Binding of calcium ions on acid polysaccharides of peach gum and distribution pattern of carboxyl groups in the macromolecule

1979 ◽  
Vol 44 (8) ◽  
pp. 2517-2525 ◽  
Author(s):  
Rudolf Kohn ◽  
Jozef Rosík ◽  
Jozef Kubala ◽  
Anna Malovíková

The acid polysaccharide of peach gum and its macromolecular products of a gradual degradation by acid hydrolysis were characterized by molecular weight (Mw) and molar ratios of both uronic acids and neutral saccharide units. The single-ion activity coefficient of calcium ions (γCa2+) bound to these acid polysaccharides and to the corresponding aldobiouronic acids was measured and CD spectra of potassium and calcium salts of these compounds were recorded. It was ascertained that Ca2+ ions are bound to carboxyl groups of polysaccharides under study by an electrostatic bond in molecular disperse solutions. The mean distance of the neighboring carboxyl groups b = 0.83 to 1.00 nm, calculated from the measured values γCa2+ indicates a very close arrangement of uronic acid units, which does not undergo alteration with the stepwise degradation of the macromolecule. The obtained results let us conclude that the main chain of the polysaccharide is substituted in longer segments by D-glucuronic acid units and its 4-O-methyl derivative (monomeric side chains), at least at each second D-galactose unit.

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.


Author(s):  
D. James Morré ◽  
Charles E. Bracker ◽  
William J. VanDerWoude

Calcium ions in the concentration range 5-100 mM inhibit auxin-induced cell elongation and wall extensibility of plant stems. Inhibition of wall extensibility requires that the tissue be living; growth inhibition cannot be explained on the basis of cross-linking of carboxyl groups of cell wall uronides by calcium ions. In this study, ultrastructural evidence was sought for an interaction of calcium ions with some component other than the wall at the cell surface of soybean (Glycine max (L.) Merr.) hypocotyls.


1986 ◽  
Vol 51 (10) ◽  
pp. 2250-2258 ◽  
Author(s):  
Rudolf Kohn ◽  
Zdena Hromádková ◽  
Anna Ebringerová

Several fractions of acid hemicelluloses isolated from rye bran were characterized by molar ratios of saccharides (D-Xyl, L-Ara, D-Glc, D-Gal) and 4-O-methyl-D-glucuronic acid and protein content. Binding of Pb2+ and Cu2+ ions to these acid polysaccharides was considered according to function (M)b = f([M2+]f), expressing the relationship between the amount of metal (M)b bound to 1 g of the substance and the concentration of free ions [M2+]f in the equilibrium solution and according to the association degree β of these cations with carboxyl groups of uronic acid at a stoichiometric ratio of both components in the system under investigation. Acid hemicelluloses contained only a very small portion of uronic acid ((COOH) 0.05-0.18 mmol g-1); the model polysaccharide, 4-O-methyl-D-glucurono-D-xylan of beech, was substantially richer in uronic acid content ((COOH) 0.73 mmol g-1). Consequently, the amount of lead and copper bound to acid hemicelluloses is very small ((M)b 0.017-0.025 mmol g-1) at [M2+]f = 0.10 mmol l-1. On the other hand, much greater amount of cations ((M)f 0.09-0.10 mmol g-1) was bound to the glucuronoxylan. The association degree β was like with the majority of samples (β = 0.31-0.38). The amount of lead and copper(II) bound to acid hemicelluloses from rye bran is several times lower than that bound to dietary fiber isolated from vegetables (cabbage, carrot), rich in pectic substances.


2021 ◽  
Author(s):  
Damien Degoulange ◽  
Nicolas Dubouis ◽  
Alexis Grimaud

Highly concentrated electrolytes were recently proposed to improve the performances of aqueous electrochemical systems by delaying the water splitting and increasing the operating voltage for battery applications. While advances were made regarding their implementation in practical devices, debate exists regarding the physical origin for the delayed water reduction occurring at the electrode/electrolyte interface. Evidently, one difficulty resides in our lack of knowledge regarding ions activity arising from this novel class of electrolyte, it being necessary to estimate the Nernst potential of associated redox reactions such as Li<sup>+</sup> intercalation or the hydrogen evolution reaction. In this work, we first measured the potential shift of electrodes selective to either Li<sup>+</sup>, H<sup>+</sup> or Zn<sup>2+</sup> ions from diluted to highly concentrated regimes in LiCl or LiTFSI solutions. Observing similar shifts for these different cations and environments, we establish that shifts in redox potentials from diluted to highly concentrated regime originates in large from an increase junction potential, it being dependent on the ions activity coefficients that increase with concentration. While our study shows that single ion activity coefficients, unlike mean ion activity coefficients, cannot be captured by any electrochemical means, we demonstrate that protons concentration increases by approximatively two orders of magnitude from 1 mol.kg<sup>-1</sup> to 15-20 mol.kg<sup>-1</sup> solutions. Combined with the increased activity coefficients, this increases the activity of protons and thus the pH of highly concentrated solutions which appears acidic.


CrystEngComm ◽  
2016 ◽  
Vol 18 (1) ◽  
pp. 157-163 ◽  
Author(s):  
Heng Yang ◽  
Shiqiang Chai ◽  
Yuzhe Zhang ◽  
Yurong Ma

High Mg calcites in pure phase with controlled magnesium contents were synthesized by using amorphous precursor through a hydrothermal process in the absence of organic additives. It is found that the Mg contents in the high Mg calcites increase with the increase of the molar ratios of carbonate and calcium ions in the mother solutions.


1927 ◽  
Vol 8 (6) ◽  
pp. 543-599 ◽  
Author(s):  
S. P. L. Sørensen ◽  
K. Linderstrøm-Lang ◽  
Ellen Lund

Introduction. A description is given of the principle followed in the experimental determination of the ionisation of egg albumin, its capacity to combine with acids and bases. Egg albumin is regarded as an ampholyte, and in accordance with J. N. Brønsted's definition of acids and bases, ampholytes are considered as substances capable of both taking up and giving off hydrogen ions. The theoretical treatment of the capacity of ampholytes to combine with acids (and bases) has been carried out on this basis. Section A. Several experimental series are noted, comprising the determination of the activity coefficient of the hydrogen ion (fH) in ammonium chloride solutions of different concentration. Section B. The general method of experimental determination of the ionisation (capacity to combine with adds and bases) of egg albumin in ammonium chloride and potassium chloride solutions is briefly described, and the results of the experiments are compared. Section C. 1). In a brief theoretical survey we have suggested that distinction should be made between isoelectric and isoionic reaction of an ampholyte, the former defined as the hydrogen ion activity (value of paH) at which the mean valency of the ampholyte is 0, the latter as the hydrogen ion activity at which the quantity of acid or base combined with the ampholyte is 0; or, as we prefer to express it, the hydrogen ion activity at which the specific hydrogen ionisation of the ampholyte is 0. If the ampholyte does not combine with other ions than the hydrogen ion, then isoelectric and isoionic reaction coincide. Isoionic reaction is determined by acid-combining experiments. The principle of this determination is briefly described. A theoretical investigation of the alteration with salt concentration of both isoelectric (isoionic) reaction and the shape and direction of the ionisation curves is made, with regard to ampholytes capable only of combining with hydrogen ions, on the basis of the Debye-Hückel formulæ and Linderstrøm-Lang's theory for the ionisation of polyvalent ampholytes of simple type. It is shown that the salt effect, in accordance with the theory, and in qualitative agreement with the experiments, consists in a turning of the ionisation curves, indicating the relation between the quantity of combined acid (specific hydrogen ionisation) and paH, and the turning of the curves, which leaves the isoelectric reaction unaltered, tends in such a direction that the quantity of combined acid at constant ampholyte concentration and constant pan increases with increasing salt concentration. The possibility of chemical combining of other ions than the hydrogen ion is discussed. 2). Following on 1), a brief survey of the experimental results is given. 3). The isoionic reaction is found from the experimental material and proved to be independent of the ammonium chloride concentration. As the mean of all determinations we have paH0 = 4.898 (isoionic reaction). The difference between this value and that formerly found for ammonium sulphate solutions (4.844) is discussed. 4). Finally, on the basis of the theory in Section 1), some simple calculations of the ionisation curves for egg albumin are made, and it appears that the theory can reproduce the experimental results in a rough quantitative way when we assume that the egg albumin has a radius of 2.21·10–7 cm. (answering to a molecular weight of 35,000 in aqueous solution), and contains 30 acid and base groups.


2002 ◽  
Vol 46 (5) ◽  
pp. 1510-1515 ◽  
Author(s):  
S. Gupta ◽  
M. M. Thapar ◽  
W. H. Wernsdorfer ◽  
A. Björkman

ABSTRACT The interactions of artemisinin with atovaquone, quinine, and mefloquine were investigated in three Plasmodium falciparum strains (strains F-32, FCR-3, and K-1) by an in vitro culture assay. The parasites were cultured for 48 h in the presence of different concentrations and proportions of two drugs at a time in a checkerboard design. The response parameters were determined, and the sums of the fractional inhibitory concentrations (ΣFICs) of the drug combinations were calculated for different degrees of inhibition (50% effective concentration [EC50], EC90, and EC99). Within therapeutically relevant molar ratios (19 to 200), the combination of quinine and artemisinin showed mean ΣFICs of 1.71 at the EC50, 0.36 at the EC90, and 0.13 at the EC99, indicating increasing synergism. Within the range of molar ratios of 4.3 to 50, the combination of mefloquine and artemisinin yielded mean ΣFCIs of 0.93, 0.44, and 0.31 at the EC50, EC90, and EC99, respectively, indicating synergism. The atovaquone combination showed additive activity to synergism at atovaquone/artemisinin proportions considered relevant to the in vivo situation, i.e., between 4.3 and 200, with the mean ΣFICs decreasing from 1.34 at the EC50 to 0.85 and 0.23 at the EC90 and EC99, respectively. Interstrain differences in the degree of drug interaction were seen with the three strains for all combinations. Synergism was most consistent with quinine.


1990 ◽  
Vol 70 (3) ◽  
pp. 531-536 ◽  
Author(s):  
M. De NOBILI ◽  
M. CONTIN ◽  
L. LEITA

A new precipitation titration method, employing cetyltrimethylammonium (CTA+), is proposed for analysis of carboxyl groups of humic substances in solution. The method was tested with polyphenol-polycarboxylic acids standard solutions: recovery factors ranged from 0.94 to 1.09. Results obtained by performing precipitation of humic acids samples at pH = 9.8 and at 7.0 are compared with those obtained by the Ca-acetate method. The difference between the number of COOH per unit weight of humic preparation calculated by precipitation with CTA+ at pH = 7.0 and by the Ca-acetate exchange reaction ranged between 1 and 45%. In most samples overestimation of COOH groups by the Ca-acetate method appears to be higher than the mean relative error of the CTA+ precipitation method (5%). Key words: Carboxylic group determination, humic substances, cetyltrimethylammonium


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