The structure of j/i-hybrid carrageenans II. Coil–helix transition as a function of chain composition

Abstract

This paper describes the effect of the k/i-ratio on the physical properties of k/i-hybrid carrageenans (synonyms: kappa-2, k-2, weak kappa, weak gelling kappa). To this end, a series of k/i-hybrid carrageenans ranging from almost homopolymeric k-carrageenan (98 mol% k-units) to almost homopolymeric-carrageenan (99 mol% i-units) have been extracted from selected species of marine red algae (Rhodophyta). The k/i-ratio of these k/i-hybrids was determined by NMR spectroscopy. Their rheological properties were determined by small deformation oscillatory rheology. The gel strength (storage modulus, G0) of the j/i-hybrids decreases with decreasing j-content. On the other hand, the gelation temperature of the k-rich k/i-hybrids is independent of their composition. This allows one to control the gel strength independent of the gelation or melting temperature. The conformational order–disorder transition of the k/i-hybrids was studied using optical rotation and high-sensitivity differential scanning calorimetry. High-sensitivity DSC showed that the total transition enthalpy of the k/i-hybrids goes through a minimum at 60 mol% k-units, whereas for the mixture of j- and i-carrageenan, the total transition enthalpy is a linear function of the composition. With respect to the ordering capability, the k/i-hybrid carrageenans seem to behave as random block copolymers with length sequence distributions truncated from the side of the small lengths. Intrinsic thermodynamic properties (e.g., transition temperature and enthalpy) of k- and i-sequences in these copolymers are close to those of their parent homopolymers. The critical sequence length for k-sequences is 2-fold of that for i-sequences.