Background. Metal complexes of biologically active ligands had considerable interests. L-cysteinate residue, L-Cys, is a biologically abundant and important versatile binding site of proteins. Diphenylamine, DPA, is an important aromatic amine containing two phenyl groups. Complexation equilibria of the divalent metal ions, Ca2+ and Zn2+ with the bio- relevant α-amino acid, L-cysteine and the nitrogen-containing diphenylamine ligand were investigated by means of the potentiometric technique at 25.0 ± 0.1°C and constant ionic strength of 0.200 ± 0.001 mol·dm-3 NaNO3. Objective. The stability constants and standard free energy changes of the α-amino acid, L-cysteine and diphenylamine complex species were determined at 0.200 ± 0.001 mol·dm-3ionic strength. Methods. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes were inferred from the potentiometric titrations. Results. The concentration distribution of L-cysteine species formed in solution was evaluated. The dissociation constants of the α-amino acid and diphenylamine were determined at different ionic strength. The stability constants of these binary and ternary systems were calculated. The values of ∆ log10 K, percent relative stabilization, %R.S. and log10 X for the ternary systems were evaluated and discussed. Concussion. The ternary complex formation occurred in a stepwise manner with L-cysteine acting as the primary ligand. The obtained values of ∆ G0 indicated that Complex formation reactions are spontaneous. Also, for all systems studied, the ternary complexes formed are more thermodynamically stable than the binary complexes.
Published in | American Journal of Chemical Engineering (Volume 10, Issue 2) |
DOI | 10.11648/j.ajche.20221002.12 |
Page(s) | 23-31 |
Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
Copyright |
Copyright © The Author(s), 2022. Published by Science Publishing Group |
Potentiometric Studies, Metal (II) Ions, L-Cysteine, Ternary Systems
[1] | Frausto da Silva, J. J. R., Williams, R. J. P.: The Biological Chemistry of the Elements; The Inorganic Chemistry of Life. Clarendon Press, Oxford (1991). |
[2] | Bertini, I., Gray, H. B., Lippard, S. J., Valentine, J. S.: Bioinorganic Chemistry. University Science Books, Mill Valley (1994). |
[3] | Goodman Gilman, A., Goodman, L. S.: Goodman and Gilman’s he Pharmacological Basis of Therapeutics, 10th edn. Mc-Graw Hill, New Jersey (2002). |
[4] | Kimura, E., Kurogi, Y., Shionoya, M., Shira, M.: Synthesis, properties, and complexation of a new imidazole-pendant macrocyclic 12-membered triamine ligand. Inorg. Chem. 30, 4524–4529 (1991). |
[5] | Schayer, R. W.: The metabolism of ring labeled histamine. J. Biol. Chem. 196, 469–475 (1952). |
[6] | Baldridge, R. C., Tourtellotte, C. D.: The metabolism of histidine. III. Urinary metabolites. J. Biol. Chem. 233, 125–127 (1958). |
[7] | Khandelwal, J. K., Prell, G. D., Morrishow, A. M., Green, J. P.: Presence and measurement of imidazoleacetic acid, a c-aminobutyric acid agonist, in rat brain and human cerebrospinal fluid. J. Neurochem. 52, 1107–1113 (1989). |
[8] | Garcı´a-Raso, A., Fiol, J. J., Adrover, B., Tauler, P., Pons, A., Mata, I., Espinosa, E., Molins, E.: Reactivity of copper(II) peptide complexes with bioligands (benzimidazole and creatinine). Polyhedron. 22, 3255–3264 (2003). |
[9] | Ranford, J. D., Sadler, P. J.: Cytotoxicity and antiviral activity of transition-metal salicylato complexes and crystal structure of bis(diisopropylsalicylato)(1,10-phenanthroline)copper(II). Dalton Trans. 22, 3393–3399 (1993). |
[10] | Majella, G., Vivienne, S., Malachy, M., Michael, D., Vickie, M.: Synthesis and anti-candida activity of copper(II) and manganese(II) carboxylate complexes: X-ray crystal structures of [Cu(sal)(bipy)] _C2H5OH_H2O and [Cu(norb)(phen)2]_6.5H2O (salH2 = salicylic acid; norbH2 = cis-5-norbornene- endo-2,3-dicarboxylic acid; bipy = 2,20-bipyridine; phen = 1,10-phenanthroline). Polyhedron 18, 2931–2939 (1999). |
[11] | Saha, D. K., Sandbhor, U., Shirisha, K., Padhye, S., Deobagkar, D., Ansond, C. E., Powell, A. K.: A novel mixed-ligand antimycobacterial dimeric copper complex of ciprofloxacin and phenanthroline. Bioorg. Med. Chem. Lett. 14, 3027–3032 (2004). |
[12] | Zoroddu, M. A., Zanetti, S., Pogni, R., Basosi, R.: An electron spin resonance study and antimicrobial activity of copper(II)–phenanthroline complexes. J. Inorg. Biochem. 63, 291–300 (1996). |
[13] | Sigel, H.: Metal Ions in Biological Systems, vol. 3. Marcel Dekker, New York (1974). |
[14] | Lau, S., Sarkar, B.: Kinetic studies of copper(II)-exchange from L-histidine to human serum albumin and diglycyl-L-histidine, a peptide mimicking the copper(II)-transport site of albumin. Can. J. Chem. 53, 710–715 (1975). |
[15] | Bensichem, M. V., Crystal and molecular structure of trans-dichlorobis (thiazole) platinum(II). Inorg. Chem. 31, 634–639 (1992). |
[16] | Acta Cryst. Diphenyamine (2003). E59, o1123-o1125. |
[17] | Khalil M. M.; Attia, A. E.; Potentiometric Studies on the Binary and Ternary Complexes of Copper(II) Containing Dipicolinic Acid and Amino Acids. J. Chem. Eng. Data, 1999, 44, 180-184. |
[18] | Khalil, M. M.; Complexation Equilibria & Determination of Stability Constants of Binary and Ternary Complexes with Ribonucleotides (AMP, ADP, and ATRP) and Salicylhydroxamic Acid as Ligands. J. Chem. Eng. Data, 2000, 45, 70-74. |
[19] | Khalil, M. M.; Solution Equilibria & Stabilities of Binary and Ternary Complexes with N-(2-Acetamido) iminodiacetic Acid and Ribonucleotides (AMP, ADP, and ATP). J. Chem. Eng. Data, 2000, 45, 837-840. |
[20] | Khalil, M. M.; Attia, A. E.; Potentiometric Studies on the Formation Equilibria of Binary and Ternary Complexes of some Metal Ions with Dipicolinic Acid and Amino Acids. J. Chem. Eng. Data, 2000, 45, 1108- 1110. |
[21] | Khalil, M. M.; Taha, M.; Equilibrium Studies of Binary and Ternary Complexes involving Tricine and some Selected Amino Acids. Monatschefte fur Chemie, 2004, 135, 385-395. |
[22] | Khalil, M. M.; Fazary, A. E.; Potentiometric Studies on Binary and Ternary Complexes of Di- and Trivalent Metal Ions involving some Monats Chem., 2004, 135, 1455- 1474. |
[23] | Khalil, M. M.; El-Deeb, M. M.; Mahmoud, R. K.; Equilibrium Studies of Binary Systems involving Lanthanide and Actinide Metal Ions and some selected Aliphatic and Aromatic Monohydroxamic Acids. J. Chem. Eng. Data, 2007, 52, 1571- 11579. |
[24] | Khalil, M. M.; Mahmoud, R. K.; New Insights into M(II)-Hydroxamate Interactions: The Electro-Analytical Behavior of Metal(II) Complexes Involving Monohydroxamic Acids and Diamines in an Aqueous medium, J. Chem. Eng. Data, 2008, 53, 2318-2327. |
[25] | Khalil, M. M.; Radalla, A. M.; Mohamed, A. G.; Potentiometric Investigation on Complexation of Divalent Transition Metal Ions with Some Zwitterionic Buffers and Triazoles. J. Chem. Eng. Data, 2009 (in press). |
[26] | Khalil, M. M.; Radalla, A. M; Mohamed, N. A.; Solution Equilibria and Thermodynamic studies on Complexation of Divalent Transition Metal Ions with Some Triazoles and Biologically Important Aliphatic Dicarboxylic Acids in Aqueous Media. The First Scientific Conference for Postgraduate Students. Beni-Suef University, Beni-Suef, Egypt, 2009, Jun. 26-28. P-200. |
[27] | Khalil, M. M.; Radalla, A. M.; Qassim, F.; Equilibrium and Thermodynamic Studies on Binary and Ternary Complex Systems Including Some Triazoles and Aromatic Carboxylic Acids. The First Scientific Conference for Postgraduate Students. Beni-Suef University, Beni-Suef, Egypt 2009, Jun. 26-28. P-400. |
[28] | Khalil, M. M.; Mohamed, S. A.; Radalla, A. M.; Potentiometric and Conductometric Studies on the Binary and Mixd-ligand Complexes in Solution: MII-Dipicolinic Acid-Glycine Systems. Talanta, 1997, 44, 1365-1369. |
[29] | Khalil M. M.; Radalla, A. M.; Binary and Ternary Complexes of Inosine Talanta, 1998, 46, 53-61. |
[30] | Gran, G. Determination of the Equivalence Point in Potentiometric Titration. Analyst 1952, 77, 6, 61-671. |
[31] | Welcher, F. J. The Analytical Uses of Ethylenediaminetetraacetic acid; Von Nostrand: Princeton, NJ, 1965. |
[32] | Gans, P.; O’Sullivan, B. Glee, a New Computer Program for Glass pH-Electrode Calibration. Talanta 2000, 51, 33-37. |
[33] | Longhi, P.; D'Andrea, F.; Mussini, T.; Rondinini, S.; Verification of the approximate equitransference of the aqueous potassium chloride salt bridge at high concentrations. Anal. Chem., 1990, 62, 1019-1021. |
[34] | Irving, H. M.; Rossotti, H. S. Methods for Computing Successive Stability Constants from Experimental Formation Curves. J. Chem. Soc., 1953, 3397-3405. |
[35] | Irving, H. M.; Rossotti, H. S. The Calculation of Formation Curves of Metal Complexes from pH Ttitration Curves in Mixed Solvent. J. Chem. Soc. 1954, 2904. |
[36] | Martell, A. E.; Smith, R. M.; Critical Stability Constants. Plenum Press, New York, 1976. |
[37] | Inezedy, J.; Determination of Equilibrium Constants, In: Analytical Applications of Complex Equilibria. Ellis Horwood, Chechester, 1976. |
[38] | C. D. Kennedy; Ionic Strength and the Dissociation of Acids. Biochemical Education, 1990, 18 35-40. |
[39] | James, P. D., Parameswaran, K. N., Acidic Dissociation Constants of Thiols. J Chem. Eng. Data, 1955, 6, 386-389. |
[40] | Elliott, D. C. Dawson, R. M.; James, K. M.; Data for Biochemical Research, Oxford Science Publications, 3rd ed, 1986, pp 1-31. |
[41] | Martin, R. B.; Prados, R. J.; Some Factors Influencing Mixed Complex Formation. J. Inorg. Nucl. Chem., 1974, 36, 1665-1674. |
[42] | H. Sigel: Metal Ions In Biological Sytems, Vol. 2. Marcel Dekker, New, York, 1973. |
[43] | Martell, A. E.; Smith, R. M.; Critical Stability Constants. Plenum Press, New York, 1974. |
[44] | Laurie, S. H.; James, C.; Binary and Ternary Complexes of hydroxmic Acids. Inorg. Chim. Acta, 1983, 78, 225-229. |
[45] | J. B. Chaires; Calorimetry and thermodynamics in drug design. Annu. Rev. Biophys., 2008, 37, 135-151. |
[46] | Shahbazi, Mina, Farzaneh Mehrzad, Masoud Mirzaei, Hossein Eshtiagh-Hosseini, Joel T. Mague, Mehdi Ardalani, and Mojtaba Shamsipur. "Synthesis, single crystal X-ray characterization, and solution studies of Zn (II)-, Cu (II)-, Ag (I)-and Ni (II)-pyridine-2, 6-dipicolinate N-oxide complexes with different topologies and coordination modes." Inorganica Chimica Acta 458 (2017): 84-96. |
[47] | Mirzaei, Masoud, Hossein Eshtiagh-Hosseini, Zahra Karrabi, Behrouz Notash, Antonio Bauzá, Antonio Frontera, Morteza Habibi, Mehdi Ardalani, and Mojtaba Shamsipur. "Synthesis, structure, solution and DFT studies of a pyrazine-bridged binuclear Cu (II) complex: On the importance of noncovalent interactions in the formation of crystalline network." Journal of Molecular Structure 1079 (2015): 78-86. |
[48] | Mirzaei, Masoud, Hossein Eshtiagh-Hosseini, Mojtaba Shamsipur, Mahdi Saeedi, Mehdi Ardalani, Antonio Bauzá, Joel T. Mague, Antonio Frontera, and Morteza Habibi. "Importance of polarization assisted/resonance assisted hydrogen bonding interactions and unconventional interactions in crystal formations of five new complexes bearing chelidamic acid through a proton transfer mechanism." RSC Advances 5, no. 89 (2015): 72923-72936. |
[49] | Hosseini-Hashemi, Zahra, Masoud Mirzaei, Ameneh Jafari, Peyman Hosseinpour, Mohammad Yousefi, Antonio Frontera, Mahmoud Lari Dashtbayaz, Mojtaba Shamsipur, and Mehdi Ardalani. "Effects of N-oxidation on the molecular and crystal structures and properties of isocinchomeronic acid, its metal complexes and their supramolecular architectures: experimental, CSD survey, solution and theoretical approaches." RSC advances 9, no. 44 (2019): 25382-25404. |
[50] | Hosseini Hashemi, Zahra, Masoud Mirzaei, Hossein Eshtiagh-Hosseini, Fereshteh Sadeghi, Mojtaba Shamsipur, Mehdi Ardalani, and Alexander J. Blake. "Solid and solution states studies of two Mn (II) complexes based on N-oxidized pyridine-2, 5-dicarboxylic acid." Journal of Coordination Chemistry 71, no. 24 (2018): 4058-4071. |
[51] | Soleimannejad, J., F. Moghzi, Sh Hooshmand, Z. Dankoob, M. Ardalani, and M. Shamsipur. "A comparison of ligand behaviors and interactions during supramolecular assembly using molecular dynamics simulation: Synthesis, solid state and solution studies of two Ni (II) compounds." Polyhedron 133 (2017): 24-32. |
APA Style
Abdelatty Mohamed Radalla. (2022). Complexation Equilibria and Determination of Stability Constants of Some Divalent Metal Ion Complexes of L-Cysteine and Diphenylamine in Aqueous Media. American Journal of Chemical Engineering, 10(2), 23-31. https://doi.org/10.11648/j.ajche.20221002.12
ACS Style
Abdelatty Mohamed Radalla. Complexation Equilibria and Determination of Stability Constants of Some Divalent Metal Ion Complexes of L-Cysteine and Diphenylamine in Aqueous Media. Am. J. Chem. Eng. 2022, 10(2), 23-31. doi: 10.11648/j.ajche.20221002.12
AMA Style
Abdelatty Mohamed Radalla. Complexation Equilibria and Determination of Stability Constants of Some Divalent Metal Ion Complexes of L-Cysteine and Diphenylamine in Aqueous Media. Am J Chem Eng. 2022;10(2):23-31. doi: 10.11648/j.ajche.20221002.12
@article{10.11648/j.ajche.20221002.12, author = {Abdelatty Mohamed Radalla}, title = {Complexation Equilibria and Determination of Stability Constants of Some Divalent Metal Ion Complexes of L-Cysteine and Diphenylamine in Aqueous Media}, journal = {American Journal of Chemical Engineering}, volume = {10}, number = {2}, pages = {23-31}, doi = {10.11648/j.ajche.20221002.12}, url = {https://doi.org/10.11648/j.ajche.20221002.12}, eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajche.20221002.12}, abstract = {Background. Metal complexes of biologically active ligands had considerable interests. L-cysteinate residue, L-Cys, is a biologically abundant and important versatile binding site of proteins. Diphenylamine, DPA, is an important aromatic amine containing two phenyl groups. Complexation equilibria of the divalent metal ions, Ca2+ and Zn2+ with the bio- relevant α-amino acid, L-cysteine and the nitrogen-containing diphenylamine ligand were investigated by means of the potentiometric technique at 25.0 ± 0.1°C and constant ionic strength of 0.200 ± 0.001 mol·dm-3 NaNO3. Objective. The stability constants and standard free energy changes of the α-amino acid, L-cysteine and diphenylamine complex species were determined at 0.200 ± 0.001 mol·dm-3ionic strength. Methods. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes were inferred from the potentiometric titrations. Results. The concentration distribution of L-cysteine species formed in solution was evaluated. The dissociation constants of the α-amino acid and diphenylamine were determined at different ionic strength. The stability constants of these binary and ternary systems were calculated. The values of ∆ log10 K, percent relative stabilization, %R.S. and log10 X for the ternary systems were evaluated and discussed. Concussion. The ternary complex formation occurred in a stepwise manner with L-cysteine acting as the primary ligand. The obtained values of ∆ G0 indicated that Complex formation reactions are spontaneous. Also, for all systems studied, the ternary complexes formed are more thermodynamically stable than the binary complexes.}, year = {2022} }
TY - JOUR T1 - Complexation Equilibria and Determination of Stability Constants of Some Divalent Metal Ion Complexes of L-Cysteine and Diphenylamine in Aqueous Media AU - Abdelatty Mohamed Radalla Y1 - 2022/03/29 PY - 2022 N1 - https://doi.org/10.11648/j.ajche.20221002.12 DO - 10.11648/j.ajche.20221002.12 T2 - American Journal of Chemical Engineering JF - American Journal of Chemical Engineering JO - American Journal of Chemical Engineering SP - 23 EP - 31 PB - Science Publishing Group SN - 2330-8613 UR - https://doi.org/10.11648/j.ajche.20221002.12 AB - Background. Metal complexes of biologically active ligands had considerable interests. L-cysteinate residue, L-Cys, is a biologically abundant and important versatile binding site of proteins. Diphenylamine, DPA, is an important aromatic amine containing two phenyl groups. Complexation equilibria of the divalent metal ions, Ca2+ and Zn2+ with the bio- relevant α-amino acid, L-cysteine and the nitrogen-containing diphenylamine ligand were investigated by means of the potentiometric technique at 25.0 ± 0.1°C and constant ionic strength of 0.200 ± 0.001 mol·dm-3 NaNO3. Objective. The stability constants and standard free energy changes of the α-amino acid, L-cysteine and diphenylamine complex species were determined at 0.200 ± 0.001 mol·dm-3ionic strength. Methods. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes were inferred from the potentiometric titrations. Results. The concentration distribution of L-cysteine species formed in solution was evaluated. The dissociation constants of the α-amino acid and diphenylamine were determined at different ionic strength. The stability constants of these binary and ternary systems were calculated. The values of ∆ log10 K, percent relative stabilization, %R.S. and log10 X for the ternary systems were evaluated and discussed. Concussion. The ternary complex formation occurred in a stepwise manner with L-cysteine acting as the primary ligand. The obtained values of ∆ G0 indicated that Complex formation reactions are spontaneous. Also, for all systems studied, the ternary complexes formed are more thermodynamically stable than the binary complexes. VL - 10 IS - 2 ER -