Abstract
Complexation of alginate models, built of beta-D-mannuronic units (M) linked by a 1-4 glycosidic bridge, to Al3+, Sc3+, Cr3+, Fe3+, Ga3+, and La3+ cations was studied by applying the quantum chemical density functional theory (DFT) based method. The binding modes and energies were obtained for complexes with one, two, and three truncated alginate chain(s). In all the hydrated structures a monodentate binding mode is established to be the energetically most favored with shorter M3+center dot center dot center dot O(COO-) bonds than M3+center dot center dot center dot O(OH) bonds. Coordination bond lengths are found to be specific to each cation and to depend very little on the water in the coordination sphere and on the number of saccharide units used to model an alginate chain. The binding energy tendency Fe3+ approximate to Cr3+ > Al3+ approximate to Ga3+ >> Sc3+ >= La3+ is not affected by the alginate models, the coordination to water molecules, and the number of chains. A significant covalent contribution that arises predominantly from a charge donation from the carboxylate oxygen to the metal cation was established from the orbital population analysis. An exothermic chain-chain association is predicted by the computed enthalpy variations. A comparison between the structural features of alginate complexation to trivalent and divalent cations is provided and discussed.