Photoinduced Electron Transfer in Reactions of 6-Oxofascaplysine with Biomolecules Studied by the Chemically Induced Dynamic Nuclear Polarization

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription or Fee Access

Abstract

A new approach for the synthesis of the anticancer agent 6-oxofascaplysine has been developed and its photochemical activity has been studied for the first time using the method of chemically induced dynamic nuclear polarization. It was found that 6-oxofascaplysine in triplet excited state enters into electron transfer reaction with biomolecules – aromatic amino acids (tryptophan and tyrosine) and 1,4-dihydropyridine (NADH analogue), as well as into energy transfer reaction with oxygen molecule with formation of singlet oxygen. The structure of the radical intermediate of 6-oxofascaplysine has been established. These data may be useful for evaluating the prospects for the use of 6-oxofascaplysine in photodynamic therapy.

About the authors

N. E. Polyakov

Voevodsky Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences

630090 Novosibirsk, Russian Federation

M. A. Ulyanova

Voevodsky Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences

630090 Novosibirsk, Russian Federation

V. A. Timoshnikov

Voevodsky Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences

630090 Novosibirsk, Russian Federation

N. I. Komarova

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

630090 Novosibirsk, Russian Federation

V. I. Krasnov

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

630090 Novosibirsk, Russian Federation

V. V. Fomenko

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

Email: fomenko@nioch.nsc.ru
630090 Novosibirsk, Russian Federation

N. F. Salakhutdinov

N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

630090 Novosibirsk, Russian Federation

References

  1. Zhidkov M.E., Kantemirov A.V., Koisevnikov A.V., Andin A.N., Kuzmich A.S. // Tetrahedr. Lett. 2018. V. 59. P. 708–711. https://doi.org/10.1016/J.TETLET.2018.01.023
  2. Luo L., Xu G. // Int. J. Mol. Sci. 2022. V. 23. P. 13774. https://doi.org/10.3390/ijms232213774
  3. Khokhar S., Feng Y., Campitelli M.R., Ekins M.G., Hooper J.N.A., Beattie K.D., Sadowski M.C., Nelson C.C., Davis R.A. // Bioorg. Med. Chem. Lett. 2014. V. 24. № 15. P. 3329–3332. https://doi.org/10.1016/j.bmcl.2014.05.104
  4. Wang C., Wang S., Li H., Hou Y., Cao H., Hua H., Li D. // Mar. Drugs. 2023. V. 21. P. 226. https://doi.org/10.3390/md21040226
  5. Kaptein R. // J. Chem. Soc. D: Chem. Commun. 1971. № 14. P. 732–733. https://doi.org/10.1039/C29710000732
  6. Salikhov K.M., Molin Yu.N., Sagdeev R.Z.б Buchachenko A.L. Spin polarization and magnetic effects in radical reactions. Molin Yu.N. (ed.). Budapest, Hungary, Academiai Kiadó,1984. 419 p.
  7. Leshina T.V., Kruppa A.I., Taraban M.B. CIDNP Applications. In: Encyclopedia of spectroscopy and spectrometry. Third Edition. 2017. P. 256–262. http://dx.doi.org/10.1016/B978-0-12-803224-4.00121-7
  8. Morozova O.B., Ivanov K.L., Kiryutin A.S., Sagdeev R.Z., Köchling T., Vieth H.-M., Yurkovskaya A.V. // Phys. Chem. Chem. Phys. 2011. V. 13. № 14. P. 6619–6627. https://doi.org/10.1039/c0cp02449j
  9. Morozova O.B., Ivanov K.L. // Chem. Phys. Chem. 2019. V. 20. № 2. P. 197–215. https://doi.org/10.1002/cphc.201800566
  10. Goez M. Elucidating organic reaction mechanisms using photo-CIDNP spectroscopy. In: Hyperpolarization methods in NMR spectroscopy. Kuhn L.T. (ed.). Berlin, Heidelberg, 2013. P. 1–32. https://doi.org/10.1007/128_2012_348
  11. Kuhn L.T., Bargon J. Exploiting nuclear spin polarization to investigate free radical reactions via in situ NMR. In: In situ NMR methods in catalysis. Bargon J., Kuhn L.T. (eds.). Berlin, Heidelberg, 2007. P. 125–154. https://doi.org/10.1007/128_2007_119
  12. Polyakov N.E., Khan V.K., Taraban M.B., Leshina T.V., Luzina O.A., Salakhutdinov N.F., Tolstikov G.A. // Org. Biomol. Chem. 2005. V. 3. P. 881–885. https://doi.org/10.1039/b416133e
  13. Taraban М.В., Kruppa A.I., Polyakov N.E., Leshina T.V., Lūsis V., Muceniece D., Duburs G. // J. Photochem. Photobiol. A Chem. 1993. V. 73. P. 151–156. https://doi.org/10.1016/1010-6030(93)80044-A
  14. Mastova A.V., Selyutina O.Yu., Polyakov N.E. // Membranes. 2022. V. 12. P. 460. https://doi.org/10.3390/membranes12050460
  15. Baram G.I., Grachev M.A., Komarova N.I., Perelroyzen M.P., Bolvanov Y.A., Kuzmin S.V., Kargaltsev V.V., Kuper E.A. // J. Chromatogr. A. 1983. V. 264. № 1. P. 69–90. https://doi.org/10.1016/S0021-9673(01)95007-1
  16. Hermosilla L., Calle P., García de la Vega J.M., Sieiro C. // J. Phys. Chem. A. 2005. V. 109. № 6. P. 1114–1124. https://doi.org/10.1021/jp0466901
  17. Weigend F. // Phys. Chem. Chem. Phys. 2006. V. 8. № 9. P. 1057–1065. https://doi.org/10.1039/b515623h
  18. Neese F., Wennmohs F., Hansen A., Becker U. // Chem. Phys. 2009. V. 356. № 1–3. P. 98–109. https://doi.org/10.1016/j.chemphys.2008.10.036
  19. Barone V., Cossi M. // J. Phys. Chem. A. 1998. V. 102. № 11. P. 1995–2001. https://doi.org/10.1021/jp9716997
  20. Oberg C., Buthelezi M.T. Binding of Cu2+ ions to indigo derivatives in aqueous media. 2023. Available at SSRN: http://dx.doi.org/10.2139/ssrn.4455433
  21. Mao Y., Chen H., Zhu W., Ni S., Luo S., Tang S., Chen Z., Wang Q., Xu J., Tu Q., Chen H., Zhu L. // J. Inflam. Res. 2025. V. 18. P. 883–894. https://doi.org/10.2147/JIR.S498340

Supplementary files

Supplementary Files
Action
1. JATS XML
Download

Copyright (c) 2025 Russian Academy of Sciences