Structural behaviour differences in low methoxy pectin solutions in the presence of divalent cations (Ca2+ and Zn2+): a process driven by the binding mechanism of the cation with the galacturonate unitElectronic supplementary information (ESI) available: Details of all the MD simulations performed; schematic structure of the Gal unit; potentials of mean force for the interaction of cations with Gal and associated representative configurations; figure and movies on the binding of Gal chains in th

• Main Authors: Assifaoui, Ali, Lerbret, Adrien, Uyen, Huynh T. D, Neiers, Fabrice, Chambin, Odile, Loupiac, Camille, Cousin, Fabrice
• Format: Journal Article
• Language: English
• Published: 17.12.2014
• ISSN: 1744-683X; 1744-6848
• DOI: 10.1039/c4sm01839g

In this paper, we compare the interactions between low methoxy pectin (LMP) and either Ca 2+ or Zn 2+ in semi-dilute solutions. Intrinsic viscosity and turbidity measurements reveal that pectin-calcium solutions are more viscous, but yet less turbid, than pectin-zinc ones. To get a molecular understanding of the origin of this rather unexpected behavior, we further performed isothermal titration calorimetry, small angle neutron scattering experiments, as well as molecular dynamics simulations. Our results suggest that calcium cations induce the formation of a more homogeneous network of pectin than zinc cations do. The molecular dynamics simulations indicate that this difference could originate from the way the two cations bind to the galacturonate unit (Gal), the main component of LMP: zinc interacts with both carboxylate and hydroxyl groups of Gal, in a similar way to that described in the so-called egg-box model, whereas calcium only interacts with carboxylate groups. This different binding behavior seems to arise from the stronger interaction of water molecules with zinc than with calcium. Accordingly, galacturonate chains are more loosely associated with each other in the presence of Ca 2+ than with Zn 2+ . This may improve their ability to form a gel, not only by dimerization, but also by the formation of point-like cross-links. Overall, our results show that zinc binds less easily to pectin than calcium does. Pectin chains form a more heterogeneous network with Zn 2+ than with Ca 2+ and associate in an egg-box-like configuration only with Zn 2+ .