Study of the Interaction between Bovine Serum Albumin and Three Copper(II)-imine Complexes by Electronic Absorption Spectroscopy

Document Type : Research Article

Authors

Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, Zahedan, I.R. IRAN

Abstract

Three complexes: bis(2,2′-bipyridine)-, bis(1,10-phenanthroline)- and (2,2′-bipyridine)(1,10-phenanthroline)-chlorocopper(II) chloride with molecular formula of [Cu(bpy)2Cl]Cl, [Cu(phen)2Cl]Cl and [Cu(bpy)(phen)Cl]Cl, having trigonal-bipyramidal geometry were prepared according to the reported procedure via the reaction of CuCl2 with bpy and phen ligands. The interaction of these complexes with bovine serum albumin (BSA) was studied by electronic absorption spectroscopy at two temperatures of 296 and 310 K in Tris buffer medium (pH = 7) containing sodium chloride (10 mM). These interactions include the determination of the binding constant of each metal complex to serum albumin (K), the midpoint concentration of each metal complex that can denature half of the BSA molecules present in the medium (L1/2), and the thermodynamic studies. The binding constant values obtained in the range of 2.08 ‒ 65.7 × 104 M‒1 indicate the proper interaction of each complex with BSA. In the titration of BSA with each of the complexes, it was found that the conformation of this protein changed upon the addition of these compounds. It is because the absorbance of BSA at 280 nm showed a significant decrease with increasing the concentration of each compound. While studying thermodynamic parameters: the negative values of Gibbs free energy changes in the interaction of all three complexes with BSA, confirmed the spontaneous nature of the reaction between them. The positive values of standard enthalpy changes for the [Cu(bpy)2Cl]Cl and [Cu(bpy)(phen)Cl]Cl and the negative value for the [Cu(phen)2Cl]Cl indicate that these processes are endothermic and exothermic, respectively. In addition, the positive values of the standard entropy changes for the [Cu(bpy)2Cl]Cl and [Cu(bpy)(phen)Cl]Cl indicate the irregularity of the system (entropy driven) and its negativity for the [Cu(phen)2Cl]Cl indicates ordering. The positive values of ΔH° and ΔS° for the [Cu(bpy)2Cl]Cl and [Cu(bpy)(phen)Cl]Cl and the negative values for [Cu(phen)2Cl]Cl complexes indicate hydrophobic and H-binding + van der Waals interactions, respectively.

Keywords

Main Subjects


[1] Loehrer P.J., Einhorn L.H., Cisplatin, Ann. Intern. Med., 100(5): 704–713 (1984).
[2] Dasari S., Tchounwou P.B., Cisplatin in Cancer Therapy: Molecular Mechanisms of Action, Eur. J. Pharmacol. 740: 364–378 (2014).
[3] Psalti I.S.M., Ward R.J., Crichton R.R., Lallemand F., "Biological Inorganic Chemistry: An Introduction", Elsevier Science Limited, (2008).
[4] Constable E.C., Housecroft C.E., The Early Years of 2,2′-Bipyridine-a Ligand in Its Own Lifetime, Molecules, 24(21): 3951 (2019).
[5] Liu H., Shi X., Xu M., Li Z., Huang L., Bai D., Zeng Z., Transition Metal Complexes of 2,6-di ((Phenazonyl-4-Imino)Methyl)-4-Methylphenol: Structure and Biological Evaluation, Eur. J. Med. Chem., 46(5): 1638–1647 (2011).
[6] Sanna D., Buglyó P., Tomaz A.I., Pessoa J.C., Borović S., Micera G., Garribba E., VIV O and CuII Complexation by Ligands Based on Pyridine Nitrogen Donors, Dalton Trans., 41(41): 12824–12838 (2012).
[7] Sleep D., Belfield G.P., Goodey A.R., The Secretion of Human Serum Albumin from the Yeast Saccharomyces Cerevisiae Using Five Different Leader Sequences, Biotechnology, 8(1): 42–46 (1990).
[9] Chakrabarty A., Mallick A., Haldar B., Das P., Chattopadhyay N., Binding Interaction of a Biological Photosensitizer with Serum Albumins: A Biophysical Study, Biomacromolecules, 8(3): 920–927 (2007).
[10] Detoni C., Carvalho N.M.F., Aranda D.A.G., Louis B., Antunes O.A.C., Cyclohexane and Toluene Oxidation Catalyzed by 1,10-Phenantroline Cu(II) Complexes, Appl. Catal. A-Gen., 365(2): 281–286 (2009).
[11] Canhota F.P., Salomão G.C., Carvalho N.M.F., Antunes O.A.C., Cyclohexane Oxidation Catalyzed by 2,2′-Bipyridil Cu(II) Complexes, Catal. Commun., 9(1): 182–185 (2008).
[12] Stephens F.S., Tucker P.A., Crystal and Molecular Structure of Chlorobis (2,2′-Bipyridyl) Copper (II) Chloride Hexahydrate, J. Chem. Soc. Dalton, 21: 2293–2297 (1973).
[14] Sohn J.R., Lee, S. Il, Adsorption Study of Acetylacetone on Cation-Exchanged Montmorillonite by Infrared Spectroscopy, Langmuir, 16(11): 5024–5028 (2000).
[15] Chi Z., Liu R., Phenotypic Characterization of the Binding of Tetracycline to Human Serum Albumin, Biomacromolecules, 12(1): 203–209 (2011).
[16] Campos-Vallette M.M., Clavijo R.E., Mendizabal F., Zamudio W., Baraona R., Diaz G., Infrared Spectrum of the Bis-(1,10-Phenanthroline) Cu(I) and Cu(II) Perchlorate Complexes, Vib. Spectrosc., 12(1): 37–44 (1996).
[17] Onawumi O.O., Adekunle F.A., Ibrahim A.O., Rajasekharan M. V, Odunola O.A., Synthesis, Characterization, and Crystal Structures of [Cu(phen)2Cl]Cl·6.5H2O and [Cu(phen)2Br]Br, Synth. React. Inorg. M., 40(2): 78–83 (2010).
[20] Kashanian S., Khodaei M.M., Roshanfekr H., Shahabadi N., Rezvani A., Mansouri G., DNA Binding, DNA Cleavage, and Cytotoxicity Studies of Two New Copper (II) Complexes, DNA Cell Biol., 30(5): 287–296 (2011).
[21] Kauffman G.B., "Synthesis and Technique in Inorganic Chemistry (Angelici, Robert J.)", ACS Publications (1970).
[22] Jain S., Bhar K., Kumar S., Bandyopadhyaya S., Tapryal S., Mandal C.C., Sharma A.K., Homo-and Heteroleptic Trimethoxy Terpyridine–Cu(II) Complexes: Synthesis, Characterization, DNA/BSA Binding, DNA Cleavage and Cytotoxicity Studies, Dalton T., 49(13): 4100–4113 (2020).
[23] Vignesh G., Arunachalam S., Vignesh S., James R.A., BSA Binding and Antimicrobial Studies of Branched Polyethyleneimine–Copper(II) Bipyridine/Phenanthroline Complexes, Spectrochim Acta A., 96: 108–116 (2012).
[24] Ross P.D., Subramanian S., Thermodynamics of Protein Association Reactions: Forces Contributing to Stability, Biochemistry, 20(11): 3096–3102 (1981).