Determination of stability constants of metal(II)-methionine and metal(II)-methionine-cystiene (binary and mixed) complexes using the Paper Ionophoretic Technique

Mixed complexation reactions of methionine and cysteine with copper(II) and cobalt(II) have been studied in solution phase using the paper electrophoretic technique at ionic strength 0.1 M and temperature 35°C. The binary equilibria copper(II)-methionine and cobalt(II)-methionine have also been studied, since this is a prerequisite to the investigation of mixed complexes. The stability constants of copper(II)-methionine-cysteine and cobalt(II)-methionine-cysteine mixed complexes were found to be 2.80 ± 0.07 and 2.44 ± 0.11 (logarithm of stability constant values), respectively.     

Trace metal speciation in sea water — a paper electrophoretic approach

Stability constants of individual trace metal complexes form the basis for calculations predicting the distribution of trace metal species in complexing media, such as sea water. In this study, the electrophoretic mobility of radiotracer ²¹⁰Pb is measured as a function of ligand concentration in chloride and sulfate solutions of constant ionic strength and temperature. A theoretically-derived expression, relating mobility to ligand concentration and complex stability constants, is fitted by the method of least squares to the experimental data to obtain estimates of the conditional stability constants of lead(II) chloro and sulfato complexes at 23°C and ionic strength 0.7 i.e., under conditions resembling those of ocean water. The values obtained are: log β₁ = 0.999 ± 0.014, log β₂ = 1.037± 0.032, log β₃ = 1.250 ± 0.015 for lead(II) chloro complexes, and log β₁ = 1.048 ± 0.015 and log β₂ = 1.183 ± 0.025 for lead(II) sulfato complexes. Experiments with eight other metal ions [Au(III), Bi(III), Cd(II), Co(II), Cu(II), Hg(II), Ni(II), and Po(IV)] and with sea water as electrolyte indicate the general applicability of the method.     

Determination of Stability Constants of Metal(II)-Methionine and Metal(II)-Methionine-Cysteine (Binary and Mixed) Complexes with a Paper Ionophoretic Technique

A mixed complexation reaction of methionine and cysteine with copper(II) and cobalt(II) has been studied in solution phase using the paper electrophoretic technique at ionic strength 0.1 M and a temperature of 35°C. The binary equilibria copper(II)-methionine and cobalt(II)-methionine have also been studied, since this is prerequisite for the investigation of mixed complexes. The stability constants of copper(II)-methionine-cysteine and cobalt(II)-methionine-cysteine mixed complexes were found to be 2.80 ± 0.07 and 2.44 ± 0.11 (logarithm of stability constant values), respectively. This article was submitted by the authors in English.     

Physico-chemical studies of Ni(II), Co(II), Zn(II) and Cd(II) ions-p-bromobenzoylacetonate systems

The thermodynamic dissociation constant (pk_D) of p-bromobenzoylacetone and overall stability constants (log β₂) of its complexes with Ni(II), Co(II), Zn(II) and Cd(II) have been determined potentiometrically in dioxane-water mixture (75%, v/v) at 30±0·1°C in 0·1 M sodium perchlorate. On incorporating pH corrections, the pk_D of the ligand became 11·76±0·02. The thermodynamic values of log β₂ have been evaluated using correction-term method, linear plot and method of least squares. The values of log β₂ obtained from the latter method turned out to be 18·64±0·03, 17·94±0·04, 17·53±0·03 and 14·75±0·03 for Ni(II), Co(II), Zn(II) and Cd(II) complexes, respectively. This order is consistent with the Irving-William's series.The solid bis(p-bromobenzoylacetonate) dihydrate complexes of these metals have been synthesised and characterised.     

simple and mixed ligand complexes of copper(II) with polyfunctional phenolic compounds as models of natural substances

In order to analyse metal complexation with polyfunctional phenolic compounds as ligand models of natural substances, a detailed examination is described for five simple binary complexes and three ternary mixed ligand complexes at 25°C (μ = 0.1 M NaClO₄). The ligands are tyrosine, 4,5-dihydroxy-1,3-benzene disulfonic acid, disodium salt (tiron), 3,4-dihydroxycinnamic acid (caffeic acid), 3,4,5-trihydroxy-1 -cyclohexene-1 -carboxylic acid (shikimic acid) and 1,3,4,5-tetrahydroxycyclohexanecarboxylic acid 3-(3,4-dihydroxycinnamate) (chlorogenic acid). The ternary systems are Cu(II)/H_qA/tiron, where H_qA is tyrosine, caffeic or chlorogenic acids. Potentiometric data were used successively to evaluate the protonation of each individual ligand, to detect simple and mixed complexes (including protonated species) and to determine their stability constants (a set of 33 values of constants with several original data is provided). The calculated distribution (speciation) of each species as a function of pH is indicated. Mixed coordination enhances the stability of complexes and the stabilization is expressed in terms of various parameters. The results emphasize that mixed ligand complex formation is essential to studies of multiple equilibria.     

Mixed ligand complex formation of copper(II) and zinc(II) ions with 3-hydroxynaphthoate and picolinate ions as ligands in dioxane-water mixtures

Cu(II)-hydroxynaphthoate-picolinate and Zn(II)-hydroxynaphthoate-picolinate ternary systems were studied in dioxane-water (1 : 1, ν/ν) solutions at a 0.2 mol dm⁻³ ionic strength and 25°C. From EMF data the mixed ligand complexes M(hna)(pic) for M = Cu(II) and Zn(II) and M(hna)(pic)₂ for M = Zn(II) were detected and their formation constants evaluated (log K_f = 18.94± 0.03, 18.09±0.08 and 23.4±0.07, respectively). Factors contributing to the stabilization of these complexes are discussed and optimum experimental conditions for their predominance established.     

The Interaction of Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) with Mixed Donor Macrocycles Containing Pendant Carboxylic Acid Functions

The syntheses of mixed oxygen-nitrogen donor macrocycles incorporating two or three pendant carboxylic acid groups are described. Potentiometric titrations in water (I = 0.1; KNO₃) at 25°C have been used to determine the stability constants for the 1: 1 (metal:ligand) complexes of Co(II). Ni(II), Cu(II), Zn(II), and Cd(II). The constants obtained are compared with the previously determined values for the corresponding complexes of the unsubstituted macrocyclic precursors. The results of these studies indicate that each carboxylate function participates in binding to the central metal. For some metal-ion/ligand systems there is evidence that ring size effects influence the overall stability patterns and that, in such cases, both the ether oxygens as well as the tertiary amines of the macrocyclic rings appear to bind to the metal.     

Composition and stability constants of copper(II) complexes with succinic acid determined by capillary electrophoresis

The advantage of capillary electrophoresis was demonstrated for studying a complicated system owing to the dependence of direction and velocity of the electrophoretic movement on the charge of complex species. The stability constants of copper(II) complexes with ions of succinic acid were determined by capillary electrophoresis, including the 1?:?2 metal to ligand complexes which are rarely mentioned. The measurements were carried out at 25 °C and ionic strength of 0.1, obtained by mixing the solutions of succinic acid and lithium hydroxide up to pH 4.2–6.2. It was shown that while pH was more than 4.5 the zone of copper(II) complexes with succinate moves as an anion. It is impossible to treat this fact using only the complexes with a metal-ligand ratio of 1?:?1 (CuL⁰, CuHL⁺). The following values of stability constants were obtained: log β(CuL) = 2.89 ± 0.02, log β(CuHL⁺) = 5.4 ± 0.5, log β(CuL₂^2?) = 3.88 ± 0.05, log β(CuHL₂^?) = 7.2 ± 0.3.     

Polarographic Determination of the Formation Constants of the Mixed Ligand Complexes of Cd(II) and Pb(II) with Thiosulphate and Halide Ions

The mixed ligand complexes of Cd(II) and Pb(II) with thiosulphate as a primary ligand and chloride, bromide of iodide (individually) as a secondary ligand have been polarographically, investigated at 30°C and at a constant ionic strength of μ = 1.0 M (NaClO₄). Two mixed ligand complexes were formed with the Cd(II) ion: log β₁₂ = 4.77, 5.30 and 6.78 for the chloride, bromide and iodide ions, respectively; and log β₂₁ = 5.36, 5.04 and 6.22 for the same ions. For the Pb(II)-Ts-Cl system, only one mixed ligand complex was formed with a log stability constant log β₂₁ =4.35. For the Pb(II)-Ts-Br system, three mixed ligand complexes are obtained with log β₁₁ = 3.63, log β₁₂ = 4.51 and log β₂₁ = 4.85.     

Studies on the Interaction of Lead(II) and Uranyl(II) with Methylcysteine and Penicillamine Bioactive Sulfur-Containing Ligands

Quantitative indication of a complex formation comes from the estimation of the stability or formation constants characterizing the equilibria corresponding to the successive addition of ligands. The binary equilibria of metal(II)-methylcysteine and also mixed equilibria metal(II)-methylcysteine-penicillamine are studied using paper electrophoretic technique. The method is based on the migration of a spot of metal ion with the complexones added to a background electrolyte at the pH 8.5. The stability constants of the mixed complexes Pb(II)-methylcysteine-penicillamine and UO₂(II)-methylcysteine-penicillamine are found to be 2.80 ± 0.09 and 3.40 ± 0.07 (logarithm of stability constant values) at a ionic strength of 0.1 M (HClO₄/NaClO₄) and a temperature of 35°C.__________From Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 344–348.Original English Text Copyright © 2005 by Tewari.This text was submitted by the author in English.     

Paper electrophoretic determination of the stability constants of biologically significant binary complexes of beryllium(II) and cobalt(II) with sarcosine

Quantitative indication of the process of forming a complex comes from the evaluation of the stability constants or formation constant, which characterize the equilibria corresponding to the successive addition of ligands. Paper electrophoretic technique is described for the study of beryllium(II) and cobalt(II) biologically significant binary complexes with sarcosine. The stability constants of ML and ML₂ complex species of Be(II)/Co(II)—sarcosine have been found to be (6.17 ± 0.09, 4.06 ± 0.04) and (4.27 ± 0.07, 2.98 ± 0.11) (log-arithm stability constant values), respectively at ionic strength 0.1 Mol L⁻¹ and a temperature of 35°C.     

Aqueous complexation studies of lead(II) and cadmium(II) with 1,3-bis(tris(hydroxymethyl)methylamino)propane pH buffer

Hydrogen buffers are important in biological studies, as a steady hydrogen concentration is of great importance in most scientific studies. One of these buffers is 1,3-bis(tris(hydroxymethyl)methylamino)propane (BTP), which, considering its structure, has complexing capabilities, as previously shown for other metals. In order to know the stability constants for Cd(II) or Pb(II) with BTP, glass electrode potentiometry and direct current polarography studies were carried out. Our results show that both metals form metal complexes, with Pb(II) forming stronger complexes with BTP as evidenced by its higher stability constants. In the Pb-BTP system, five species were described; PbHL, PbL, PbL₂, PbL₂(OH), and PbL₂(OH)₂, and their stability constants were determined to be 11.4 ± 0.3, 4.7 ± 0.3, 8.8 ± 0.2, 14.4 ± 0.3, and 18.4 ± 0.3, respectively. For the Cd-BTP system, four complexes were detected; CdHL, CdL, CdL(OH), and CdL(OH)₂, and their stability constants were also determined as 10.9 ± 0.4, 4.10 ± 0.07, 8.2 ± 0.2, and 10.9 ± 0.2, respectively. These complexes decrease considerably the amount of free metal in solution within the buffering pH range. This fact should be considered when planning experiments were BTP and Pb(II) and/or Cd(II) ions are present.     

Paper electrophoretic technique in the study of metal complexes

A new method, paper electrophoresis, involving the use of a ionophoretic technique is described for the study of equilibria in binary complex system in solution. The stability constants of ML and ML₂ complex species of metal(II)-α-aminobutyric acid and metal(II) — homoserine were found to be [(8.09 ± 0.03, 6.89 ± 0.09) (3.58 ± 0.07, 2.67 ± 0.11) (7.66 ± 0.06, 6.13 ± 0.02)]; [(7.80 ± 0.07, 6.45 ± 0.02) (2.93 ± 0.04, 1.97 ± 0.01) (7.41 ± 0.011, 4.67 ± 0.06)] for copper(II), manganese(II) and uranyl(II) complexes, respectively at an ionic strength 0.1 M and 35°C. Published in Russian in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 7, pp. 1196–1199. The article is published in the original.     

Potentiometric and Theoretical Studies of (2Z, 3Z)-2H-benzo[b][1,4]thiazine-2,3(4H)-dionedioxime with Some Divalent Transition Metal Ions

The protonation equilibria of (2Z, 3Z)-2H-benzo[b][1,4]thiazine-2,3(4H)-dionedioxime (BTDH₂) together with the equilibria of its bis- binary complexes of Co(II), Ni(II), Cu(II) and Zn(II) were investigated potentiometrically. The investigation was carried out at 25 ± 0.1 °C, in aqueous solution, with a constant ionic strength of 0.100 mol·dm^?3 NaCl. The protonation constants of the ligand together with the stability constants of a variety of complexes were determined potentiometrically in 10 % ethanol–water mixed solution using the SUPERQUAD computer program. Theoretical calculations were set up to assist in understanding the protonation sequence in the ligand molecule via the semi-empirical molecule orbital method of parameterized model number 3. Results are discussed in connection to the basicity of the donor atoms and structural arrangement of the ligand. Although BTDH₂ has two dissociable protons, four protonation constants can be measured under the experimental conditions presented. These four protonation constants (as log₁₀ βs) are 10.245, 19.397, 22.414 and 25.176.     

Complexation behaviour of benzilmono(Iepidyl)hydrazone (BLH) toward bivalent metal ions: A potentiometric study

Potentiometric investigations on metal complexes of various bivalent metal ions, viz. UO₂(II), Cu(II), Ni(II), Co(II), Cd(II), Pb(II), Zn(II) and Mn(II) with benzilmonol(lepidy!)hydrazone (BLH) have been carried out at different ionic strengths and at different temperatures in order to determine stability constants of the complexes. Thermodynamic parameters ΔC, ΔH and ΔS have also been evaluated from temperature coefficient data. The effect of varying the dielectric constant of the medium on the stability constants of complexes has also been investigated at 30±0.5°C and μ = 0.1MNaCl. Thermodynamic stability constants and thermodynamic stabilization energies for the first transition metals have also been discussed.     

Electrophoretic studies on the mixed nitrilotriacetate-penicillamine complexes of Pb2+ and UO 2 2+

A technique involving the use of paper electrophoresis is described for the study of binary and mixed-complex systems in solution. This technique is based on the movement of a spot of metal ion in an electric field with the complexants added in the background electrolyte at pH 8.5. The concentration of primary ligand (nitrilotriacetate) was kept constant, while that secondary ligand (penicillamine) was varied. A graph of log[penicillamine] versus mobility was used to obtain information on the mixed complexes and to calculate stability constants. The stability constants of mixed-ligand complexes lead(II)-nitrilotriacetate-penicillamine and uranyl(II)-nitrilotriacetate-penicillamine have been found to be 5.68 ± 0.09 and 6.56 ± 0.05 (logarithm stability constant values), respectively, at ionic strength 0.1 M and a temperature of 35°C. The text was submitted by the author in English.     

Potentiometric study of the protonation and binary complexation equilibria between the hydrogen ion,copper(II) ion and zinc(II) ion and the picolinate ion in dioxane-water mixtures

Protonation constants of picolinic acid and stability constants of Cu(II) and Zn(II) picolinate complexes were determined potentiometrically in 50% (v/v) dioxane-water solution at 25°C and 0.2 M KNO₃. The values obtained for the constants were: protonation constants for picolinate ion: logβ₁ = 5.36±0.01 and logβ₂ = 6.80±0.04; stability constants for copper(II) complexes: logβ_1.1 = 7.766±0.001 and logβ_1.2 = 16.826±0.007; stability constants for the Zn(II) complexes: logβ_1.1 = 6.10±0.05, logβ_1.2 = 11.47±0.03 and logβ_1.3 = 15.77±0.08. No protonated nor hydroxo-complex was detected in the metal ion-picolinate systems.     

Polarographic study of mixed ligand complexes of Pb(II) with carboxylate ions and imidazole

Mixed complexes of Pb(II) with some carboxylate ions, viz. tartrate (tart^2?), malonate (mal^2?) and citrate (citr^3?); and imidazole (im) have been studied polarographically at 25°C and at constant ionic strength μ = 2.0 (NaNO₃) and at pH 6. The polarographic reduction of the complexes in each case is reversible and diffusion-controlled. Pb(II) forms a single mixed complex with tartrate and imidazole, viz [Pb(tart)(im)] with stability constant log β₁₁ = 4.19; with mal^2? and im, three mixed complexes, [Pb(mal)(im)], [Pb(mal)(im)₂] and [Pb(mal)₂(im)]^2? with stability constants log β₁₁ = 4.3, log β₁₂ = 7.3 and log β₂₁ = 5.5 respectively are formed. With citr^3? and im a single mixed species, [Pb(citr)(im)]^? with stability constant log β₁₁ = 8.0 is formed. Various equilibria involved in the mixed systems have been discussed.     

Proton-ligand and metal ligand stability constants ofN-o-chlorophenylbenzohydroxamic acids with manganese(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II)

Summary The thermodynamic proton-ligand and metal ligand stability constants of the newN-o-chlorophenylbenzohydroxamic acids with manganese, nickel, copper, zinc, cadmium and mercury have been determined in 1 : 1 dioxan : water at 25°.The stability of the complexes mostly follow the ligand basicity order and also the metal ion electron affinities as measured by their ionization potential. The stability constants of the metal complexes follow the order: Cu^(II) > Zn^(II) > Ni^(II) > Mn^(II) > Hg^(II) > Cd^(II).     

Binary and ternary complexes of Cu(II) ions with saccharin and cysteine

The square-wave voltammetric behaviour of cysteine and saccharin was studied at a static mercury drop electrode at pH 7.4 in the presence of Cu(II) ions. In the presence of excess Cu(II), cysteine exhibited three reduction peaks for Hg(SR)₂ (−0.086 V), free Cu(II) (−0.190 V) and Cu(I)SR (−0.698 V), respectively. Saccharin produced a catalytic hydrogen peak at −1.762 V. In the presence of Cu(II), saccharin gave a new peak (−0.508 V), corresponding to the reduction of Cu(II)–saccharinate, which in the presence of cysteine formed a mixed ligand complex (−0.612 V), CuL₂A₂ (L=saccharin and A=cysteine). The peak potentials and currents of the obtained complexes were dependent on the ligand concentration and accumulation time. The stoichiometries and overall stability constants of these complexes were determined by Lingane's method (voltammetrically) and Job’s method (spectrophotometrically). The mixed ligand complex in the molar ratio 1:2:2 (log β=33.35) turned out to be very much stronger than the 1:1 Cu(I)SR (log β=21.64) and 1:2 Cu(II)–saccharinate (log β=16.68) complexes. Formation of a mixed ligand complex can be considered as a type of synergism.