Collect. Czech. Chem. Commun. 1981, 46, 1701-1707

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

Rudolf Kohn and Anna Malovíková

Institute of Chemistry, Slovak Institute of Sciences, 809 33 Bratislava


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.