INTERACTION OF AQUACOBALAMIN WITH DIHYDROXYBENZENES
Abstract
The interaction of aquacobalamin (H2OCbl) with dihydroxybenzenes – hydroxyquinone, catechol, resorcinol in aqueous solutions has been studied using UV-vis spectrometry. The rate constants of redox reactions have been determined. Their reaction mechanisms have been suggested. It is shown that reaction of aquacobalamin with hydroquinone is accompanied by reduction of Cbl(III) to Cbl(II). The structure of corrin ligand does not change. Reduction of aquacobalamin is accompanied by substitution of water by hydroquinone with formation of unstable complex Cbl(III)-hydroquinone decomposing to Cbl(II) and phenoxy radical – the latter further disproportionates to p-benzoquinone and hydroquinone. The rate of reaction between aquacobalamin and hydroquinone in weakly acidic, neutral and weakly alkaline solutions is decreasing with the increase in pH due to formation of inert hydroxocobalamin. Reaction of aquacobalamin with catechol also gives Cbl(II), but this reaction proceeds much slower than reduction of aquacobalamin with hydroquinone under the same conditions. Reaction of aquacobalamin with resorcinol in acidic, neutral and alkaline solutions does not lead to any changes in UV-vis spectra. Therefore it is assumed that resorcinol does not react with H2OCbl. Based on the previous data and data obtained in this work the following sequence of reducing activity of dihydroxybenzenes in aqueous solutions was proposed: hydroquinone >> catechol > resorcinol. The stability of dihydroxybenzenes in aqueous solutions in the presence of aquacobalamin and in the absence of oxygen increases in the reverse order. The reason of high reducing ability of hydroquinone is assumed to be low dipole moment of hydroquinone molecule.
For citation:
Makarov S.V., Kiseleva A.G., Makarova A.S., Logacheva O.I. Interaction of aquacobalamin with dihydroxybenzenes. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2025. V. 68. N 3. P. 36-41. DOI: 10.6060/ivkkt.20256803.7163.
References
Marques H.M. Corrins and porphyrins: two of nature’s pigments of life. J. Coord. Chem. 2024. V. 77. N 11. P. 1161-1210. DOI: 10.1080/00958972.2024.2343109.
Erina A.A., Borodulin V.B., Dereven’kov I.A., Makarov S.V., Ischenko A.A. Destruction of vitamin B12 during interaction with active oxygen species. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 6-18 (in Russian). DOI: 10.6060/ivkkt.20246707.7043.
Nazhat N.B., Golding B.T., Alastair Johnson G.R., Jones P. Destruction of vitamin B12 by reaction with ascorbate: The role of hydrogen peroxide and the oxidation state of cobalt. J. Inorg. Biochem. 1989. V. 36. N 2. P. 75–81. DOI: 10.1016/0162-0134(89)80014-5.
Salnikov D.S., Dereven’kov I.A., Makarov S.V., Artyushina E.N. Interaction of cyanocobalamin with glu-cose. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2011. V. 54. N 12. P. 47-50 (in Russian).
Salnikov D.S., Dereven’kov I.A., Artyushina E.N., Makarov S.V. Interaction of cyanocobalamin with sulfur-containing reducing agents in aqueous solutions. Russ. J. Phys. Chem. 2013. V. 87. N 1. P. 44–48. DOI: 10.1134/S0036024413010226.
Dereven'kov I.A., Salnikov D.S., Makarov S.V, Boss G.R., Koifman O.I. Kinetics and mechanism of oxidation of super-reduced cobalamin and cobinamide species by thiosulfate, sulfite and dithionite. Dalton Trans. 2013. P. 15307 - 15316. DOI: 10.1039/C3DT51714D.
Salnikov D.S., Dereven’kov I.A., Makarov S.V., Lupan A., Surducan M., Silaghi-Dumitrescu R. Kinetics of re-duction of cobalamin by sulfoxylate in aqueous solutions. Rev. Roum. Chim. 2012. V. 57. N 4-5. P. 353-359.
Makarov S.V., Horváth A.K., Makarova A.S. Reactivity of Small Oxoacids of Sulfur. Molecules. 2019. V. 24. N 15. 2768. DOI: 10.3390/molecules24152768.
Salnikov D.S., Kucherenko P.N., Dereven'kov I.A., Makarov S.V., van Eldik R. Kinetics and mechanism of the reaction of hydrogen sulfide with cobalamin in aqueous solution. Eur. J. Inorg. Chem. 2014. V. 2014. N 5. P. 852-862. DOI: 10.1002/ejic.201301340.
Wingert V., Mukherjee S., Esser A.J., Behringer S., Tanimowo S., Klenzendorf M., Derevenkov I.A., Makarov S.V., Jacobsen D.W., Spiekerkoetter U., Hannibal L. Thiolatocobalamins repair the activity of pathogenic variants of the human cobalamin processing enzyme CblC. Biochimie. 2021. V. 183. P. 108-125. DOI: 10.1016/j.biochi.2020.10.006.
Bazarnova Yu.G. Biologically active compounds of wild plants and its application in food technologies. SPb.: “Professiya”. 2016. 240 p. (in Russian).
Clarke C.J., Gibbard J.A., Brittain W.D.G., Verlet J.R.R. Prediction the increase in electron affinity of phenoxy upon fluorination. J. Fluorine Chem. 2024. V. 277. P. 1100306. DOI: 10.1016/j.jfluchem.2024.110306.
Koolman J., Roehm K-R. Visual biochemistry. M.: Laboratoriya znanii. 2021. 509 p. (in Russian).
Dereven’kov I.A., Shpagilev N.I., Valkai L, Salnikov D.S., Horváth A.K., Makarov S.V. Reactions of aquaco-balamin and cob(II)alamin with chlorite and chlorine dioxide. J. Biol. Inorg. Chem. 2017. V. 22. P. 453-459. DOI: 10.1007/s00775-016-1417-0.
Xia L., Cregan A.G., Berben L.A., Brasch N.E. Studies of the Formation of Glutathionylcobalamin: Any Free Intra-cellular Aquacobalamin Is Likely to Be Rapidly and Irreversibly Converted to Glutathionylcobalamin. Inorg. Chem. 2004. V. 43. N 21. P. 6848-6857. DOI: 10.1021/ic040022c.
Dereven’kov I.A., Salnikov D.S., Silaghi-Dumitrescu R., Makarov S.V., Koifman O.I. Redox chemistry of cobalamin and its derivatives. Coord. Chem. Rev. 2016. V. 309. P. 68-83. DOI: 10.1016/j.ccr.2015.11.001.
Fónagy O., Szabo-Bẚrdos E., Horvẚth O. 1,4-Benzoquinone and 1,4-hydroquinone based determination of electron and superoxide radical formed in heterogeneous photocatalytic systems. J. Photochem. Photobiol. A: Chem. 2021. V. 407. P. 113057. DOI: 10.1016/j.jphotochem.2020.113057.
Yap K.-L, Ho L.-N, Ong S.-A., Guo K., Liew Y.-M., Thor S.-H., Tan S.-M., Teoh T.-P. Comparative study of dihydroxybenzene isomers degradation and bioelectricity generation using CuO as cathodic catalyst in double chambered microbial fuel cell. J. Water Process Eng. 2022. V. 49. P. 103114. DOI: 10.1016/j.jwpe.2022.103114.
Elboughdiri N., Mahjouli A., Shawabheh A., Khasawheh N.E., Jamoussi B. Optimization of Hydroquinone, Resorcinol and Catechol Using Response Surface Methodology. Adv. Chem. Eng. Sci. 2015. V. 5. P. 111-120. DOI: 10.4236/aces.2015.52012.
Johns P.W., Das A., Kuil E.M., Jacobs W.A., Schimp K.J., Schmitz D.J. Cocoa polyphenols accelerate vitamin B12 degradation in heated chocolate milk. Int. J. Food Technol. 2015. V. 56. P. 421-430. DOI: 10.1111/ijfs.12632.
