title: The structure of kappa/iota-hybrid carrageenans II. Coil-helix transition as a function of chain composition.
abstract: This paper describes the effect of the kappa/iota-ratio on the physical properties of kappa/iota-hybrid carrageenans (synonyms: kappa-2, kappa-2, weak kappa, weak gelling kappa). To this end, a series of kappa/iota-hybrid carrageenans ranging from almost homopolymeric kappa-carrageenan (98 mol-% kappa-units) to almost homopolymeric-carrageenan (99 mol-% iota-units) have been extracted from selected species of marine red algae (Rhodophyta). The kappa/iota-ratio of these kappa/iota-hybrids was determined by NMR spectroscopy. Their rheological properties were determined by small deformation oscillatory rheology. The gel strength (storage modulus, G') of the kappa/iota-hybrids decreases with decreasing kappa-content. On the other hand, the gelation temperature of the kappa-rich kappa/iota-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 kappa/iota-hybrids was studied using optical rotation and high-sensitivity differential scanning calorimetry. High-sensitivity DSC showed that the total transition enthalpy of the kappa/iota-hybrids goes through a minimum at 60 mol-% kappa-units, whereas for the mixture of kappa- and iota-carrageenan, the total transition enthalpy is a linear function of the composition. With respect to the ordering capability, the kappa/iota-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 kappa- and iota-sequences in these copolymers are close to those of their parent homopolymers. The critical sequence length for kappa-sequences is 2-fold of that for iota-sequences.
authors.affiliation: Wageningen Centre for Food Sciences, PO Box 557, 6700 AN Wageningen, The Netherlands. fred.van.de.velde@nizo.nl
authors.forename: Fred
authors.initials: F
authors.lastname: van de Velde
authors.forename: Anna S
authors.initials: AS
authors.lastname: Antipova
authors.forename: Harry S
authors.initials: HS
authors.lastname: Rollema
authors.forename: Tatiana V
authors.initials: TV
authors.lastname: Burova
authors.forename: Nataliya V
authors.initials: NV
authors.lastname: Grinberg
authors.forename: Leonel
authors.initials: L
authors.lastname: Pereira
authors.forename: Paula M
authors.initials: PM
authors.lastname: Gilsenan
authors.forename: R Hans
authors.initials: RH
authors.lastname: Tromp
authors.forename: Brian
authors.initials: B
authors.lastname: Rudolph
authors.forename: Valerij Ya
authors.initials: VY
authors.lastname: Grinberg
mesh_terms: D002351:Carrageenan / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013696:Temperature; D013816:Thermodynamics
chemical_list: D002351:Carrageenan