Effect of anionic micelles on speciation of L-glutamine in presence/absence of metals

Abstract

Protonation equilibria of L-glutamine and speciation of its complexes with Co(II), Ni(II) and Cu(II) have been studied in 0–2.5% w/v SLS–water media using pH-metric method. The protonation constants and binary stability constants have been calculated with the computer program MINIQUAD75. Selection of the best fit chemical models is based on standard deviation in stability constants and residual analysis using crystallographic R-factor and sum of squares of residuals in all mass-balance equations. The trend in the variation of stability constants of the complexes with mole fraction of the medium is attributed to the compartmentalisation of complexation equilibria. Distribution of species and effect of influential parameters on chemical speciation have also been presented.     

Antibiotic as ligand. Coordinating behavior of the cephalexin towards Zn(II) and Cd(II) ions

The complex formation equilibria of Zn(II) and Cd(II) with cephalexin have been studied through potentiometric titrations. Experimental data were analyzed using the least squares computer program SUPERQUAD. The stability constants were 1g beta ZnCEX+ = 2.40, 1g beta Zn(CEX)(OH) = -4.54, 1g beta CdCEX+ = 2.18, and 1g beta Cd(CEX)(OH) = -5.18 (I = 0.1 M NaNO3), CEX complexes of formulae Zn(CEX)2(3)H2O and Cd(CEX)(OH)H2O have been synthesized and characterized by elemental analysis, IR spectra, conductivity measurements, and electronic and NMR spectra. The thermal behavior of the synthesized compounds were studied by TGA and DTA. We conclude that the metal ion interacts with the amido group of CEX.     

Chemical speciation of 2,3-dihydroxybenzoic acid complexes with some biologically essential metal ions in 1, 2-propanediol–water mixtures

Abstract

Chemical speciation of Co(II), Ni(II), Cu(II) and Zn(II) complexes of 2,3-dihydroxybenzoic acid in 0.0-60.0% v/v 1, 2-propanediol-water mixtures maintaining an ionic strength of 0.16 mol dm^-3 at 303±0.1 K has been studied pH metrically. The predominant complexes formed are ML, ML₂ and ML₂H₂ for Co(II), Ni(II) and Zn(II) and ML, ML₂, ML₂H and ML₂H₂ for Cu(II). Models containing different numbers of species were refined by using the computer program MINIQUAD75. Selection of the best fit chemical models was based on statistical parameters and residual analysis. The trend in variation of complex stability constants with dielectric constant of the medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of species, formation equilibria and effect of influential parameters on the stability constants have been presented. The possible structures of the various species are elucidated on the basis of the analysis of the pH-metric data.     

Stability constants for,and structural investigation of,divalent metal ion complexes with polyene antibiotics

The stability constants for the formation of complexes between Ca(II), Mg(II), Cu(II), Zn(II) and Ni(II) with nystatin and amphotericin-B (polyene antibiotics) have been determined by both a potentiometric and a solubility method. The structures of the complexes have been investigated by NMR, ESR and CD spectroscopy. The transition metal stability constants are consistent with the Irving- Williams series. The structural results are discussed and related to the importance of such complexes in mode of action theories.     

Speciation studies of ternary complexes of some essential divalent metal ions with L-histidine and L-glutamic acid in DMSO-water mixtures

Abstract

Chemical speciation of ternary complexes of Ca(II), Mg(II) and Zn(II) ions with L-histidine as the primary ligand (L) and L-glutamic acid as the secondary ligand (X) has been studied pH metrically in the concentration range of 0.0-60.0% v/v DMSO-water mixtures maintaining an ionic strength of 0.16 mol L^-1 using sodium chloride at 303.0 K. Titrations were carried out in different relative concentrations (M:L:X = 1.0:2.5:2.5, 1.0:2.5:5.0, 1.0:5.0:2.5) of metal (M) to L-histidine to L-glutamic acid with sodium hydroxide. Stability constants of ternary complexes were refined with MINIQUAD75. The best-fit chemical models were selected based on statistical parameters and residual analysis. The predominant species detected for Ca(II), Mg(II) and Zn(II) are ML₂XH₂, MLXH₂ and MLX₂. Extra stability of ternary complexes compared to their binary complexes was explained to be due to electrostatic interactions of the side chains of ligands, charge neutralisation, chelate effect, stacking interactions and hydrogen bonding. The species distribution with pH at different compositions of DMSO and the plausible equilibria for the formation of species are discussed.     

Formation constants and coordination in transition metal complexes of glycinehydroxamic acid

Formation constants of Mn(II), Co(II), Zn(II) and Cd(II) complexes with glycinehydroxamic acid (GHA) have been determined in aqueous solution at 25.0 °C and 0.1 M (NaClO₄) by potentiometric measurements. The mathematical models which explained the experimental data better included the formation of mononuclear species with ligand to metal ratios 1:1 and 2:1, as well as protonated and hydrolysed species for all the systems studied. Species with ligand to metal ratio of 3:1 (for cobalt(II)) and 3:2 (for zinc(II)) are also postulated. The stability of the complexes follows the Irving-Williams order. The amino group of GHA is found not to be involved in coordination, exept in the case of the nickel(II) and copper(II) ions.     

Ap4A is not an efficient Zn(II) binding agent. A concerted potentiometric, calorimetric and NMR study

Diadenosine 5',5'-P(1)P(4) tetraphosphate (Ap(4)A) has been considered as an intracellular partner for Zn(II). We applied potentiometry, ITC and NMR to study protonation equilibria of Ap(4)A and Zn(II) complexation by this dinucleotide. The values of binding constants obtained by these three techniques under various experimental conditions coherently demonstrated that Ap(4)A binds Zn(II) weakly, with an apparent binding constant of ca. 10(4) at neutral pH. Such a low stability of Zn(II) complexes with Ap(4)A excludes a possibility for interactions between these two agents in vivo.     

Some bivalent metal complexes of Schiff bases containing N and S donor atoms

Schiff bases have been synthesized by the reaction of p-nitrobenzaldehyde, o-nitrobenzaldehyde and p-toluyaldehyde with 4-amino-5-mercapto-1,2,4-triazole. The ligands react with Co(II), Ni(II) and Zn(II) metals to yield (1:1) and (1:2) [metal:ligand] complexes. Elemental analyses, IR, 1H NMR, electronic spectral data, magnetic susceptibility measurements, molar conductivity measurements and thermal studies have investigated the structure of the ligands and their metal complexes. The electronic spectral data suggests octahedral geometry for Co(II), Ni(II) and Zn(II). The antibacterial activities of the ligands and their metal complexes have been screened in vitro against three Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis and Bacillus subtilis) and two Gram-negative (Salmonella typhi and Pseudomonas aeruginosa) organisms. The coordination of the metal ion had a pronounced effect on the microbial activities of the ligands and the metal complexes have higher antimicrobial effect than the free ligands.     

Coordinative binding of divalent cations with ligands related to bacterial spores. Equilibrium studies

It has been repeatedly postulated that the high heat resistance of bacterial spores is due to stabilization of biopolymers in the spore interior by a solid deposit of protective cement consisting of coordination complexes of ligands with divalent metal ions. This report presents data on metal-binding characteristics of some of the ligands related to spores as determined by means of potentiometric equilibrium measurements under conditions of temperature and ionic strength (t = 25.0°C; μ = 1.0 KNO₃) identical with those reported earlier by the authors in order to facilitate correlation by using comparable data. The spore ligands investigated in this study included 2,6-pyridinedicarboxylic acid (DPA), α,ε-diaminopimelic acid, D-glutamic acid, and D-alanine in a ratio of 1:1 with metal ions which are known to play a role in heat resistance of spores. Stability constants of the chelates of these spore ligands with metal ions such as Ca(II), Mg(II), Cu(II), Ni(II), Zn(II), Co(II), and Mn(II) have been determined. In general the metal chelates of DPA exhibited the greatest stability. On the basis of a consideration of the stability data together with the known configurations of the ligand and the coordination requirements of the metal ions, possible structures indicating the coordinate binding of the spore ligands with the metal ions are presented. All the metal chelates except those of Ca(II) were found to undergo hydrolysis and separation of solid phase in the pH range 7-8.5. The relatively greater hydrolytic stability of Ca(II) chelates and the high affinity of DPA for metal ions appear to be of biological significance insofar as these two spore components are more widely associated with the heat resistance of bacterial spores.     

Inhibition of mugineic acid-ferric complex uptake in barley by copper, zinc and cobalt

The interfering effects of copper, zinc, and cobalt on the uptake of mugineic acid-ferric complex were studied in barley ( Hordeum vulgare , cv. Minorimugi) grown in nutrient solution. Short-term uptake experiments of 3 h were performed utilizing both ionic and mugineic acid-complex forms of each metal at two different concentrations. Copper was most effective in decreasing iron uptake when added in an ionic form at either concentration. The inhibition order at higher concentrations followed Cu(II) > Zn(II) ≥ Co(II), Co(III), which is consistent with the stability constants of these metal complexes with mugineic acid. The displacement of iron from its mugineic acid complex by these metals is suggested as a probable explanation for the decreased iron uptake. The inhibitory effect of metal complexes with mugineic acid on iron uptake was only found in cases with higher concentrations of Cu(II) and Zn(II) complexes. Deformation of the specific iron transport system in the plasma membrane due to their adsorption may be responsible for this effect.     

Spectropotentiometric analysis of metal binding to structural zinc-binding sites: accounting quantitatively for pH and metal ion buffering effects

Studies of the metal-binding affinity of protein sites are ubiquitous in bioinorganic chemistry and are valuable for the information that they can provide about metal speciation and exchange in biological systems. The potential for error in these studies is high, however, since many competing equilibria are present in solution and must be taken into consideration. Here, we report a new spectropotentiometric titration apparatus that allows pH and UV-vis absorption to be monitored simultaneously on small samples under inert atmosphere. In addition, we explain how data obtained from the complex equilibria can be combined with tabulated information about the protonation and metal-binding constants for common buffers to provide detailed, quantitative information about metal-protein interactions. Application of this approach to the investigation of metal binding to structural zinc-binding domains and common pitfalls encountered when performing these experiments are also discussed. We have used this approach to reevaluate the metal-binding constants of the N-terminal zinc-binding peptide from the HIV-1 nucleocapsid protein (10(-8)M相似文献   

Preparation, characterization and pH-metric measurements of 4-hydroxysalicylidenechitosan Schiff-base complexes of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(III), Rh(III), Pd(II) and Au(III)

The 4-hydroxysalicylidenechitosan Schiff-base (2CS-Hdhba) was prepared by the condensation of 2,4-dihydroxybenzaldehyde with chitosan, and its metal complexes, [M(2CS-dhba)Cl₂(H₂O)₂] (M(III) = Fe, Ru, Rh), [M′(2CS-dhba)(AcO)(H₂O)₂] (M′(II) = Co, Ni, Cu, Zn), [Pd(2CS-dhba)Cl(H₂O)] and [Au(2CS-dhba)Cl₂], are reported. These complexes were characterized by elemental analysis, by spectral data (FTIR, solid-phase ¹³C NMR, UV–vis and ESR spectroscopy), by morphological observations (SEM and XRD), and by magnetic and thermal measurements. The Schiff base (2CS-Hdhba) behaves as a bidentate chelate with a single negative charge. The azomethine nitrogen and the deprotonated 2-hydroxy centres with the pendant glucosamine hydroxy functionality play no role in coordination. The dissociation constants of 2CS-Hdhba and the stability constants of some of its metal complexes have been determined pH-metrically.     

Thermodynamics of vanadyl(IV)—carboxylate complex formation in aqueous solution

The stability constants and the heats of formation of vanadyl(IV)—acetate, —glycolate, and —glycine complexes have been determined in aqueous solution by means of potentiometric and calorimetric measurements. In the pH range where the protolitic equilibria of VO²⁺ is certainly negligible the acetate forms two mononuclear complexes, the glycolate three whereas the glycine reacts in its zwitterionic form. The stabilities of the glycolate complexes are considerably higher than the acetate ones, in spite of its lower basicity, indicating that the complex formation involves the coordination of the hydroxyl group to the metal ion. The enthalpy changes are positive except for the glycolate where a small negative value is found. For all systems the entropy changes are positive and therefore favourable to the complex formation.     

CHELATOR: an improved method for computing metal ion concentrations in physiological solutions.

An algorithm is presented for the calculation of metal ion concentrations from given total metal concentrations (and vice versa) in physiological media containing metal-chelating compounds. In such media, conditions differ from those used for stability constant determination of metal-chelator equilibria; therefore calculated metal ion concentrations are incorrect. We recompute stability constants to reflect the effects of ionic strength and temperature of physiological solutions. Twelve different equilibria can be considered per metal-chelator pair. The computer program also calculates the contribution of ionized species of metals, chelator, complexes and pH buffers to ionic strength. Measurements with a Ca-selective electrode and with fura-2 show that calculated ionic Ca2+ concentrations are correct from 10 nM up to the millimolar range. The importance of the correct calculation of metal ion concentrations in physiological experiments is demonstrated by data, and derived kinetic parameters, on Na+/Ca2+ exchange and the ATP-dependent Ca2+ pump of enterocyte plasma membrane vesicles. The program is written in Turbo Pascal and will run on IBM-compatible computers. It is menu-driven and supports the use of a Microsoft mouse.     

Speciation of ternary complexes of lead(II), cadmium(II) and mercury(II) with L-dopa and phenanthroline in propanediol-water mixtures

Abstract

The formation constants of ternary complexes of title systems have been determined pH-metrically in biologically relevant conditions at an ionic strength of 0.16 mol dm^-3 and 303 K. The overall stability constants have been evaluated using MINIQUAD75 computer program. The complexation equilibria have been derived on the basis of species distribution diagram. In the present study L-Dopa and 1, 10-phenanthroline are found to be compatible ligands, proving greater stability of ternary complexes as compared to binary ones. The trend in variation of stability constants with change in dielectric constant of medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of propanediol-water mixtures are also presented. The factors responsible for the compatibility of both the ligands have also been discussed.     

Kinetic analysis of the effect of zinc ion on the inorganic pyrophosphatase reaction.

A kinetic study is presented in which the effect of Zn(II) on yeast inorganic pyrophosphatase was quantitatively determined. A dual role model for metal ion effect, previously determined for the Mg(II)-pyrophosphatase system (O. A. Moe and L. G. Butler, 1972, J. Biol. Chem.247, 7308–7315), was applied successfully to the analysis of the kinetics for Zn(II)-pyrophosphatase and Zn(II), Mg(II)-pyrophosphatase systems. The model, assigning an activator role to free Zn(II) ion and a substrate role to the Zn(II)-pyrophosphate complex, gave an excellent fit to the data. Inhibition of the Mg(II)-pyrophosphatase system by Zn(II) was analyzed by a model in which competitive binding of the Mg(II)-pyrophosphate and Zn(II)-pyrophosphate complexes occurred at the enzyme active site, with both complexes undergoing reaction at different rates. Relative maximal velocities and enzymeligand dissociation constants for the Zn(II)-pyrophosphate complex were determined for the cases where the metal ion activator role was fulfilled by Zn(II) and Mg(II), respectively. The maximal velocity parameter showed a dependence on the nature of the activator metal ion, demonstrating that the role of the latter is associated both with the process of substrate binding and with the mechanism of catalysis. Values for all kinetic parameters are reported for an ionic strength of 0.2, pH 7.0, and 25.0 °C.     

Hydroxyquinoline based binders: promising ligands for chelatotherapy?

We report here a thorough physico-chemical study of the coordination properties of clioquinol, an oxine-type active neurological drug in Alzheimer's disease, toward biologically relevant divalent metal ions (Cu, Zn, Ni, Co and Mn). Using a fruitful combination of electrospray mass spectrometry, absorption spectrophotometry and potentiometry, we have characterized the mono- and bis-chelated metal ion species. The determination of the stability constants showed a classical thermodynamic behavior along the studied series with the cupric complexes being by far the most stable species. Our data are discussed within the scope of Alzheimer's disease.     

Lead (II)-dithiothreitol equilibria and their potential influence on lead inhibition of 5-aminolevulinic acid dehydratase in in vitro assays

Dithiothreitol (threo-2,3-dihydroxy-1,4-dithiobutane = DTT) has recently been used to activate 5-aminolevulinic acid dehydratase in kinetic studies for the inhibition of this zinc enzyme by lead. Since the DTT molecule contains donor groups capable of forming metal ion complexes, its presence in the experimental medium used for this kind of assay may largely influence the concentration of lead available for the active sites of the enzyme. Before any quantitative investigation of this phenomenon can be contemplated, all possible complexes formed by lead with DTT must first be identified and their stabilities determined. Accordingly, formation equilibria of DTT complexes with lead(II) have been investigated under physiological conditions (37 degrees C, NaCl, 0.15 mol. dm-3 using glass electrode potentiometry. Corresponding stability constants were refined with MINIQUAD and ESTA computer programs. DTT log protonation constants have been found equal to 9.811 +/- 0.002 and 18.672 +/- 0.002. The following lead-dithiothreitol complexes have been characterized: ML (12.243 +/- 0.063), MLH-1 (2.391 +/- 0.061), M2LH-1 (13.285 +/- 0.059), and M4L3 (51.668 +/- 0.157). Appropriate computer simulations show that the interactions of the two reactants are indeed most significant under the pH and concentration conditions used in the above mentioned biological investigations. In particular, the influence of lead(II)-DTT equilibria on the free concentration of lead available for the active sites of the enzyme is described.     

Metal Complexation in Xylem Fluid : II. THEORETICAL EQUILIBRIUM MODEL AND COMPUTATIONAL COMPUTER PROGRAM

Theoretical considerations of metal complex formation in aqueous solutions were used to develop a computer program (CHELATE) to calculate all equilibrium species (free metal ions, metal complexes, etc.) in any user-defined system, such as xylem fluid. Mass-balance equations were established to describe each free metal ion and each free ligand concentration as a function of solution pH, total metal or total ligand, hydrogen-association constants, and the stability constants of known metal complexes. A default data base can be altered by the user to define any desired system covered by the stored equilibrium data. The program can currently handle nine metal ions, 35 ligands, and 500 complex species. The validity of the program was confirmed by using experimental test systems in which free-metal ion activity measurements were made with ion-selective electrodes.