The spatial and electronic structures of complexes consisting of a carnosine molecule with one cobalt ion Co(II) or Co(III) were investigated using the molecular mechanics MM+ and the semi-empirical method of quantum chemistry РМ3. The impact of the cobalt atom on the geometric and energy parameters of the complexes in both tautomeric forms of the imidazole ring of carnosine N1H and N3H was studied. In the studied complexes N1H+Co+H and N3H+Co+H, the Co(II) atom is joined by a coordination bond with one of the nitrogen atoms of the imidazole ring. For the complex of carnosine with Co(III) ion a structure was chosen where the cobalt atom has a coordination number of four and forms a chelate ring of seven bonds. The energy preference of complexes with the tautomeric form of N3H is shown. The carnosine complex in the tautomeric form of N3H with the cobalt ion Co(III) is more stable, the nitrogen atom of the imidazole ring of which is an electron donor. A complex consisting of four carnosine molecules, coordinated by two cobalt ions connected by an oxygen bridge and water molecules, was also investigated. In the process of binding, each cobalt atom forms coordination cavities in the form of two six-membered chelate rings and an imidazole carnosine ring, which has a common coordination bond with the chelate ring. This complex turned out to be the most energy stable.
carnosine, complexes, cobalt, quantum chemical calculations, structure
1. Boldyrev A.A. Karnozin. M.: Izd-vo MGU, 1998, 320 c. @@ [Boldyrev A.A. Carnosine. Moscow: Publishing house of the Moscow State University, 1998, 320 p. (In Russ.)]
2. Boldyrev A.A. Problemy i perspektivy issledovaniya biologicheskoy roli karnozina. Biohimiya, 2000, t. 65, № 7, s. 884-890. @@[Boldyrev A.A. Problemy i perspektivy issledovaniya biologicheskoi roli karnozina. Biokhimiya, 2000, vol. 65, no. 7, pp. 884-890. (In Russ.)]
3. Boldyrev A.A., Aldini G., Derave W. Physiology and pathophysiology of carnosine. Physiological Reviews, 2013, vol. 93, no. 4, pp. 1803-1845. DOI:https://doi.org/10.1152/physrev.00039.2012.
4. Cararo J.H., Streck E.L., Schuck P.F., Ferreira G.da C. Carnosine and Related Peptides: Therapeutic Potential in Age-Related Disorders. Aging and Disease, 2015, vol. 6, no. 5, pp. 369-379. DOI:https://doi.org/10.14336/AD.2015.0616.
5. Kawahara M., Tanaka K.-I., Kato-Negishi M. Zinc, Carnosine, and Neurodegenerative Diseases. Nutrients, 2018, vol. 10, no. 2, p. 147. DOI:https://doi.org/10.3390/nu10020147.
6. Zhao J., Posa D.K., Kumar V., Hoetker D., Kumar A., Ganesan S., Riggs D.W., Bhatnagar A., Wempe M.F., Baba S.P. Carnosine protects cardiac myocytes against lipid peroxidation products. Amino Acids, 2019, vol. 51, no. 1, pp. 123-138.
7. Peters V., Lanthaler B., Amberger A., Fleming T., Forsberg E., Hecker M., Wagner A.H., Yue W.W., Hoffmann G.F., Nawroth P., Zschocke J., Schmitt C.P. Carnosine metabolism in diabetes is altered by reactive metabolites. Amino Acids, 2015, vol. 47 no. 11, pp. 2367-2376. DOI:https://doi.org/10.1007/s00726-015-2024-z.
8. Beran E.H. Metallokompleksy karnozina. Biohimiya, 2000, t. 65, № 7, c. 928-937. @@[Baran E.J. Metal complexes of carmnosine. Biochemistry (Moscow), 2000, vol. 65, no. 7, pp. 789-797. Translated from Biokhimiya, 2000, vol. 65, no. 7, pp. 928-937]
9. Demukhamedova S.D., Alieva I.N., Godjayev N.M. Spatial and electronic structure of monomeric and dimeric complexes of carnosine with zinc. J. Struct. Chem., 2010, vol. 51, no. 5, pp. 824-832. DOI:https://doi.org/10.1007/s10947-010-0127-7.
10. Demukhamedova S.D., Alieva I.N., Gajiyev Z.I. Quantum chemistry investigation of the carnosine polymer complex with zinc. Fizika, 2010, vol. XVI, no. 2, pp.597-600.
11. Demuhamedova S.D., Alieva I.N., Gadzhiev Z.I., Godzhaev N.M. Ab initio issledovanie struktury i kolebatel'nogo spektra molekuly karnozina. Journal of Qafqaz University, 2009, № 27, c. 15-25. @@[Demukhamedova S.D., Alieva I.N. Hadjiev Z.I., Godjayev N.M. Ab initio issledovanie strukturi i kolebatelnogo spectra molekuli karnozina. Journal of Qafqaz University, 2009, no. 27, pp. 15-25. (In Russ.)]
12. Kustin K., Pasternack R.F. The Reaction of L-Carnosine with Cobalt. Journal of the American Chemical Society, 1968, vol. 90, p. 11.
13. Brown C.E., Antholine W.E. Multiple forms of the cobalt(II)-carnosine complex. Biochemical and Biophysical Research Communications, 1979, vol. 88, no. 2, pp. 529-536. DOI:https://doi.org/10.1016/0006-291X(79)92080-1.
14. Ken-ichi O., Takaji Y., Hiroshi K., Tomoharu A., Jinsai H. Unusual Coordination Mode of Carnosine (β-Alanyl-L-histidine) in a Cobalt(III) Complex. Chemistry Letters, 1988, pp. 335-338. DOI:https://doi.org/10.1246/cl.1988.335.
15. Tomoharu A., Hiroshi K., Masato U., Norio K., Takaji Y. Metal Complexes of Peptides. IV. Cobalt(III) Complexes with β-Alanyl-L-histidine (Carnosine) Functioning as a Quadridentate Ligand. Bulletin of the Chemical Society of Japan, 1989, vol. 62, no. 11, pp. 3464-3468. DOI:https://doi.org/10.1246/bcsj.62.3464.
16. Saha M.K., Mukhopadhyay U., Bernal I. Cleavage of the peptide bond of β-alanyl-L-histidine (carnosine) induced by a CoIII-amine complexes: reaction, structure and mechanism. Dalton Trans., 2004, no. 9, pp. 1466-1473. DOI:https://doi.org/10.1039/B402571G.
17. Torreggiani A., Taddei P., Fini G. Characterization of dioxygenated cobalt(II)-carnosine complexes by Raman and IR spectroscopy. Biopolymers, 2002, vol. 67, no. 1, pp. 70-81. DOI:https://doi.org/10.1002/bip.10025.
18. Torreggiania A., Taddeib P., Tintib A., Finib G. Vibrational study on the cobalt binding mode of Carnosine. Journal of Molecular Structure, 2002, vol. 641, no. 1, pp. 61-70
19. Torreggiani A., Trinchero A., Tamba M., Fini G. Vibrational characterisation and biological activity of carnosine and its metal complexes. Ital. J. Biochem., 2003, vol. 52, no. 2, pp. 87-97.
20. Tidjani-Rahmouni N., Djebbar S., Benali-Baitich O. Synthesis, spectroscopic and electrochemichal characterization of mixed cobalt complexes with aminoacids and isonitrosoacetophenone. Biological activities. Mediterranean Journal of Chemistry, 2012, vol. 2, no. 2, pp. 424-437. DOI:https://doi.org/10.13171/mjc.2.2.2012.12.11.22.
21. Alabdali A.J., Al-Amery M.H. A. Synthesis, Thermal Study and Biological Activity of Cobalt (II) and Copper (II) Mixed Ligand Complexes Using (N-4-Methoxy Phenyl) Amino Phenyl Acetonitrile and Histidine Ligands. J. Pharm. Sci. & Res., 2019, vol. 11, no. 1, pp. 155-158.
