13): 2855. https://doi.org/10.1021/ic000088h

38. Schuster Th. Fluorescence Quenching upon Binding of Copper Ions in Dye?Doped and Ligand?Capped Polymer Nanoparticles: A Simple Way to Probe the Dye Accessibility in Nano?Sized Templates. Adv. Funct. Mater. 17(15): 2746. https://doi.org/10.1002/adfm.200601056

39. Patent UA 102532. Eremenko A.M., Smirnova N.P., Petrik I.S., Surmasheva O.V., Korchak G.I., Romanenko L.I. Method for obtaining bactericidal material based on nanoscale silver and copper composite. 2015.

40. Patent UA 146170. Petrik I.S., Eremenko A.M., Smirnova N.P., Rudenko A.V., Tretyak V.V., Bavina O.M., Rybalko S.L., Starosila D.B. Method for obtaining bactericidal material with antiviral and bactericidal action based on a nanoscale composite of silver and copper. 2020.

41. Eremenko A., Petrik I., Rudenko A., Tananaiko O., Lelyushok S., Ishchenko N. The peculiarities of Ag and Cu ions release from bactericidal textiles in water and their influence on spectral, electrical and biocide properties of textile. J. Nanosci. Nanomed. 2018. 2(1): 20.

42. Eremenko A., Petrik I., Rudenko A., Tananaiko O., Kyrpel T., Ishenko M. Ion Release and Bactericidal Activity of Ag/Tryptophan and Ag/Cu/Tryptophan Complexes in the Structure of Cotton Tissue. J. Nanomed. 2020. 3(1): 1025. https://doi.org/10.33582/2578-8760/1025