A series of pectins with different levels and patterns of methyl esterifica
tion was produced by treatment of a very highly methylated pectin with acid
, alkali, plant pectin methyl esterase and fungus pectin methyl esterase. T
he intrinsic pK values, as well as the free fractions of monovalent and cal
cium counterions, were determined on pectin salt-free solutions. The variat
ions of pK(a) versus the ionisation degree were found to depend on the de-e
sterification process but a unique value of 2.90 +/- 0.15 was estimated for
the intrinsic pK value. Calcium binding properties of chemically and enzym
atically de-esterified pectins were investigated and experimental results w
ere compared to Manning's theoretical values. A progressive dimerisation pr
ocess for pectins with a blockwise distribution of carboxyl groups in the p
resence of calcium ions is hypothesised. (C) 2001 Elsevier Science Ltd. All
rights reserved.