scholarly journals Equilibrium of aliphatic amino acids on ion exchangers forming complexes in the presence of copper (II) and nickel (II) cations

Author(s):  
L. P. Bondareva ◽  
Y. S. Peregudov ◽  
A. V. Astapov

The task of isolating and separating amino acids from aqueous solutions exists in various industries. The traditional method of isolation is ligand exchange chromatography. When choosing a cation for ligand-binding chromatography based on its binding strength with the ion exchanger, often used as a sulfonated polystyrene ion exchanger keeps the copper (II) firmly enough, and therefore, it is easily replaced by other cations. Chelating ion exchangers charge cations of copper (II), which hold these ions firmly enough. In this case, separating a mixture of substances, it is due to differences in the constants of complexation agents and complexes distribution coefficients. The study of the interaction of amino acids with the aliphatic carboxylic acid, the exchange of phosphoric acid cations and the amino carboxylic and amino phosphonic polyampholytes has shown a significant effect of the pH of the medium on the nature of the sorption equilibria. Under certain conditions, in the phase of the ion exchanger in the form of complexing metal cations, the formation of new sorption centers is possible, which occur upon sorption of amino acids in the formation of mixed ligand compounds: the sorbent complex may simultaneously comprise amino acids and attached functional groups of the sorbent as ligands. The influence of the hydrogen index of the medium primarily affects the change in the nature of the formed complex compounds in the sorbent phase and the equilibrium solution and the ratio of their stability constants. If the stability constant of the ion exchanger complex is higher than the stability constant of the compound with a low molecular weight ligand, then the sorbed copper cations interact with incoming methionine ions without breaking the metal – functional group of the ion exchanger coordination bond. If the ratio of stability constants is the opposite, then the predominant elution of copper (II) cations occurs with the formation of complex compounds with an amino acid in an aqueous solution.

Author(s):  
Alexandr I. Lytkin ◽  
Natalya V. Chernyavskaya ◽  
Darya K. Smirnova

Lanthanides have a high affinity toward ligands containing donor oxygen atoms, especially amino acids and complexons. The study of the processes of complexation of amino acids with f-element cations provides valuable information for solving problems of supramolecular chemistry, molecular recognition and chiral sensitivity of biological substrates. As a rule, f-elements are not components of biopolymers, but they are spectral label probes, which are important in the bioinorganic chemistry of metals. Quantitative estimation of the stability of complexes is necessary, first of all, to search for an internal connection between the constants themselves and then to find correlations between the stability of complexes and the properties of the complexing agent, the ligand, and the system as a whole. Such correlation dependencies make it possible to calculate a priori, or at least estimate the stability constants of new complexes, and also to better understand the influence of the nature of the chemical bond and the properties of the system as a whole on the formation and stability of complex compounds. In the present work, the complexation of neodymium, lanthanum with L-asparaginat ion and samarium, cerium with L-leucinat ion at 298.15 K and ionic strength values of 0.5 mol/l was studied by potentiometric titration and the stability constants of the complexes formed were determined. The values of the stability constants found allow us to perform rigorous thermodynamic calculations of the equilibria of these amino acids in salt solutions. The data obtained, in particular, can be used to reliably interpret the results of calorimetric studies of the complexation of lanthanides with the participation of the studied amino acids.Forcitation:Lytkin A.I., Chernyavskaya N.V., Smirnova D.K. Stability constants of L-asparagine and L-leucine complexes with some lanthanide in aqueous solutions at 298.15 K. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 1. P. 37-41


1963 ◽  
Vol 41 (1) ◽  
pp. 18-20 ◽  
Author(s):  
Vladimir Palaty

The stability constant of the sodium chelate of EDTA was determined by means of a sodium-sensitive glass electrode. It appears that a hydrogen chelate of the formula NaHY2− is formed in the neutral solution of EDTA, but is very unstable. The stability constants, pKNaY = −2.61 and pKNaHY = 0.03, are comparable to the value obtained by Schwarzenbach and Ackermann under different experimental conditions by a less sensitive method.


1987 ◽  
Vol 33 (3) ◽  
pp. 405-407 ◽  
Author(s):  
R B Martin ◽  
J Savory ◽  
S Brown ◽  
R L Bertholf ◽  
M R Wills

Abstract An understanding of Al3+-induced diseases requires identification of the blood carrier of Al3+ to the tissues where Al3+ exerts a toxic action. Quantitative studies demonstrate that the protein transferrin (iron-free) is the strongest Al3+ binder in blood plasma. Under plasma conditions of pH 7.4 and [HCO3-]27 mmol/L, the successive stability constant values for Al3+ binding to transferrin are log K1 = 12.9 and log K2 = 12.3. When the concentration of total Al3+ in plasma is 1 mumol/L, the free Al3+ concentration permitted by transferrin is 10(-14.6) mol/L, less than that allowed by insoluble Al(OH)3, by Al(OH)2H2PO4, or by complexing with citrate. Thus transferrin is the ultimate carrier of Al3+ in the blood. We also used intensity changes produced by metal ion binding to determine the stability constants for Fe3+ binding to transferrin: log K1 = 22.7 and log K2 = 22.1. These constants agree closely with a revision of the reported values obtained by equilibrium dialysis. By comparison with Fe3+ binding, the Al3+ stability constants are weaker than expected; this suggests that the significantly smaller Al3+ ions cannot coordinate to all the transferrin donor atoms available to Fe3+.


Soil Research ◽  
1997 ◽  
Vol 35 (6) ◽  
pp. 1279 ◽  
Author(s):  
S. B. Pandeya ◽  
A. K. Singh

The stability constants for the complexes formed between iron species existing in ambient soil environment and fulvic acids (FA) extracted from organic wastes like sewage sludge, farm yard manure (FYM), poultry manure, and press mud were determined in aqueous media of pH 5·0 and 8·5 by discontinuous spectrocolorimetric titration method. The values of stability constant (log K) of Fe–FA complexes estimated at pH 5·0 were 6·026, 6·212, 6·270, and 6·342 for FYM, sludge, poultry manure, and press mud, respectively. The respective values at pH 8·5 were 6·145, 6·276, 6·350, and 6·940. The order of the values of log K for different preparations of fulvic acids was press mud > poultry manure > sludge > FYM. The functional group contents, their pH of neutralisation, and electrostatic properties of the FA such as pKINT, pKm, and 0·868 nW, were found to be the determining factors for maximum binding ability of FA for metal cations and the stability constant of Fe–FA for different FA preparations. The basic assumptions and the limitations of the discontinuous spectrocolorimetric estimation of stability constants for Fe–FA are discussed.


1989 ◽  
Vol 44 (11) ◽  
pp. 1402-1406 ◽  
Author(s):  
W. Kuhr ◽  
G. Peters ◽  
W. Preetz

By 103Rh NMR spectroscopy the ten compounds of the system [RhCl„Br6_„]3-, n = 0-6 are identified by separate signals. A downfield shift of approximately 160 ppm is observed per substitution of Cl by Br, and the stereoisomers for n = 2, 3, 4 are separated by at least 4 ppm. From the relative intensities of the 103Rh signals in equilibrated solutions, whose total contents of Rh. Cl and Br are known, six individual stability constants are calculated. Their product gives the overall stability constant, indicating [RhBr6]3- to be 36,300 times more stable than [RhCl6]3-. On treatment of [RhBr6]3- with HCl cis/fac isomers are formed stereospecifically, whereas the reaction of [RhCl6]3- with HBr gives trans isomers, n = 2 and 4, containing 20—30% of the cis compounds; only mer-[RhCl3Br3] 3- is obtained pure. The high resolution spectra of [RhCl6]3- and [RhBr6]3- are exhibit five signals each, reflecting the intensity patterns of the most abundant isotopomers within [Rh35Cln37Cl6-n]3-, n = 2-6, and [Rh79Br„81Br6_„]3-, n = 1-5, respectively.


1967 ◽  
Vol 45 (14) ◽  
pp. 1643-1647 ◽  
Author(s):  
P. G. Manning

Stepwise stability constants have been determined for the 1:1 and 1:2 Eu3+:mandelate− and Eu3+:tartronate2− complexes in water. Measurements were made at low ionic strength and the temperature was 25 °C. The solvent-extraction–radiotracer method was used.For the mandelate system at an ionic strength of 0.104, K1 = 5.0 × 102, K2 = 1.58 × 102, and K1:K2 = 3.1. The K1:K2 ratios suggest monodentate ligandcy.The stepwise stability constants for the two stages of tartronate ion association are: K1 = 7.1 ( ± 15%) × 104 and K1K2 = 4.2 ( ± 5%) × 108. The magnitudes of the stability constants suggest that tartronate is a tridentate ligand. The stability constant ratios are discussed with reference to the ratios for piperidinedicarboxylate and iminodiacetate complexes.


Sign in / Sign up

Export Citation Format

Share Document