Conductometric, Spectrophotometric and Computational Investigation of Binary and Ternary Complexes of Co(II) and Cu(II) Bivalent Metal Ions with L-Valine Amino Acid and Paracetamol Drug

Year 2023, Volume: 10 Issue: 3, 703 - 718, 30.08.2023

Aisha Alabbsi , Mohamed Zidan Nouria Shnin Bakr Aldoori

https://doi.org/10.18596/jotcsa.1275299

Cited By: 1

Abstract

The conductivity and spectrophotometry techniques were employed to evaluate the binary and ternary complexes of the divalent metal ions Co(II) and Cu(II) with the physiologically relevant amino acid L-Valine (Val) and the analgesic paracetamol. The conductivity experiments were generated by direct conductivity equation from conductivity titration data, while the spectrophotometry experiments were performed using the continuous variations approach (Job's method). Both techniques were accomplished in an aqueous solution with a constant concentration of 0.004 M of divalent metal ions at (40.0 ± 0.1) °C. The binary complexes of Co(II) and Cu(II) have a 1:1 binding ratio of metal to paracetamol (M:para). However, the binary complexes of Co(II) and Cu(II) have metal: Val binding ratios of either 1:1 or 2:1. In addition, the Cu(II) binary complexes of both ligands have a higher stability constant than Co(II) binary complexes of paracetamol and Val ligands, which was in good agreement with the Rossotti-Willime order. The ternary complexes of Co(II) and Cu(II) have a 1:1:1 binding ratio of metal to paracetamol: L-valine, (M:para:Val). The stability constants were in order: The ternary metal complexes > The binary metal-L-Val complexes > The binary metal-para complexes. DFT (Density Functional Theory) simulations were used in order to gain a better understanding of the molecular interactions of Co(II) and Cu(II) divalent metal ions with L-Val and paracetamol. Calculations were made on the electronic structure, HOMOs and LUMOs, and molecular geometry of complexes and their corresponding ligands. The findings unequivocally demonstrate that the metal ion is bound to both the amide nitrogen in the paracetamol ligand and the oxygen atom of the carbonyl group. Moreover, the metal ion is bound to the nitrogen atom of the amine NH2 group and the oxygen atom of the hydroxyl group for the L-Val ligand.

Keywords

binary complexes, ternary complexes, conductometry, spectrophotometry, L-valine, paracetamol, stability constant

Thanks

We would like to thank the Chemistry Department of Sebha University for supporting this work.

References

• 1. Karges J, Stokes R, Cohen S. Metal complexes for therapeutic applications. Trends Chem. 2021;3(7):523-34.
• 2. Yin X, Ma K, Wang Y, Sun Y, Shang X, Zhao Z, et al. Design, synthesis, and antifungal evaluation of 8-hydroxyquinoline metal complexes against phytopathogenic fungi. J Agric. Food Chem. 2020;68(40):11096-104.
• 3. Shi J, Shu R, Shi X, Li Y, Li J, Deng Y, et al. Multi-activity cobalt ferrite/MXene nanoenzymes for drug-free phototherapy in bacterial infection treatment. RSC Adv. 2022;12(18):11090-9.
• 4. Li Y, Liu B, Shi H, Wang Y, Sun Q, Zhang Q. Metal complexes against breast cancer stem cells. Dalton Trans. 2021;50(41):14498-512.
• 5. Nelson J, Schelter E. Sustainable inorganic chemistry: metal separations for recycling. Inorg. Chem. 2019;58(2):979-90.
• 6. Bhattacharya P, Samnani P. Metal ions in biochemistry: CRC Press; 2020.
• 7. Ahmed N, Al-Omar M, A. A, Obaidullah A, Bhat M, Kalmouch A, et al. Synthesis, characterization, and anti-diabetic activity of some novel vanadium-folate-amino acid materials. Biomolecules. 2020;10(5):781.
• 8. Suhud K, Heng L, Rezayi M, Al-abbasi A, Hasbullah S, Ahmad M, et al. Conductometric Studies of the Thermodynamics for Complexation of 1,1-Diethyl-3-(4-methoxybenzoyl)thiourea and Cobalt(II) Cation in Aqueous Binary Mixtures of Polar Organic Solvents. Journal of Solution Chemistry. 2015;44(2):181-92.
• 9. Al-abbasi A, Mohamed T., Kassim M. N-(Pyrrolidin-1-ylcarbothioyl)benzamide. Acta Crystallographica Section E. 2012;68(1):o201.
• 10. Al-abbasi A, Mohamed Tahir M, Kassim M. 1,1-Diethyl-3-(4-methoxybenzoyl)thiourea. Acta Crystallographica Section E. 2011;67(12):o3414.
• 11. Su J, Suo B, Cassam-Chenaï P. Theoretical Study of the Anisotropy Spectra of the Valine Zwitterion and Glyceraldehyde. J Phys. Chem. A. 2020;124(34):6824-33.
• 12. Kamatchi K, Umarani P, Radhakrishnan T, Raja C. Investigation on organic-inorganic hybrid NLO crystal L-Valine Potassium Penta Borate octa hydrate (LVPPB) for NLO applications. Optik. 2018;172:674-9.
• 13. Afzal Siddiqui H, Nadeem M, Azeem M, Arshad M, Haider A, Malik M. Topological properties of supramolecular chain of different complexes of N-Salicylidene-L-Valine. Polycycl. Aromat. Compd. 2022;42(9):6185-98.
• 14. Martín J, Alés M, Asuero A. An overview on ligands of therapeutically interest. Pharm. Pharmacol. Int. J. 2018;6(3):198-214.
• 15. Chen A, Adamek R, Dick B, Credille C, Morrison C, Cohen S. Correction to Targeting Metalloenzymes for Therapeutic Intervention. Chem. Rev.. 2019;119(12):7719-.
• 16. Hejaz H, Kanan A, Al Mohtaseb M, Ja’bari A. Development and characterization of paracetamol medicated lollipops. Pharm. Technol. Hosp. Pharm. 2020;5(1).
• 17. Alsamarrai K, Ameen S. Simultaneous Ratio Derivative Spectrophotometric Determination of Paracetamol, Caffeine and Ibuprofen in Their Ternary Form. Baghd. Sci J. 2022:1276-.
• 18. Belkher N, Al-abbas A, Zidan M. Potentiometric Studies on Stability Constant of the Complexes of Some Essential Transition Metal Ions with L-Valine. Journal of Pure & Applied Sciences. 2019;18(3):59-63.
• 19. Al-abbası A. BN, Ahmida K., Zidan M. . Potentiometric Studies on Binary and Ternary Complexes of Ni(II) and Cu(II) Ions with L-Valine and Paracetamol. Journal of the Turkish Chemical Society Section A: Chemistry. 2023;10(2):325-38.
• 20. Yang L, He X, Dincă M. Triphenylene-bridged trinuclear complexes of Cu: Models for spin interactions in two-dimensional electrically conductive metal–organic frameworks. J Am. Chem. Soc. 2019;141(26):10475-80.
• 21. Upadhyay S, Hari O. Spectrophotometric and conductometric study of the interaction of saponin with chromium (VI) and lead (II). International Journal of Environmental Science and Technology. 2019;16(12):7997-8004.
• 22. Helmy E, Gomaa E, Elleef EA, Negm A. Conductometric, Spectrophotometric and In vivo Investigation of the Interaction of Ca (II) Ion with Oxytetracycline Hydrochloride. International Journal of Pharma Medicine and Biological Sciences. 2015;4(3):197.
• 23. Chandrathilaka A, Ileperuma, O. Hettiarachchi, C. Spectrophotometric and pH-metric studies on Pb(II), Cd(II), Al(III) and Cu(II) complexes of paracetamol and ascorbic acid. Journal of the National Science Foundation of Sri Lanka. 2013;41(4):337–44.
• 24. Perdew J, Burke K, Wang Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Physical Review B. 1996;54(23):16533.
• 25. Jon B, Alain K, Bernard D. The generation and use of delocalized internal coordinates in geometry optimization: AIP; 1996. 192-212 p.
• 26. Becke A. Density-functional exchange-energy approximation with correct asymptotic behavior. Physical Review A. 1988;38(6):3098.
• 27. Lee C, Yang W, Parr R. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B. 1988;37(2):785.
• 28. Fouad R, Shaaban I, Ali T, Assiri M, Shenouda S. Co (ii), Ni (ii), Cu (ii) and Cd (ii)-thiocarbonohydrazone complexes: spectroscopic, DFT, thermal, and electrical conductivity studies. RSC. Adv. 2021;11(60):37726-43.
• 29. Al-Abachi M, Abed S. Spectrophotometric determination of phenylephrine hydrochloride and salbutamol sulphate drugs in pharmaceutical preparations using diazotized metoclopramide hydrochloride. Baghd. Sci. J. 2015;12(1):167-77.
• 30. Abdel-Rahman L, Ismail N, Ismael M, Abu-Dief A, Ahmed E, Abdel-Hameed. Synthesis, characterization, DFT calculations and biological studies of Mn (II), Fe (II), Co (II) and Cd (II) complexes based on a tetradentate ONNO donor Schiff base ligand. J Mol. Struct. 2017;1134:851-62.
• 31. Stauffer M, Weller W, Kubas K, Casoni K. Limiting reactants in chemical analysis: influences of metals and ligands on calibration curves and formation constants for selected iron-ligand chelates. Stoichiometry and Research–The Impotance of Quantity in Biomedicine2012. p. 311-34.
• 32. Mandal S, Das G, Askari H. Physicochemical investigations of the metal complexes of l-valine with doubly charged ions of nickel, copper and zinc: a combined experimental and computational approach. RSC Adv.. 2014;4(47):24796-809.
• 33. D. T, L. C. Metal Binding Affinity and Selectivity in Metalloproteins: Insights from Computational Studies. Annual Review of Biophysics. 2008;37(1):97-116.
• 34. Leach B, Angelici R. Stereoselective interaction of optically active amino acids and esters with (L; valine-N-monoacetato) copper (II). Journal of the American Chemical Society. 1969;91(23):6296-300.
• 35. Fayad N, Al-Noor T, Mahmood A, Malih I. Synthesis, Characterization, and Antibacterial Studies of Mn (II), Fe (II), Co (II), Ni (II), Cu (II) and Cd (II) Mixed-Ligand Complexes Containing Amino Acid (L-Valine) And (1, 10-phenanthroline). Synthesis. 2013;3(5).
• 36. Fayad N, Al-Noor T, Ghanim F. Synthesis, characterization, and antibacterial activities of manganese (II), cobalt (II), iron (II), nickel (II), zinc (II) and cadmium (II) mixed-ligand complexes containing amino acid (L-Valine) and saccharin. Advances in Physics Theories and Applications. 2013;9:1-13.
• 37. Refat M, El-Korashy S, Hussien M. Ligational, Spectroscopic (Infrared and Electronic) and Thermal Studies on the Mn (II), Co (II), Fe (II) and Cu (II) Complexes with Analgesic Drugs. Canadian Chemical Transactions. 2014;2(1):24-35.
• 38. Refat M, Mohamed G, El-Sayed M, Killa H, Fetooh H. Spectroscopic and thermal degradation behavior of Mg (II), Ca (II), Ba (II) and Sr (II) complexes with paracetamol drug. Arabian Journal of Chemistry. 2017;10:S2376-S87.
• 39. Amolegbe S, Adewuyi S, Akinremi C, Adediji J, Lawal A, Atayese A, et al. Iron(III) and copper(II) complexes bearing 8-quinolinol with amino-acids mixed ligands: Synthesis, characterization and antibacterial investigation. Arabian Journal of Chemistry. 2014;24.
• 40. Lawal A, Obaleye J. Synthesis, characterization and antibacterial activity of aspirin and paracetamolmetal complexes. Biokemistri. 2007;19(1).
• 41. Babamale H, Lawal A, Rajee O, Oloyede E. Synthesis, characterization and biological activity studies of mixed paracetamol-ascorbic acid metal complexes. Journal of Applied Sciences and Environmental Management. 2016;20(4):1157-61.
• 42. Neeraja R, Hima Bindu G. Speciation study involving mononuclear binary transition metal (CoII, NiII and CuII) complexes of L-methionine in non-ionic micellar medium. Heliyon. 2021;7(4):e06729.
• 43. Zheng C, Shi R, Jin X, Qiu Q, Li H. Three complexes with helical frameworks based on l-glutamine and l-asparagine: Crystal structures and circular dichroism properties. Inorganic Chemistry Communications. 2016;65:16-20.
• 44. Doğan A, Kiliç E. Potentiometric studies on the stability constants of some α-amino acid-copper(II) and nickel(II) systems in ethanol-water mixture. Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry. 2003;42:1632-5.
• 45. Wu Y, Koch W, Berezansky P, Holland L. The dissociation constant of amino acids by the conductimetric method: I. pK1 of MOPSO-HCl at 25°C. Journal of Solution Chemistry. 1992;21(6):597-605.
• 46. Singh S, Ranjit K, Ranjit. Complexation reaction of metal ions with peptide systems. VII. Equilibrium studies of N-benzoyl-L-valine, N-benzoyl-glycyl-L-valine and isovaleric acid with metal(II) ion systems. Thermochimica Acta. 1980;40(2):305-9.
• 47. Madkour L, Elshamy I. Experimental and computational studies on the inhibition performances of benzimidazole and its derivatives for the corrosion of copper in nitric acid. International Journal of Industrial Chemistry. 2016;7(2):195-221.
• 48. Al-abbasi A, Kassim M. 1-Ethyl-1-methyl-3-(2-nitrobenzoyl)thiourea. Acta Crystallographica Section E. 2011;67(7):o1840.
• 49. Al-abbasi A, Tan S, Kassim M. 1-Benzoyl-3-(4-hydroxyphenyl)thiourea. Acta Crystallographica Section E. 2010;66(12):o3181.