Thermodynamics of Conformational Ordering of ι-Carrageenan in KCl Solutions Using High-Sensitivity Differential Scanning Calorimetry

Thermodynamic properties of aqueous solutions of iota-carrageenan as affected by KCl (0.15-1.2 M) or iota-carrageenan (0.5-6 mg/mL) content were studied by high-sensitivity differential scanning calorimetry. The polysaccharide was found to undergo two consecutive cooperative conformational transitions, which can be represented by the scheme: [H2]2<-->2H2<-->4C where C is the random coil, H2 is the double helix, and [H2]2 is the double helix dimer. The first transition follows by the "all or none" mechanism. The profile of the second transition resembles that of a second-order phase transition. The parameter sigma (of order 1), estimated for this latter transition, suggests that the stacking effect in helices of iota-carrageenan is rather small. The cooperativity of the transition is mainly defined by the loop factor. Free energies of both transitions at 273 K were calculated as a function of salt concentration. These experimental data were found to agree with Manning's theory.