Intramolecular binding of calcium ions to L-guluronan and D-galacturonan

1981 ◽  
Vol 46 (7) ◽  
pp. 1701-1707 ◽  
Author(s):  
Rudolf Kohn ◽  
Anna Malovíková
Keyword(s):  
Activity Coefficients ◽  
Calcium Ions ◽  
Uronic Acid ◽  
Total Activity ◽  
Polymeric Chain ◽  
Polymerization Degree ◽  
Pectic Acid ◽  
Calcium Salts ◽  
Macromolecule Chain ◽  
Derivatives Of

The values of activity coefficients γCa2+, determined earlier in solutions of calcium oligoguluronates and oligogalacturonates of various polymerization degree n, were interpreted. Values γCa2+ corresponding to an intramolecular Ca2+ bond to a polymeric chain of L-guluronan and D-galacturonan were obtained by extrapolation of functions γCa2+ = f(1/n) and γCa2+ = f((n-2)/n) to lim n → ##h. The γCa2+ values were compared with those determined in solutions of calcium salts of O-acetyl derivatives of pectic acid and D-mannuronan. In molecular disperse solutions the Ca2+ ions are bound to L-guluronan and D-galacturonan by an electrostatic bond. The course of the above-mentioned functions leads to the conclusion that both terminal uronic acid units in polyuronates under study bind Ca2+ ions less firmly than do the inner units in the macromolecule chain. The linear course of the function γCa2+ = f((n-2)/n) for L-guluronan proves the additivity of contribution of the terminal and inner uronic acid units to the total activity of Ca2+ counterions bound to L-guluronan.

Binding of lead cations to oligogalacturonic acids

1982 ◽  
Vol 47 (12) ◽  
pp. 3424-3431 ◽  
Author(s):  
Rudolf Kohn
Keyword(s):  
Human Body ◽  
Calcium Ions ◽  
Galacturonic Acid ◽  
Uronic Acid ◽  
The Other ◽  
Carboxyl Groups ◽  
Polymeric Chain ◽  
Polymerization Degree ◽  
Strong Decrease ◽  
Nitrate Ions

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.

Binding of calcium ions to 2,3-dicarboxy derivatives of pectic acid

1986 ◽  
Vol 51 (10) ◽  
pp. 2259-2270 ◽  
Author(s):  
Anna Malovíková ◽  
Rudolf Kohn
Keyword(s):  
Activity Coefficient ◽  
Calcium Ions ◽  
High Selectivity ◽  
Carboxyl Groups ◽  
Free Enthalpy ◽  
Pectic Acid ◽  
Considerable Degradation ◽  
Oxidation Degradation ◽  
Derivatives Of ◽  
Low Activity

Using a two-step oxidation of pectic acid (85% of D-galacturonan in the preparation) a series of 2,3-dicarboxy derivatives (Na+ form) was prepared containing 4.2 to 8.5 mmol of carboxyl groups per gram (COOH g-1). After the centrifugation of the diluted suspensions of the Ca-salts of these polyacids the activity of the calcium counterions (aCa2+) was determined using the metallochromic indicator (tetramethylmurexide) and the activity coefficient γCa2+ was calculated. Using potentiometric titrations of polyacids with potassium and calcium hydroxides the decrease in electrostatic free enthalpy, Δ(Gel/N)KCa, of the cation exchange Ca2+ → 2 K+ was determined. In the course of the oxidation, degradation of the macromolecules took place, characterized by the limit viscosity number [η]. In spite of the considerable degradation, preparations with higher oxidation degrees display a high selectivity in the exchange of cations Ca2+ → 2 K+, similar to that determined recently by us in 2,3-dicarboxy derivatives of starch and amylose. The strong binding of Ca2+ ions to the investigated substances is also documented by very low activity coefficient values, γCa2+, ranging from 0.057 to 0.037.

Binding of calcium ions to 2,3-dicarboxy derivatives of starch and amylose

1984 ◽  
Vol 49 (9) ◽  
pp. 2116-2129 ◽  
Author(s):  
Rudolf Kohn ◽  
Karol Tihlárik
Keyword(s):  
Calcium Ions ◽  
Corn Starch ◽  
Spatial Arrangement ◽  
Ring Cleavage ◽  
Carboxyl Groups ◽  
Linear Charge ◽  
Oxidation Degree ◽  
Linear Charge Density ◽  
Macromolecule Chain ◽  
Derivatives Of

A series of 2,3-dicarboxy derivatives of oxidation degree DO(d.c.) 0.13 to 0.90 was prepared by a two-stage oxidation of corn starch and amylose. The activity coefficient γCa2+ of calcium counterions was estimated in solutions of calcium salts of these carboxy derivatives in a 3.00 mmol (COOCa0.5)l-1 concentration by a metallchromic indicator (tetramethylmurexide) method. A loss of electrostatic free enthalpy, Δ(Gel/N)KCa, due to the exchange of Ca2+ → 2K+ cations was determined by potentiometric titrations of the investigated polyacids and pectinic acids of various linear charge density of the macromolecule employing potassium and calcium hydroxides. 2,3-Dicarboxy derivatives of starch and amylose show a considerably strong binding of calcium ions even at low oxidation degree of the starting polysaccharides in contrast to solutions of the corresponding pectinates and carboxymethyl derivatives of cellulose and amylose. The strong bond of calcium ions to 2,3-dicarboxy derivatives of starch and amylose is ascribed to a favourable spatial arrangement of two neighbouring carboxyl groups at C(2) and C(3) of the oxidized D-glucose units due to a flexibility of the macromolecule chain at sites of the pyrane ring cleavage.

The role of secondary alcoholic groups of D-galacturonan in its degradation with exo-D-galacturonanase

1980 ◽  
Vol 45 (2) ◽  
pp. 427-434 ◽  
Author(s):  
Kveta Heinrichová ◽  
Rudolf Kohn
Keyword(s):  
Acetyl Derivative ◽  
Competitive Inhibitor ◽  
Hydroxyl Groups ◽  
Pectic Acid ◽  
Substrate Complex ◽  
Enzyme Substrate ◽  
The Individual ◽  
Degradation Degree ◽  
Derivatives Of

The effect of exo-D-galacturonanase from carrot on O-acetyl derivatives of pectic acid of variousacetylation degree was studied. Substitution of hydroxyl groups at C(2) and C(3) of D-galactopyranuronic acid units influences the initial rate of degradation, degree of degradation and its maximum rate, the differences being found also in the time of limit degradations of the individual O-acetyl derivatives. Value of the apparent Michaelis constant increases with increase of substitution and value of Vmax changes. O-Acetyl derivatives act as a competitive inhibitor of degradation of D-galacturonan. The extent of the inhibition effect depends on the degree of substitution. The only product of enzymic reaction is D-galactopyranuronic acid, what indicates that no degradation of the terminal substituted unit of O-acetyl derivative of pectic acid takes place. Substitution of hydroxyl groups influences the affinity of the enzyme towards the modified substrate. The results let us presume that hydroxyl groups at C(2) and C(3) of galacturonic unit of pectic acid are essential for formation of the enzyme-substrate complex.

scholarly journals Molecular cohesion in plant cell walls. Methylation analysis of pectic polysaccharides from the cotyledons of white mustard

1969 ◽  
Vol 115 (3) ◽  
pp. 431-439 ◽  
Author(s):  
D. A. Rees ◽  
N. J. Wight
Keyword(s):  
Plant Cell ◽  
Cell Walls ◽  
Uronic Acid ◽  
Structural Elements ◽  
Plant Cell Walls ◽  
White Mustard ◽  
Methylation Analysis ◽  
Structural Units ◽  
Pectic Polysaccharides ◽  
Derivatives Of

Methylation analysis was used to characterize the pectic polysaccharides from mustard cotyledons, a tissue with potential for rapid biological change involving the walls. The methylated sugars were identified by g.l.c. and paper chromatography after conversion of uronic acid derivatives into [3H]hexoses, and confirmed by the formation of crystalline derivatives of most of the main products, which were: 2,3-di-O-methyl-d-[6−3H]galactose, 2-O-methyl-d-[6−3H]galactose, 3,4-di-O-methylrhamnose, 3-O-methylrhamnose, 2,3,5-tri-O-methyl-l-arabinose, 2,3-di-O-methyl-l-arabinose, 2-O-methyl-l-arabinose, 2,3,4-tri-O-methyl-d-xylose and 2,3,4,6-tetra-O-methyl-d-galactose in the molar proportions 1·00:1·14:0·54:0·74:2·86:2·50:2·24:1·88:0·32. The structural units present are similar to those in wellknown polysaccharides from mature tissues, but their proportions are strikingly different. Uninterrupted and unbranched galacturonan segments can therefore contribute little cohesion to these walls, and it is suggested that this correlates with a function of the wall matrix to hydrate and permit readjustment, during germination, of structural elements or wall surfaces or both.

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