A molecular modeling approach to understand conformation-functionality relationships of galactomannans with different mannose/galactose ratios

Conformations of simulated galacomannans with different mannose/galactose ratios were investigated using molecular modelling software (Insight II/Discover_3 and RIS program, Version 4.0.0). The mannose/galactose ratios used in the present study were 4/1, 3/1, 2/1 and 1/1 respectively to simulate locust bean gum, tara gum, guar gum and fenugreek gum. Conformational parameters, Lp, C_∞ and Rg, were calculated. The results showed that the insertion of galactosyl groups could cause bending of the chains. The conformation of locust bean gum was much stiffer than the other three gums. Among the other three gums, fenugreek gum behaved as the most compact and flexible chain which might be due to the interactions along the side groups; guar gum behaved as the stiffest chain among the three gums, and tara gum was in the middle range. No ordered structures were observed in the fully substituted fenugreek gum chain. It was assumed that intra-chain interactions, both through side groups or smooth regions, could affect chain conformations. The results could explain the synergistic interactions between galactomannans and cellulosic polysaccharides: a more flexible chain can help with penetrating through networks in solutions, while the side groups can help with forming stronger “hyperentanglements” which themselves could increase viscosity; the stiffer chain with more unsubstituted regions can form junction zones with the cellulosic molecules.