Binding of zinc cations to pectin and its oligomeric fragments

1983 ◽  
Vol 48 (11) ◽  
pp. 3154-3165 ◽  
Author(s):  
Anna Malovíková ◽  
Rudolf Kohn

The activity of Zn2+ ions bound to carboxyl groups of pectin of esterification degree E 0 to 90% and to oligomeric potassium galacturonates of polymerization degree 1 to 7 was estimated by the metallochromic indicator (tetramethylmurexide) method. The zinc ions are stoichiometrically bound to pectin, one Zn2+ cation to two free carboxyl groups. The stability constant K of zinc pectinates strongly decreases with the increasing esterification degree in a relationship close to a linear logarithmic function, log K = f(E) similarly, as with the binding of Ca2+ ions to pectin. Pectin reveals a little higher selectivity to Zn2+ ions when considering this couple of cations. The zinc ions are bound to the monomeric D-galacturonic acid to a very low extent in contrast to some toxic cations as e.g. Pb2+, Cu2+, and Cd2+. A continuous increase of the degree of association of Zn2+ ions with carboxyl groups of oligomers takes place with the increasing polymerization degree. The validity of the increment additivity of terminal and inner uronic acid units to the final activity of zinc counterions bound to these oligomers was proved. The results are discussed from the standpoint of application of pectin as an active component of prophylactic diets against poisoning with cations of toxic metals with respect to the excretion of Zn2+ ions from the human body. Findings concerning the interaction of Zn2+ ions with pectin in dependence on its esterification degree (E) constitute a theoretical basis for a potential application of pectin as a useful ligand of Zn2+ ions in medical treatment of zinc deficiency in the human body.

1982 ◽  
Vol 47 (12) ◽  
pp. 3424-3431 ◽  
Author(s):  
Rudolf Kohn

The activity of Pb2+ ions in solutions of lead oligogalacturonates of polymerization degree DP 1 to 5 (starting concentration of the investigated solutions 3.00 mmol (COOPb0.5) l-1, the ionic strenght of the solution I = 0.01 mol l-1, electrolyte KNO3, was determined by lead specific ion electrodes. The activity aPb2+ is independent on the kind of anion in very diluted solutions of lead perchlorate and nitrate. Ions of lead become bound quite firmly even to the monomeric D-galacturonic acid (association degree of Pb2+ ions to carboxyl groups of uronic acid β = 0.43). The increase of polymerization degree is associated with a strong decrease of the lead oligogalacturonate solubilities on one hand, and increase of the bond strenght of the Pb2+ ions to these oligomers on the other. The association degree of Pb2+ ions to carboxyl groups of the pentamer (β = 0.96) almost reaches the value found for the polymeric chain of pectate molecule (D-galacturonan); here, the stoichiometric binding of Pb2+ to two carboxyl groups takes place with a great deal of probability. Lead has been found to bind highly preferentially to oligogalacturonates even in the presence of calcium ions. Results presented in this paper help to clear the mechanism of elimination of lead from the human body through pectin and its oligomeric fragments.


1983 ◽  
Vol 48 (7) ◽  
pp. 1922-1935 ◽  
Author(s):  
Rudolf Kohn ◽  
Kveta Heinrichová ◽  
Anna Malovíková

The binding of Cu2+ and Cd2+ ions to potassium oligogalacturonates of polymerization degree DP 1 to 9 was investigated by ion-specific electrodes and by the metallochromic indicator method. The interaction was evaluated on the basis of degree of association β of cations (M2+) with carboxyl groups of the compounds examined and the single-ion activity coefficients of counterions γM2+. The results were compared with values corresponding to an electrostatic bond of Ca2+ ions to these oligomers. The Cd2+, and especially Cu2+ ions were bound in a considerable measure already to mono- and oligogalacturonates of a low polymerization degree very probably by a chelate bond. Precipitation of Cu- and Cd-oligogalacturonates takes place at a polymerization degree DP 5 and 8, respectively. Interpretation of results by the multiple equilibria theory evidenced that the Cu2+ ions were stoichiometrically bound to mono- and oligogalacturonates (one cation to two carboxyl groups) similarly, as with polymeric D-galacturonan. The results revise the early conception concerning the formation of a positively charged complex of Cu2+ ions (similarly also of Cd2+ and Pb2+ ions) with monogalacturonic acid of (MA)+ type, where A- is the anion of uronic acid. The results are a contribution to the elucidation of the elimination mechanism of these toxic cations from human body involving the oligomeric fragments of pectin as products of its enzymic degradation in the digestive tract.


1985 ◽  
Vol 50 (2) ◽  
pp. 445-453 ◽  
Author(s):  
Jana Podlahová ◽  
Josef Šilha ◽  
Jaroslav Podlaha

Ethylenediphosphinetetraacetic acid is bonded to metal ions in aqueous solutions in four ways, depending on the type of metal ion: 1) through an ionic bond of the carboxylic groups to form weak complexes with a metal:ligand ratio of 1 : 1 (Ca(II), Mn(II), Zn(II), Pb(II), La(III)); 2) through type 1) bond with contributions from weak interaction with the phosphorus (Cd(II)); 3) through coordination of the ligand as a monodentate P-donor with the free carboxyl groups with formation of 2 : 1 and 1 : 1 complexes (Cu(I), Ag(I)); 4) through formation of square planar or, for Hg(II), tetrahedral complexes with a ratio of 1 : 2 with the ligand as a bidentate PP-donor with the free carboxyl groups (Fe(II), Co(II), Ni(II), Pd(II), Pt(II)). On acidification of the complex solution, the first two protons are bonded to the carboxyl groups. The behaviour during further protonation depends on the type of complex: in complexes of types 1) and 2) phosphorus is protonated and the complex dissociates; in complexes of types 3) and 4) the free carboxyl groups are protonated and the phosphorus-metal bond remains intact. The results are based on correlation of the stability constants, UV-visible, infrared, 1H and 31P NMR spectra and magnetic susceptibilities of the complexes in aqueous solution.


2010 ◽  
Vol 29 (2) ◽  
pp. 215 ◽  
Author(s):  
Tatjana Anđelković ◽  
Ružica Nikolić ◽  
Aleksandar Bojić ◽  
Darko Anđelković ◽  
Goran Nikolić

The binding of Cd(II) to soil humic acid (HA) at pH 6.5 and in 0.1 mol/L KNO3 ionic medium, was studied by potentiometric titration with a cadmium ion selective electrode. The influence of carboxyl groups in cation-humic interactions was investigated by selective blocking of humic acid carboxyl groups with thionyl chloride and methanol. Infrared spectroscopic analysis confirmed that esterification took place. Differences between underivatized and derivatized HA complexation properties are ascribed to carboxyl groups. The Scatchard plots and incremental formation constants were used to obtain values for Cd-binding constants, for both HAs. The derivatization decreased the number of HA complexing sites by approximately 60 %, which correlates with acid-base properties of both HAs, studied by barium hydroxide and calcium acetate exchange methods. The stability constants for binding at the strongest sites (logKINT) was larger for underivatized HA (5.40) than for derivatized HA (4.92), indicating greater stability in the case when carboxyl groups are involved in complexation reaction.


2002 ◽  
Author(s):  
Ke Yu ◽  
Albert C. J. Luo

The human-body in a vehicle traveling on the rough terrain is modeled through the lumped mass approach and its periodic impact motions and stability are investigated through a linear model of vehicle and passenger systems. The linear model assumes the motion response of vehicle is very small compared to passenger’s rotational motion since the vehicle chassis has a very large mass and moment of inertia. The period-1 impact motion for two impacts respectively on two walls for a specific number of periods is predicted analytically and numerically. The stability and bifurcation of such a period-1 impact motion are developed analytically. The phase planes of the periodic impact motions are illustrated for a better understanding of the human-body impacting motion in the vehicle.


1968 ◽  
Vol 21 (4) ◽  
pp. 821 ◽  
Author(s):  
Anne FW oodlock ◽  
BS Harrap

In the acid pH region, the relative effects of various salts on the thermal stability of the collagen helix are quite different from their effects at neutral pH. The magnitude of the decrease in thermal stability brought about by the salts studied depends mainly on the nature and concentration of the anion and very little on the nature of the cation, whereas at neutral pH the nature of both anions and cations affects the collagen helix stability, the effects of the two ions being roughly additive. The magnitude of the effect of salts at acid pH is much greater than that at neutral pH whereas for a non-ionized denaturant, urea, the magnitudes at both neutral and acid pH are similar. The data are discussed in terms of possible interactions between salts and the positively charged protein with particular consideration of the effects of salts on the pKa of protein carboxyl groups.


2020 ◽  
Vol 32 (16) ◽  
pp. 2000338 ◽  
Author(s):  
Yanrong Wang ◽  
Caixing Wang ◽  
Zhigang Ni ◽  
Yuming Gu ◽  
Bingliang Wang ◽  
...  

2014 ◽  
Vol 52 (1) ◽  
pp. 93-104 ◽  
Author(s):  
Junqiang Xia ◽  
Roger A. Falconer ◽  
Yejiang Wang ◽  
Xuanwei Xiao

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