SYNTHESIS AND ANTIBACTERIAL ACTIVITY OF Cu+ MALEINATE COMPLEXES WITH INCREASED STABILITY
DOI:
https://doi.org/10.15421/jchemtech.v33i3.336780Keywords:
ascorbic acid, Cu maleate, synthesis, bactericidal activity, Staphylococcus aureus, Escherichia coliAbstract
To improve the quality of the target product, the possibility of replacing zinc with ascorbic acid in the synthesis of maleic complexes of Cu+ and copper-containing composites based on them was investigated. The analysis of the results of potentiometric titration of a solution of 1M CuSO4, 1M maleic acid (H2M) with a neutralised solution of 1M ascorbic acid (H2Asc) showed that HAsc- anions behave exclusively as a one-electron reducing agent, and the existing conjugation of the redox systems [Cu(HM)]+/[Cu(HM)] and HAsc/*Asc- contributes to a decrease in the yield of the target product, the maleate Cu+ complex. It has been found that about 50% of ascorbic acid reacts with [Cu(HM)]+ ions, and this figure is unchanged in the range of low reducing agent concentrations (up to 0,01M) and in the range of high concentrations (up to 1 M). A two-step scheme for the synthesis of the {[Cu(HM)(H2O)]xCu} composite was implemented, in which the reduction of copper ions was carried out exclusively with ascorbic acid. At the first stage, the [Cu(HM)]+ complex was reduced to [Cu(HM)]. At the second stage, the required amount of 1M CuSO4 solution was added to the suspension of [Cu(HM)] in a 1M solution of neutralised ascorbic acid to obtain the composite {[Cu(HM)(H2O)]0,5Cu}. It was found that the [Cu(HM)] complex isolated from the ascorbate solution is a highly stable form with respect to atmospheric oxygen. Microbiological studies of the effect of the obtained substances on Staphylococcus aureus and Escherichia coli strains confirmed the high bactericidal activity of the maleinate complex compared to the composite.
References
Ashraf, J., Riaz, M. A. (2022) Biological potential of copper complexes: a review. Turk. J. Chem., 46(3), 595–623. https://doi.org/10.55730/1300-0527.3356.
González-Ballesteros, N., Pérez-Álvarez, D., Rodríguez-Argüelles, M. C., Henriques, M. S., Paixão, J., Prado-López, A. S. (2016). Synthesis, spectral characterization and X-ray crystallographic study of new copper(I) complexes. Antitumor activity in colon cancer. Polyhedron, 119, 112–119. http://dx.doi.org/10.1016/j.poly.2016.08.023.
Zhang, Z., Wang, H., Wang, Q., Yan, M., Wang, H., Bi, C., Fan, Y. (2016). Anticancer activity and computational modeling of ternary copper(II) complexes with 3-indolecarboxylic acid and 1,10-phenanthroline. International Journal of Oncology, 49(2), 691–699. https://doi.org/10.3892/ijo.2016.3542.
Hussain, A., AlAjmi, M. F., Rehman, M. T., Amir, S., Husain, F. M., Alsalme, A., Khan, R. A. (2019). Copper(II) complexes as potential anticancer and Nonsteroidal anti-inflammatory agents: In vitro and in vivo studies. Scientific reports, 9(1), 5237. https://doi.org/10.1038/s41598-019-41063-x.
Wehbe, M., Lo, C., Leung, A. W., Dragowska, W. H., Ryan, G. M., Bally, M. B. (2017). Copper(II) complexes of bidentate ligands exhibit potent anti-cancer activity regardless of platinum sensitivity status. Invest. new drugs, 35(6), 682–690. https://doi.org/10.1007/s10637-017-0488-2.
Qi, J., Yao, Q., Tian, L., Wang, Y. (2018). Piperidylthiosemicarbazones Cu(II) complexes with a high anticancer activity by catalyzing hydrogen peroxide to degrade DNA and promote apoptosis. Eur. J. of Med. Chem., 158, 853–862. https://doi.org/10.1016/j.ejmech.2018.09.034.
Slassi, S., El‐Ghayoury, A., Aarjane, M., Yamni, K., Amine, A. (2020). New copper (II) and zinc(II) complexes based on azo Schiff base ligand: Synthesis, crystal structure, photoisomerization study and antibacterial activity. Applied Organometallic Chemistry, 34(4), 5503. https://doi.org/10.1002/aoc.5503.
Obaleye, J A., Ajibola, A. A., Bernardus, V. B., Hosten, E. C., Ozarowski, A. (2020). Synthesis, spectroscopic, structural and antimicrobial studies of a dimeric complex of copper(II) with trichloroacetic acid and metronidazole. Inorganica Chimica Acta, 503, 119404. http://dx.doi.org/10.1016/j.ica.2019.119404.
Harmalkar, S. S., Butcher, R. J., Gobre, V. V., Gaonkar, S. K., D'Souza, L. R., Sankaralingam, M., Dhuri S. N. (2019). Synthesis, characterization and antimicrobial properties of mononuclear copper(II) compounds of N,N′-di(quinolin-8-yl)cyclohexane-1,2-diamine. Inorganica Chimica Acta, 498, 119020. https://doi.org/10.1016/j.ica.2019.119020.
Grabchev, I., Yordanova, S., Vasileva-Tonkova, E., Bosch, P., Stoyanov S. (2015). Poly (propylenamine) dendrimers modified with 4-amino-1,8-naphthalimide: Synthesis, characterization and in vitro microbiological tests of their Cu(II) and Zn(II) complexes. Inorganica Chimica Acta, 438, 179–188. https://doi.org/10.1016/j.ica.2015.09.010.
Santiago, P. H., Santiago, M. B., Martins, C. H., Gatto C. C. (2020). Copper (II) and zinc (II) complexes with Hydrazone: Synthesis, crystal structure, Hirshfeld surface and antibacterial activity. Inorganica Chimica Acta, 508, 119632. http://dx.doi.org/10.1016/j.ica.2020.119632.
Soroceanu, A., Vacareanu, L., Vornicu, N., Cazacu, M., Rudic, V., Croitori T. (2016). Assessment of some application potentials for copper complexes of the ligands containing siloxane moiety: Antimicrobial, antifungal, antioxidant and redox activity. Inorganica Chimica Acta, 442(2), 119–123. https://doi.org/10.1016/j.ica.2015.12.006.
Kumar, S., Sharma, R. P., Venugopalan, P., Gondil, V. S., Chhibber, S., Aree, T., Ferretti V. (2018). Hybrid inorganic-organic complexes: Synthesis, spectroscopic characterization, single crystal X-ray structure determination and antimicrobial activities of three copper(II)-diethylenetriamine-p-nitrobenzoate complexes. Inorganica Chimica Acta, 469, 288–297. https://doi.org/10.1016/j.ica.2017.09.032.
Lima, F. C., Silva, T. S., Martins, C. H., Gatto C. C. (2018). Synthesis, crystal structures and antimicrobial activity of dimeric copper(II) complexes with 2-hydroxyphenyl-ethylidene-dithiocarbazates. Inorganica Chimica Acta, 483, 464–472. https://doi.org/10.1016/j.ica.2018.08.032.
Vargalyuk, V. F., Polonskyy, V. A., Sklyar, T. V., Stets, N. V., Laguta O. V. (2023). [Physico-chemical and bactericidal properties of copper-containing composites based on maleinate complexes Cu+]. Journal of Chemistry and Technologies, 31(2), 208–215 (in Ukrainian). https://doi.org/10.15421/jchemtech.v31i2.275070.
Vargaluyk, V. F., Polonskyy, V. A., Osokin, Y. S., Lahuta, O.V. (2021). [Syntesis of copper composites containing maleic acid]. Journal of Chemistry and Technologies, 29(3), 400–409. http://dx.doi.org/10.15421/jchemtech.v29i3.241965.
Yu, J. S., Kim, S. H., Man M. T., Lee, H. S. (2018). Synthesis and Characterization of Water Soluble Fluorescent Copper Nanoparticles. Applied Science and Convergence Technology, 27(4), 75–77. https://doi.org/10.5757/ASCT.2018.27.4.75.
Vargalyuk, V. F., Polonskyy, V. А., Stets, O. S., Stets, N. V., Shchukin, A. І. (2014). [Microbiological properties of copper dispersion obtained by cathodic deposition in the presence of acrylic acid]. Bulletin of Dnipropetrovsk University. Series Chemistry, 22(2), 47–51 (in Ukrainian). http://dx.doi.org/10.15421/081420.
Du, J. Cullen, Garry J. J., Buettner G. R. (2012). Ascorbic acid: Chemistry, biology and the treatment of cancer. Biochimica et Biophysica Acta, 1826(2), 443–457. https://doi.org/10.1016/j.bbcan.2012.06.003.
Vargalyuk, V. F., Polonskyy, V. A., Osokin, Y. S., Skok A. Y. (2020). [Influence of maleic acid on the composition and structure of organocopper dispersions obtained by chemical and electrochemical reduction of Cu2+-ions]. Journal of Chemistry and Technologies, 28(3), 231–241 (in Ukrainian). https://doi.org/10.15421/082025.
Navon, N., Masarwa, A., Cohen, H., Meyerstein D. (1997). pH dependence of the stability constants of copper(I) complexes with fumaric and maleic acids in aqueous solutions. Inorganica Chimica Acta, 261, 29–35. https://doi.org/10.1016/S0020-1693(96)05575-2.
Uljanionok, J., Survila, A. (2009). Formation of Cu+ compounds in the Cu/Cu(II) – maleic acid system. Chemija, 20(4), 226–230. http://mokslozurnalai.lmaleidykla.lt/publ/0235-7216/2009/4/226-230.pdf.
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