Gelation of gellan – A review

Gellan is an anionic extracellular bacterial polysaccharide discovered in 1978. Acyl groups present in the native polymer are removed by alkaline hydrolysis in normal commercial production, giving the charged tetrasaccharide repeating sequence: → 3)-β-d-Glcp-(1 → 4)-β-d-GlcpA-(1 → 4)-β-d-Glcp-(1 → 4)-α-l-Rhap-(1 →. Deacylated gellan converts on cooling from disordered coils to 3-fold double helices. The coil–helix transition temperature (Tm) is raised by salt in the way expected from polyelectrolyte theory: equivalent molar concentrations of different monovalent cations (Group I and Me4N+) cause the same increase in Tm; there is also no selectivity between different divalent (Group II) cations, but divalent cations cause greater elevation of Tm than monovalent. Cations present as counterions to the charged groups of the polymer have the same effect as those introduced by addition of salt. Increasing polymer concentration raises Tm because of the consequent increase in concentration of the counterions, but the concentration of polymer chains themselves does not affect Tm. Gelation occurs by aggregation of double helices. Aggregation stabilises the helices to temperatures higher than those at which they form on cooling, giving thermal hysteresis between gelation and melting. Melting of aggregated and non-aggregated helices can be seen as separate thermal and rheological processes. Reduction in pH promotes aggregation and gelation by decreasing the negative charge on the polymer and thus decreasing electrostatic repulsion between the helices. Group I cations decrease repulsion by binding to the helices in specific coordination sites around the carboxylate groups of the polymer. Strength of binding increases with increasing ionic size (Li+ < Na+ < K+ < Rb+ < Cs+); the extent of aggregation and effectiveness in promoting gel formation increase in the same order. Me4N+ cations, which cannot form coordination complexes, act solely by non-specific screening of electrostatic repulsion, and give gels only at very high concentration (above ∼0.6 M). At low concentrations of monovalent cations, ordered gellan behaves like a normal polymer solution; as salt concentration is increased there is then a region where fluid “weak gels” are formed, before the cation concentration becomes sufficient to give true, self-supporting gels. Aggregation and consequent gelation with Group II cations occurs by direct site-binding of the divalent ions between gellan double helices. High concentrations of salt or acid cause excessive aggregation, with consequent reduction in gel strength. Maximum strength with divalent cations comes at about stoichiometric equivalence to the gellan carboxylate groups. Much higher concentrations of monovalent cations are required to attain maximum gel strength. The content of divalent cations in commercial gellan is normally sufficient to give cohesive gels at polymer concentrations down to ∼0.15 wt %. Gellan gels are very brittle, and have excellent flavour release. The networks are dynamic: gellan gels release polymer chains when immersed in water and show substantial recovery from mechanical disruption or expulsion of water by slow compression. High concentrations of sugar (∼70 wt % and above) inhibit aggregation and give sparingly-crosslinked networks which vitrify on cooling. Gellan forms coupled networks with konjac glucomannan and tamarind xyloglucan, phase-separated networks with kappa carrageenan and calcium alginate, interpenetrating networks with agarose and gelling maltodextrin, and complex coacervates with gelatin under acidic conditions. Native gellan carries acetyl and l-glyceryl groups at, respectively, O(6) and O(2) of the 3-linked glucose residue in the tetrasaccharide repeat unit. The presence of these substituents does not change the overall double helix structure, but has profound effects on gelation. l-Glyceryl groups stabilise the double helix by forming additional hydrogen bonds within and between the two strands, giving higher gelation temperatures, but abolish the binding site for metal ions by changing the orientation of the adjacent glucuronate residue and its carboxyl group. The consequent loss of cation-mediated aggregation reduces gel strength and brittleness, and eliminates thermal hysteresis. Aggregation is further inhibited by acetyl groups located on the periphery of the double helix. Gellan with a high content of residual acyl groups is available commercially as “high acyl gellan”. Mixtures of high acyl and deacylated gellan form interpenetrating networks, with no double helices incorporating strands of both types. Gellan has numerous existing and potential practical applications in food, cosmetics, toiletries, pharmaceuticals and microbiology.