Polysaccharide chains, modeling interactions

The conformation of acidic polysaccharides and their interactions with calcium ions was examined by molecular simulation, and the authors demonstrated the existence of specific calcium binding with poly-a-L-guluronate [56, 57], The mechanism of complex formation involves calcium interactions with different oxygen atoms of two adjacent guluronic acid units and with two inter-chain units, as visualized in the egg-box model (Fig. 24.7). The mechanism of gelation is a two-step process first step is a dimer formation, followed by precipitation for small chains, or gelation for long ones formed with different types of blocks. 

Using computer modeling, jointly with x-ray fiber diffraction data, the molecular architectures of two different gel-forming polysaccharides have been examined. Preliminary results indicate that the neutral and doubly branched capsular polysaccharide from Rhizobium trifolii can form a 2-fold single helix of pitch 1.96 nm or a half-staggered, 4-fold doublehelix of pitch 3.92 nm. The molecules are likely to be stabilized by main chain — side chain interactions. 

The ability of certain galactomannans to form gel structures when mixed with these non-gelling polysaccharides implies that a network is formed by the interaction of unlike chains. Fiber diffraction evidence, and indications from computer model-building191,19- (dis-... 

In summary, the QCM-D technique has successfully demonstrated the adsorption of pectin on the BSA surface as well as determined the viscoelastic properties of the pectin layer. As pectin concentrations increase, the adsorbed mass of pectin estimated from the Voigt model show higher values than those estimated from the Sau-erbrey equation because the former takes into account the hydrated layer. But the similar increase of thickness of pectin suggests that the pectin chains form a multilayer structure. In agreement with our previous rheology results, the main elastic character of the pectin layer in terms of Q-tool software tells us the network structure of the pectin layer on the BSA surface. In summary, QCM-D cannot only help to better understand the polysaccharide/protein interactions at the interface, but also to gain information of the nanoscale structure of polysaccharide multilayers on protein surface. 

The SEC partition coefficient [6] (.K sec) was measured on a Superose 6 column for three sets of well-characterized symmetrical solutes the compact, densely branched nonionic polysaccharide, Ficoll the flexible chain nonionic polysaccharide, pullulan and compact, anionic synthetic polymers, carboxylated starburst dendrimers. All three solutes display a congruent dependence of K ec on solute radius, R. In accord with a simple geometric model for SEC, all of these data conform to the same linear plot of i sEc versus R. This plot reveals the behavior of noninteracting spheres on this column. The mobile phase for the first two solutes was 0.2M NaH2P04-Na2HP04, pH 7.0. In order to ensure the suppression of electrostatic repulsive interactions between the dendrimer and the packing, the ionic strength was increased to 0.30M for that solute. 

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