THE EFFECT OF THE INTERNAL HEAVY ATOM ON SINGLET OXYGEN GENERATION IN THE PRESENCE OF PLASMONIC NANOPARTICLES

N.Kh. Ibrayev; E.P. Menshova

doi:10.31489/2025N2/5-12

Authors

DOI:

https://doi.org/10.31489/2025N2/5-12

Keywords:

heavy atom effect, intersystem crossing, singlet oxygen, nanoplasmonics, photosensitiser

Abstract

The heavy atom effect on singlet oxygen generation in the plasmon field of silver nanoparticles was investigated. The dyes rhodamine 123 and dibromrhodamine 123 in polyvinyl butyral films were used as sensibilisers. The dye films were deposited by spin-coating onto silver island films synthesised on the quartz surface. The results showed that the presence of bromine atom in the dye molecules increased the singlet oxygen generation efficiency. The calculated Stern-Follmer constants demonstrate the enhancement of molecular oxygen quenching of triplet states of dibromorhodamine 123 dye molecules in the presence of Ag nanoparticles.

References

Sagadevan A., Hwang K.C., Su M.D. (2017) Singlet oxygen-mediated selective C–H bond hydroperoxidation of ethereal hydrocarbons. Nature Communications, 8(1), 1812. https://doi.org/10.1038/s41467-017-01906-5 DOI: https://doi.org/10.1038/s41467-017-01906-5

Schmidt R. (2006). Photosensitized generation of singlet oxygen. Photochemistry and Photobiology, 82(5), 1161–1177. https://doi.org/10.1562/2006-03-03-IR-833 DOI: https://doi.org/10.1562/2006-03-03-lR-833

Ishchenko A.A., Syniugina A.T. (2023) Structure and photosensitiser ability of polymethine dyes in photodynamic therapy: A review. Theoretical and Experimental Chemistry, 58(6), 373–401. https://doi.org/10.1007/s11237-023-09754-9 DOI: https://doi.org/10.1007/s11237-023-09754-9

Singleton D. A., Hang C., Szymanski M. J., Meyer M. P., Leach A. G., Kuwata K. T., Chen J. S., Greer A., Foote C.S., Houk K.N. (2003) Mechanism of the reactions of singlet oxygen: A two-step no-intermediate mechanism. Journal of the American Chemical Society, 125(5), 1319–1328. https://doi.org/10.1021/ja027225p DOI: https://doi.org/10.1021/ja027225p

Aerssens D., Cadoni E., Tack L., Madder A. (2022) A photosensitized singlet oxygen (1O2) toolbox for bio-organic applications: Tailoring 1O2 generation for DNA and protein labelling, targeting and biosensing. Molecules, 27(3), 778. https://doi.org/10.3390/molecules27030778 DOI: https://doi.org/10.3390/molecules27030778

Bregnhøj M., Prete M., Turkovic V., Petersen A. U., Nielsen M.B., Madsen M., Ogilby P.R. (2019) Oxygen-dependent photophysics and photochemistry of prototypical compounds for organic photovoltaics: Inhibiting degradation initiated by singlet oxygen at a molecular level. Methods and Applications in Fluorescence, 8(1), 014001. https://doi.org/10.1088/2050-6120/ab4edc DOI: https://doi.org/10.1088/2050-6120/ab4edc

Pibiri I., Buscemi S., Palumbo Piccionello A., Pace A. (2018) Photochemically produced singlet oxygen: Applications and perspectives. ChemPhotoChem, 2(7), 535–547. https://doi.org/10.1002/cptc.201800076 DOI: https://doi.org/10.1002/cptc.201800076

Wang Y., Lin Y., He S., Wu S., Yang C. (2024). Singlet oxygen: Properties, generation, detection, and environmental applications. Journal of Hazardous Materials, 461, 132538. https://doi.org/10.1016/j.jhazmat. 2023.132538 DOI: https://doi.org/10.1016/j.jhazmat.2023.132538

Khan A., Alam M., Rehman S. U., Khan G. S., Khan F.A., Khan M., Zhang Y. (2019) Rhodamine-based fluorescent probes for bioimaging applications. Chemical Reviews, 119(19), 10504–10555. https://doi.org/10.1021/acs.chemrev.9b00230 DOI: https://doi.org/10.1021/acs.chemrev.9b00230

Rao D., Singh P., Jain R. (2020) Applications of singlet oxygen in photodynamic therapy enhanced by plasmonic nanostructures. Journal of Biomedical Nanotechnology, 16(5), 843–856. https://doi.org/10.1166/jbn.2020.2914 DOI: https://doi.org/10.1166/jbn.2020.2914

Ogawa K., Kobuke Y. (2016) Heavy atom effects in photochemical and photobiological applications. Accounts of Chemical Research, 49(5), 712–721. https://doi.org/10.1021/acs.accounts.6b00027 DOI: https://doi.org/10.1021/acs.accounts.6b00027

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

Chowdhury M.H., Ray K. (2008) Plasmon-controlled fluorescence towards high-sensitivity optical sensing. Advances in Biochemical Engineering/Biotechnology, 116, 29–72. https://doi.org/10.1007/10_2008_9

Ray K., Chowdhury M.H., Zhang J., Fu Y., Szmacinski H., Nowaczyk K., Lakowicz J.R. (2009) Plasmon-controlled fluorescence towards high-sensitivity optical sensing. Advances in Biochemical Engineering/Biotechnology, 116, 29–72. https://doi.org/10.1007/10_2008_9 DOI: https://doi.org/10.1007/10_2008_9

Zhang Y., Xu C., Hao Y. (2015) Influence of heavy atoms on intersystem crossing and singlet oxygen generation in photodynamic systems. Journal of Photochemistry and Photobiology A: Chemistry, 306, 44–52. https://doi.org/10.1016/j.jphotochem.2015.04.006 DOI: https://doi.org/10.1016/j.jphotochem.2015.04.006

Ibrayev N.K., Valiev R.R., Seliverstova E.V., Menshova E.P., Nasibullin R.T., Sundholm D. (2024) Molecular phosphorescence enhancement by the plasmon field of metal nanoparticles. Physical Chemistry Chemical Physics, 26(20), 14624–14636. https://doi.org/10.1039/d4cp01281j DOI: https://doi.org/10.1039/D4CP01281J

Ibrayev N., Seliverstova E., Valiev R., Aymagambetova A., Sundholm D. (2024). The effect of heavy atoms on the deactivation of electronic excited states of dye molecules near the surface of metal nanoparticles. Physical Chemistry Chemical Physics, 26(40), 25986–25993. https://doi.org/10.1039/D4CP02621G DOI: https://doi.org/10.1039/D4CP02621G

DeRosa M.C., Crutchley R.J. (2002). Photosensitized singlet oxygen and its applications. Coordination Chemistry Reviews, 233–234, 351–371. https://doi.org/10.1016/S0010-8545(02)00034-6 DOI: https://doi.org/10.1016/S0010-8545(02)00034-6

Kamalova D.I., Abdrazakova L.R., Salakhov M.Kh. (2020) Poly(vinyl butyral)/poly(ethylene glycol) blends for gas separation membranes: Coefficients of diffusion and permeability of oxygen. Journal of Non-Crystalline Solids, 532, 120304. https://doi.org/10.1016/j.jnoncrysol.2020.120304 DOI: https://doi.org/10.1016/j.jnoncrysol.2020.120304

Ibrayev N., Seliverstova E., Temirbayeva D., Ishchenko A. (2022) Plasmon effect on simultaneous singlet-singlet and triplet-singlet energy transfer. Journal of Luminescence, 251, 119203. https://doi.org/10.1016/ j.jlumin.2022.119203 DOI: https://doi.org/10.1016/j.jlumin.2022.119203

Minaev B.F. (2007) Electronic mechanisms of molecular oxygen activation. Russian Chemical Reviews, 76(11), 988–1010. https://doi.org/10.1070/RC2007v076n11ABEH003720 DOI: https://doi.org/10.1070/RC2007v076n11ABEH003720

Seliverstova E., Ibrayev N., Omarova G., Ishchenko A., Kucherenko M. (2021) Competitive influence of the plasmon effect and energy transfer between chromophores and Ag nanoparticles on the fluorescent properties of indopolycarbocyanine dyes. Journal of Luminescence, 235, 118000. https://doi.org/10.1016/j.jlumin.2021.118000 DOI: https://doi.org/10.1016/j.jlumin.2021.118000

Kanapina A., Seliverstova E., Ibrayev N., Derevyanko N., Ishchenko A. (2023) Features of the decay of excited states of ionic dyes in the near field of metal nanoparticles. Eurasian Physical Technical Journal, 20, 2(44), 106–111. https://doi.org/10.31489/2023No2/106-111 DOI: https://doi.org/10.31489/2023NO2/106-111

Temirbayeva D., Ibrayev N., Kucherenko M. (2022). Distance dependence of plasmon-enhanced fluorescence and delayed luminescence of molecular planar nanostructures. Journal of Luminescence, 243, 118642. https://doi.org/10.1016/j.jlumin.2021.118642 DOI: https://doi.org/10.1016/j.jlumin.2021.118642

Gehlen M. H. (2020) The centenary of the Stern–Volmer equation of fluorescence quenching: From the single line plot to the SV quenching map. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 42, 100338. https://doi.org/10.1016/j.jphotochemrev.2019.100338 DOI: https://doi.org/10.1016/j.jphotochemrev.2019.100338

Krasnovsky A.A. (2008) Luminescence and photochemical studies of singlet oxygen photonics. Journal of Photochemistry and Photobiology A: Chemistry, 196(2–3), 210–218. https://doi.org/10.1016/j.jphotochem.2007.12.015 DOI: https://doi.org/10.1016/j.jphotochem.2007.12.015

THE EFFECT OF THE INTERNAL HEAVY ATOM ON SINGLET OXYGEN GENERATION IN THE PRESENCE OF PLASMONIC NANOPARTICLES