Complexes of vitamin B6—XV quaternary complexes involving pyridoxamine,glycine and ethylenediamine with Co(II), Ni(II), Cu(II) and Zn

The formation constants of quaternary Co(II), Ni(II), Cu(II) and Zn complexes comprising pyridoxamine as a first, glycine as a second and ethylenediamine as a third ligand were determined by pH-metric titration at I = 0.5 M NaNO₃ and 30°. The complexes are generally protonated in which the ligands may act as bidentate as well as monodentate. The formation of the quaternary species is discussed in relation to pertinent binary and ternary species. The validity of the Van Panthaleon van Eck equation was also tested.     

Complexes of vitamin B6. Part XI. Ternary complexes of some bivalent metal ions with ethylenediamine and pyridoxamine

Summary The stability constants of ternary Co^II, Ni^II, Cu^II, Zn^II and Cd^II complexes containing pyridoxamine as a first and ethylenediamine as a second ligand were determined by pH titration at I =0.50M NaNO₃ and 30 °C. Most of the complexes are protonated, probably on the pyridoxamine moiety. The formation of the ternary complex species is discussed in terms of binary species formation. Spectral characteristics of some of the ternary complex systems are discussed.Part X. Binary, Ternary and Quaternary Complexes Involved in Systems of Pyridoxamine-Glycine or Glycylglycine-Imidazole with Some Bivalent Metal Ions,21st Internat. Conf. on Coord. Chem., Toulouse, France (1980);     

Binary,ternary and quaternary complexes invloved in the systems pyridoxamine-glycine-imidazole with some bivalent metal ions

Equilibrium-based computer models using MINIQUAD-75 program were utilized to determine the stoichiometry and formation constants involved in the systems pyridoxamine(Pm)-glycine (Gly)-imidazole (lmd) with CO(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal ions. The data were obtained from potentiometric pH titration of the various binary and ternary quaternary systems under physiological-like conditions (0.15 M NaNO₃-37°C). Various composition ratios of metal and ligands were used. The ligand concentrations did not exceed 4 times the concentration of metal ion in the binary systems and 4 times of the metal ions in ternary systems. In case of the quaternary systems only imidazole concentrations were two or four times the concentrations of metal ions keeping those of other ligands equal to that of metal ions. The stability constants of the quaternary species are discussed in terms of binary and ternary constants as are the effect of ring size on the stability of mixed ligand species. In addition, electrostatic as well as statistical effects also are mentioned and the biological implications of these model equilibria are described.     

Equilibrium Studies of Binary and Mixed-Ligand Complexes of Zinc(II) Involving 2-(Aminomethyl)-Benzimidazole and Some Bio-Relevant Ligands

Binary and mixed-ligand complexes of zinc(II) involving 2-(aminomethyl)-benzimidazole (AMBI) and amino acids, peptides (HL) or DNA constituents have been investigated. Ternary complexes of amino acids or peptides are formed simultaneously. Amino acids form the complex Zn(AMBI)L, whereas amides form two complex species Zn(AMBI)L and Zn(AMBI)(LH_?1). The ternary complexes of zinc(II) with AMBI and DNA are formed in a stepwise process, whereby binding of zinc(II) to AMBI is followed by ligation of the DNA constituents. The stability of ternary complexes is quantitatively compared with their corresponding binary complexes in terms of the parameters ??log₁₀ K, log₁₀ ??_stat and log₁₀ X. The effect of the side chains of amino acid ligands (??_R) on complex formation is discussed. The values of ??log₁₀ K indicated that the ternary complexes containing aromatic amino acids are significantly more stable than the complexes containing alkyl- and hydroxyalkyl-substituted amino acids. This may be taken as evidence for a stacking interaction between the aromatic moiety of AMBI and the aromatic side chains of the bio-active ligands. The concentration distributions of various species formed in solution were also evaluated as a function of the pH.     

Copper(II) complexes of imino-bis(methyl phosphonic acid) with some bio-relevant ligands. Equilibrium studies and hydrolysis of glycine methyl ester through complex formation

Binary and ternary complexes of Cu(II) involving imino-bis(methyl phosphonic acid) (IdP) abbreviated as H₄A and some selected bio-ligands, amino acids, peptides and DNA constituents (L), were examined. Cu(II) forms CuA and CuAH complexes with IdP. Ternary complexes are formed in a stepwise mechanism whereby iminodiphosphonic acid binds to Cu(II), followed by coordination of amino acid, peptide or DNA. The concentration distribution of the various complex species has been evaluated. The kinetics of base hydrolysis of glycine methyl ester in the presence of Cu(II)-IdP was studied in aqueous solution at different temperatures, and in dioxane-water solutions of different compositions at 25°C. The activation parameters are evaluated and discussed.     

Complex Formation Reactions of Promethazine Copper(II) and Various Biologically Relevant Ligands. Synthesis,Equilibrium Constants,Spectroscopic Characterization and Biological Activity

Binary and ternary complexes of copper(II) involving promethazine, N,N-dimethyl-3-(phenothiazin-10-yl)propylamine (Prom) and various biologically relevant ligands containing different functional groups, were investigated. The ligands (L) are dicarboxylic acids, amino acids, amides and DNA constituents. The ternary complexes of amino acids, dicarboxylic acids or amides are formed by simultaneous reactions. The results showed the formation of Cu(Prom)(L) complexes with amino acids and dicarboxylic acids. The effect of chelate ring size of the dicarboxylic acid complexes on their stability constants was examined. Amides form both Cu(Prom)(L) complexes and the corresponding deprotonated species Cu(Prom)(LH₋₁). The ternary complexes of copper(II) with (Prom) and DNA are formed in a stepwise process, whereby binding of copper(II) to (Prom) is followed by ligation of the DNA components. DNA constituents form both 1:1 and 1:2 complexes with Cu(Prom)²⁺. The stability of these ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters Δlog₁₀ K. The values of Δlog₁₀ K indicate that the ternary complexes containing aromatic amino acids were significantly more stable than the complexes containing alkyl- and hydroxyalkyl-substituted amino acids. The concentration distribution of various complex species formed in solution was also evaluated as a function of pH. The solid complexes [Cu(Prom)L)] where L=1,1-cyclobutanedicarboxylic acid (CBDCA), oxalic and malonic acid were isolated and characterized by elemental analysis, infrared, TGA, and magnetic susceptibility measurements. Spectroscopic studies of the complexes revealed that the complexes exhibits square planar coordination with copper(II). The isolated solid complexes have been screened for their antimicrobial activities using the disc diffusion method against some selected bacteria and fungi. The activity data show that the metal complexes are found to have antibacterial and antifungal activity.     

Thermodynamique des complexes metalliques ternaires des amino acides: Etude du systeme Ni(II)—Glycine—DL-α-alanine

Standard enthalpies and entropies of formation for binary and ternary Ni(II) complexes with glycine and DL-α-alanine were calorimetrically determined at 25°C in aqueous solution (I = 1 M NaClO₄). The evolution of these values from binary to ternary complexes is discussed on the basis of the stabilization characterizing the stability constants of the ternary species which have been previously calculated under the same experimental conditions.     

Complexation Equilibria of Zn(II), Pb(II) and Cd(II) with Reduced Glutathione (GSH) and Biologically Important Zwitterionic Buffers

The interaction of zinc(II), lead(II), and cadmium(II) with Glutathione (S‐L‐glutamyl‐Lcysteinylglycine) as primary ligand and zwitterionic buffers (N‐[2‐Hydroxyethyl]piperazine‐N′‐[2‐ethanesulfonic acid]) (HEPES) and (N‐Hydroxyethyl]piperazine‐N′‐[2‐hydroxy‐propanesulfonic acid]) (HEPPSO) as secondary ligands were studied by potentiometric‐pH titration in 1:1:1 ratio at 25.0 °C and I = 0.1 mol.dm^?3 (KNO₃). The formation constants of different normal and protonated binary and ternary complex species were calculated. Formation constants for the monohydroxy, and dihydroxy complexes for the binary systems M(II) + HEPES and M(II) + HEPPSO have been evaluated. The distribution curves for the various complex species as a function of pH were constructed.     

Ternary complexes involving copper(II) and amino acids,peptides and DNA constituents. The kinetics of hydrolysis of α-amino acid esters

Binary and ternary complexes of copper(II) involving picolylamine (Pic) and amino acids, peptides (HL) or DNA constituents have been investigated. Ternary complexes of amino acids or peptides are formed by simultaneous reactions. Amino acids form the Cu(Pic)L complex, whereas peptides form Cu(Pic)L and Cu(Pic)(LH_–1). The ternary complexes of copper(II) with picolylamine and DNA are formed in a stepwise process, whereby binding of copper(II) to picolylamine is followed by ligation of the DNA components. The stability of the ternary complexes is compared with the stabilities of the corresponding binary complexes. The hydrolysis of glycine methyl ester (MeGly) is catalysed by the Cu(pic)²⁺ complex. The kinetic data is fitted assuming that the hydrolysis proceeds in two steps. The first step, involving coordination of the amino acid ester by the amino and carbonyl groups, is followed by rate-determining attack by the OH^– ion. The second step involves equilibrium formation of the hydroxo-complex, Cu(pic)(MeGly)(OH), followed by intramolecular attack.     

Complex Formation Equilibria Between Zinc(II), Nitrilo-tris(Methyl Phosphonic Acid) and Some Bio-relevant Ligands. The Kinetics and Mechanism for Zinc(II) Ion Promoted Hydrolysis of Glycine Methyl Ester

Binary and ternary complexes of zinc(II) involving nitrilo-tris(methyl phosphonic acid (H₆A) and amino acids, peptides (HL), or DNA constituents have been investigated. The stoichiometry and stability constants for the complexes formed are reported. The results show that ternary complexes are formed in a stepwise manner whereby nitrilo-tris(methylphosphonic acid) binds to zinc(II), which is then followed by coordination of an amino acid, peptide or DNA. Zinc(II) was found to form ZnA and ZnAH _n complex species where n=3, 2 or 1. The stabilities of the ternary complexes are compared with the stabilities of their corresponding binary complexes. The concentration distributions of the various complex species have been evaluated. The kinetics of the base hydrolysis of glycine methyl ester in the presence of Zn(II)-NTP complexes was studied in aqueous solution using a pH-stat technique. The pK _a for ionization of the coordinated water molecule is 9.14 as determined from the kinetic results, while direct potentiometric titration of the complex [Zn(NTP)(H₂O)] gave 9.98 (±0.02). The rate constant for the intramolecular attack of coordinated hydroxide on the ester is k=(2.65×10⁻⁴±0.003) dm³⋅mol⁻¹⋅s⁻¹.     

Linear free energy relationships between stability of complex and basicity of ligand: VII. The copper(II)-heteronuclear aromatic base-aminoacid ternary systems

The formation constants of ternary mixed ligand complex compounds formed from Cu(II)-2,2′-bipyridyl (bipy) with N-(para-substituted phenyl) glycines (pRPhG), Cu(II)-1,10-phenanthroline (phen) with N-(meta-substituted phenyl) glycines (mRPhG), Cu(II)-bipy/phen with some α-aminoacids (αA) have been determined by pH method at 25°C in the presence of 0.10 M NaClO₄. It was found that linear free energy relationships do exist between the stability of ternary complex compounds and the base strengths of the ligands in all four ternary systems investigated. The stability of the ternary complex compounds was discussed in terms of ΔlogK_M and log X values. It was found again that linear relationships exist between Δ log K_M, log X and pK₂ in the Cu(II)-phen-mRPhG ternary system.     

Binary and ternary complexes of Cd(II) involving triethylenetetramine and selected amino acids and DNA units

The formation equilibria of the binary complex of cadmium(II) with triethylenetetramine (Trien) and of ternary complexes Cd(Trien)L, where L refers to amino acids, DNA constituents and related compounds have been investigated. Cd(II) was found to form a highly stable complex with Trien. The acid-base equilibria of Cd(Trien)²⁺ were characterized. Ternary complexes of amino acids and DNA constituents are formed through stepwise mechanism, whereby Trien binds to Cd(II), followed by interaction with ligand (L), whereas thiol-containing ligands form ternary complexes through a simultaneous mechanism. The formation constants of the complexes were determined at 25 °C and , = 0.1M NaNO₃. The participation of different ligand functional groups in the complex-formation was examined.     

Equilibrium studies of organotin(IV) complexes with vitamin B(6)

The complex-formation equilibria of dimethyltin(IV), trimethyltin(IV) and tributyltin(IV) with pyridoxamine were investigated in dioxane-water mixtures and at different temperatures using a potentiometric technique. The stepwise formation constants of the complexes formed in solution were calculated using the non-linear least-square program MINIQUAD-75. The effect of dioxane as a solvent on the protonation constants of pyridoxamine and the formation constants of organotin(IV) complexes was discussed. The thermodynamic parameters DeltaH degrees and DeltaS degrees calculated from the temperature dependence of the equilibrium constants were investigated. The concentration distribution of the various complex species was evaluated as a function of pH.     

Solution equilibria of pyridinecarboxylic acids: Complexation reaction of 2-mercaptonicotinic acid-copper (II) complex with thiosalicylic acid

The reaction of 2-mercaptonicotinic-copper (II) complex (Cu²⁺-MENA, 1 3n 1) with thiosalicylic acid (TSA) has been investigated spectrophotometrically in ethanol-water solution (50%, v/v) at I=O.IM (NaClO₄) and 25°C. Under the acidic conditions encountered in this study, there are competing equilibria between protonation of the Cu²⁺-MENA binary chelate, the formation of the Cu(MENA)(TSA) ternary complex and protonation of the second ligand (TSA). The equilibrium constants for the complexation reactions and the stability of the mixed-ligand complex are determined. The optimum conditions for the predominance of the ternary complex are established and the enhancement of this complex over binary complex formation is evaluated. Complex-forming equilibria have also been examined by potentiometric-pH titrations and the experimental data are discussed in relation to various equilibria existing in solution. Structural and bonding features of the mixed-ligand complex are illustrated from considerations of the IR spectral data.     

Investigations of ternary complexes of Co(II) and Ni(II) with oxydiacetate anion and 1,10-phenanthroline or 2,2′-bipyridine in solutions

Potentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H₂O)], [Co(ODA)(bpy)(H₂O)], [Ni(ODA)(phen)(H₂O)] and [Ni(ODA)(bpy)(H₂O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.      

Mixed Ligand Complex Formation Reactions and Equilibrium Studies of Cu(II) with Bidentate Heterocyclic Alcohol (N,O) and Some Bio-Relevant Ligands

The formation equilibria of copper(II) complexes and the ternary complexes Cu(HMI)L (HMI=4-Hydroxymethyl-imidazole, L=amino acid, amides or DNA constituents) have been investigated. Ternary complexes are formed by a simultaneous mechanism. The results showed the formation of Cu(HMI)L and Cu(HMI,H₋₁)(L) complexes. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters Δlog ₁₀ K and log ₁₀ X. The effect of the side chains of amino acid ligands (Δ_R) on complex formation was discussed. The concentration distributions of various species formed in solution were also evaluated as a function of pH. The thermodynamic parameters ΔH° and ΔS° calculated from the temperature dependence of the equilibrium constants are investigated. The effects of dioxane as a solvent, on the protonation constant of HMI and the formation constants of Cu^II–HMI complexes, were discussed.     

Pyridoxamine,a scavenger agent of carbohydrates

Pyridoxamine has been found to inhibit protein glycation and to avoid the formation of advanced glycation end‐products (AGEs). One of the mechanisms by which pyridoxamine can inhibit glycation involves the scavenger of carbonyl groups with glycation capacity. In this work, we conducted a kinetic study of the reactions of pyridoxamine with various carbohydrates under physiological pH and temperature. The reactions involving hexoses were found to give a tricyclic compound ( 5 ) in addition to pyridoxal and pyridoxine. Such a tricyclic compound inhibits the Amadori rearrangement and the formation of other carbonyl compounds with glycating properties. The reactions involving pentoses gave compound 7 and pyridoxal—by transamination of the Schiff base. The transamination reaction enhances the inhibitory action of pyridoxamine. The formation rate constants for the Schiff base, k₃, were found to be similar to those for the reactions of D ‐glucose with amino acids, which suggests competition between pyridoxamine and terminal amino residues in proteins for glycating sites in sugars. These constants are dependent on the electrophilic character of the carbonyl carbon in the carbohydrate. © 2007 Wiley Periodicals, Inc. 39: 154–167, 2007     

Insight into the Complexation Mode of Bis(nitrilotriacetic acid) (NTA) Ligands with Ni2+ Involved in the Labeling of Histidine‐Tagged Proteins

According to literature reports and our own findings, the binding of new Ni²⁺‐preloaded bis(nitrilotriacetic acid) (NTA) ligands with polyhistidine‐tagged proteins has been found to be accompanied by a one‐ to two‐order‐of‐magnitude increase in affinity, compared to the binding of a single Ni²⁺‐preloaded NTA moiety. In spite of the introduction of a second NTA chelating group, a cooperative effect that is less than the theoretical maximum has been observed. Herein, we present a rational explanation for the observed stability of the ternary complex involving the postulated bis‐NTA–(Ni²⁺)₂ species and multivalent polyhistidine tags. We have found that prior to the formation of the ternary complex, the Ni²⁺‐preloading step of bis‐NTA ligands does not form the expected bis‐NTA–(Ni²⁺)₂ exclusively. Instead of the major formation of bis‐NTA–(Ni²⁺)₂ species, it appears that cyclic discrete 1:1 and 2:2 entities are predominantly formed. It is proposed that these species interact upon ring‐opening with multivalent histidine tags. The occurrence of this phenomena accounts for the overall one‐ to two‐order‐of‐magnitude increase in affinity of ternary complexes involving bis‐NTA ligands.     

Charge-transfer photochemistry of the ternary complex (dithio-diseleno-carbamato)copper(II)

Photolysis of the ternary system consisting of diethyldithiocarbamate (Et2dtc), diethyldiselenocarbamate (Et2dsc) and copper(II) (1:1:1) has been studied in isobutylmethylketone (IBMK), toluene, chloromethane and chloromethane/ROH solutions (chloromethane = CCl4, CHCl3 or CH2Cl2 and ROH = EtOH or i-PrOH). The results obtained by EPR techniques and UV-Vis data indicate that a homolytic Cu-S bond cleavage involving the dithiocarbamate (dtc) ligand appears as the primary photo-process in Cu(Et2dtc)(Et2dsc) photolysis. Further conversion of the primary photoproduct Cu(I)(Et2dsc) is discussed in terms of a specific interaction with the solvent. In chloromethanes and chloromethane/ROH Cu(I)(Et2dsc) is oxidised by the solvent to give the corresponding paramagnetic mixed-ligand Cu(II)(Et2dsc)Cl complex and/or its chloride-bridged and EPR silent dimer Cu2(Et2dsc)2Cl2. The formation of the monomeric species occurs through a co-ordination of the alcohol molecule in the xy plane of the complex. Because of its co-ordination inertness, toluene poorly stabilises the primary photoproduct Cu(I)(Et2dsc), thus providing an effective primary recombination process and lower efficiency of Cu(Et2dtc)(Et2dsc) photolysis. The formation of the bis-solvated mixed-ligand complex Cu(II)(Et2dsc)+ in IBMK is also discussed.     

Effect of chromium(III) and of other ions on the absorptiometric determination of copper with 2, 2'-biquinolyl

In the determination of small amounts of copper in certain alloys by liquid-liquid extraction of the bis-chelate of copper(I) with 2, 2'-biquinolyl, recovery of copper has been reported to be low when chromium(III) is present. The adverse effect of chromium(III) could be overcome by adding iron(II). It is now shown that the inhibiting effect of chromium is attributable to the formation of a kinetically inert ternary complex of chromium(III), copper(II) and citrate ions containing an equal number of atoms of each of the two metals. Copper can be displaced from this complex by any of the transition cations Mn(II), Fe(II), Co(II), Ni(II) and Zn(II). Zinc is shown to form a ternary complex formally analogous to that of copper. The formation of the ternary complexes has been studied polarographically. The formation of binuclear complexes of various hydroxy-acids is reviewed and a probable structure for the ternary complex is proposed which explains its stability and kinetic inertness. Analogies are drawn between this complex and ternary complexes of UO(2)(VI)-Al(III)-citrate and Cu(II)-Al(III)-tartrate which also cause interference in established analytical procedures.