Collect. Czech. Chem. Commun. 1986, 51, 2259-2270

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

Anna Malovíková and Rudolf Kohn

Institute of Chemistry, Centre for Chemical Research, Slovak Academy of Sciences, 842 38 Bratislava


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.