Russian Journal of Biological Physics and Chemisrty Russian Journal of Biological Physics and Chemisrty АКТУАЛЬНЫЕ ВОПРОСЫ БИОЛОГИЧЕСКОЙ ФИЗИКИ И ХИМИИ 2499-9962 54469 Моделирование в биофизике Modelling in biophycis Моделирование в биофизике QUANTUM-CHEMICAL STUDY OF COMPLEXES OF TWO TAUTOMERIC FORMS OF CARNOSINE WITH COBALT КВАНТОВОХИМИЧЕСКОЕ ИССЛЕДОВАНИЕ КОМПЛЕКСОВ ДВУХ ТАУТОМЕРНЫХ ФОРМ КАРНОЗИНА С КОБАЛЬТОМ Демухамедова С Д Demukhamedova S D svetlanabest@mail.ru Институт физических проблем, Бакинский государственный университет ru Institute for Physical Problems, Baku State University ru 25 12 2019 25 12 2019 4 4 505 513 20 12 2019 20 12 2019 https://rusjbpc.ru/en/nauka/article/54469/view

В работе методами молекулярной механики ММ+ и полуэмпирическим методом квантовой химии РМ3 исследовано пространственное и электронное строение комплексов, состоящих из молекулы карнозина с одним ионом кобальта Со(II) или Co(III). Изучено влияние атома кобальта на геометрические и энергетические параметры комплексов в обоих таутомерных формах имидазольного кольца карнозина N1H и N3H. В изученных комплексах N1H+Co+H и N3H+Co+H, атом Со(II) соединяется координационой связью с одним из атомов азота имидазольного кольца. Для комплекса карнозина с ионом Со(III) выбрана структура, где атом кобальта имеет координационное число четыре и образует хелатное кольцо из семи связей. Показано энергетическое предпочтение комплексов с таутомерной формой N3H. Более стабилен комплекс карнозина в таутомерной форме N3H c ионом кобальта Со(III), атом азота имидазольного кольца которого является донором электронов. Был исследован также комплекс, состоящий из четырех молекул карнозина, координированный двумя ионами кобальта, соединенными кислородным мостиком и молекулами воды. В процессе связывания каждый атом кобальта образует координационные полости в виде двух шестичленных хелатных колец и имидазольного кольца карнозина, имеющего общую координационную связь с хелатным кольцом. Этот комплекс оказался наиболее энергетически стабильным.

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.

 карнозин комплексы кобальт квантово-химические расчеты структура carnosine complexes cobalt quantum chemical calculations structure

Болдырев А.А. Карнозин. М.: Изд-во МГУ, 1998, 320 c. @@ [Boldyrev A.A. Carnosine. Мoscow: Publishing house of the Moscow State University, 1998, 320 p. (In Russ.)] 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.)] Болдырев А.А. Проблемы и перспективы исследования биологической роли карнозина. Биохимия, 2000, т. 65, № 7, с. 884-890. @@[Boldyrev A.A. Problemy i perspektivy issledovaniya biologicheskoi roli karnozina. Biokhimiya, 2000, vol. 65, no. 7, pp. 884-890. (In Russ.)] 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.)] Boldyrev A.A., Aldini G., Derave W. Physiology and pathophysiology of carnosine. Physiological Reviews, 2013, vol. 93, no. 4, pp. 1803-1845. DOI: 10.1152/physrev.00039.2012. Boldyrev A.A., Aldini G., Derave W. Physiology and pathophysiology of carnosine. Physiological Reviews, 2013, vol. 93, no. 4, pp. 1803-1845. DOI: 10.1152/physrev.00039.2012. 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: 10.14336/AD.2015.0616. 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: 10.14336/AD.2015.0616. Kawahara M., Tanaka K.-I., Kato-Negishi M. Zinc, Carnosine, and Neurodegenerative Diseases. Nutrients, 2018, vol. 10, no. 2, p. 147. DOI: 10.3390/nu10020147. Kawahara M., Tanaka K.-I., Kato-Negishi M. Zinc, Carnosine, and Neurodegenerative Diseases. Nutrients, 2018, vol. 10, no. 2, p. 147. DOI: 10.3390/nu10020147. 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. 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. 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: 10.1007/s00726-015-2024-z. 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: 10.1007/s00726-015-2024-z. Бэран Э.Х. Металлокомплексы карнозина. Биохимия, 2000, т. 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] 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] 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: 10.1007/s10947-010-0127-7. 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: 10.1007/s10947-010-0127-7. 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. 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. Демухамедова С.Д., Алиева И.Н., Гаджиев З.И., Годжаев Н.М. Ab initio исследование структуры и колебательного спектра молекулы карнозина. 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.)] 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.)] Kustin K., Pasternack R.F. The Reaction of L-Carnosine with Cobalt. Journal of the American Chemical Society, 1968, vol. 90, p. 11. Kustin K., Pasternack R.F. The Reaction of L-Carnosine with Cobalt. Journal of the American Chemical Society, 1968, vol. 90, p. 11. 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: 10.1016/0006-291X(79)92080-1. 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: 10.1016/0006-291X(79)92080-1. 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: 10.1246/cl.1988.335. 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: 10.1246/cl.1988.335. 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: 10.1246/bcsj.62.3464. 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: 10.1246/bcsj.62.3464. 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: 10.1039/B402571G. 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: 10.1039/B402571G. 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: 10.1002/bip.10025. 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: 10.1002/bip.10025. 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 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 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. 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. 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: 10.13171/mjc.2.2.2012.12.11.22. 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: 10.13171/mjc.2.2.2012.12.11.22. 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. 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.