Thermoreversible gelation of kappa-carrageenan: relation between conformational transition and aggregation.

We have studied, by optical rotation dispersion, light scattering and rheology, the kappa-Carrageenan system to elucidate the processes involved in gel formation (on decreasing the temperature) and gel melting (on increasing the temperature). Our results show that, on decreasing the temperature, a conformational transition from coils to double helices first occurs, followed by aggregation of the double helices into domains and gel formation at appropriate polymer concentration. Structural details of this sequence are better revealed by re-heating the system. Melting appears as a two-step process characterized by first a conformational change of helices involved in junction zones between aggregates, followed by the conformational transition of the helices inside the aggregates. These helices can regain the coil conformation only when the aggregates melt at higher temperature, in full agreement with the old 'domain' model. The full description of the sol-gel mechanism of this system can be useful in the search for new methods to control the gel texture, a relevant property for many industrial applications.

[1]  G. W. Skinner,et al.  Pharmaceutical applications of naturally occurring water-soluble polymers , 1998 .

[2]  Zhibing Hu,et al.  Turbidity investigation of the sol–gel transition in carrageenan gels under physiologic conditions , 1998 .

[3]  P. N. Pusey,et al.  Dynamic light scattering by non-ergodic media , 1989 .

[4]  T. M. Parker,et al.  Interaction of processes on different length scales in a bioelastomer capable of performing energy conversion. , 2001, Biopolymers.

[5]  H. Reynaers,et al.  On the Molar Mass of κ-Carrageenan in the Course of Conformational Transition from the Disordered to the Fundamental Ordered Form , 1999 .

[6]  D. Rees,et al.  Secondary and Tertiary Structure of Polysaccharides in Solutions and Gels , 1977 .

[7]  C. Rochas,et al.  Mechanism of gel formation in κ‐carrageenan , 1984 .

[8]  V. Martorana,et al.  Interacting processes in protein coagulation , 1999, Proteins.

[9]  D. Durand,et al.  Structure and kinetics of aggregating κ-carrageenan studied by light scattering , 2000 .

[10]  F. A. Varkevisser,et al.  Molecular characterisation of κ- and λ-carrageenan by gel permeation chromatography, light scattering, sedimentation analysis and osmometry , 1991 .

[11]  C. Rochas,et al.  Acid and enzymic hydrolysis of Kappa carrageenan , 1981 .

[12]  M. Huglin Light scattering from polymer solutions , 1972 .

[13]  J. Sebranek,et al.  Carrageenans and their use in meat products. , 1996, Critical reviews in food science and nutrition.

[14]  S. Paoletti,et al.  Conformational transition of .kappa.-carrageenan in aqueous solution , 1985 .

[15]  Dennis E. Koppel,et al.  Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants , 1972 .

[16]  D. Durand,et al.  Structure of aggregating κ-carrageenan fractions studied by light scattering , 2001 .

[17]  V. Martorana,et al.  Multiple interactions between molecular and supramolecular ordering , 1999 .

[18]  E. Morris,et al.  Cation-specific aggregation of carrageenan helices: Domain model of polymer gel structure. , 1980, Journal of molecular biology.

[19]  H. Reynaers,et al.  Influence of ionic effects on the ordering and association phenomena in dilute and semidilute carrageenan solutions. , 1996, International Journal of Biological Macromolecules.

[20]  D. Rees,et al.  Structure, conformation, and mechanism in the formation of polysaccharide gels and networks. , 1969, Advances in carbohydrate chemistry and biochemistry.

[21]  D. Horne,et al.  Milk protein-carrageenan interactions , 1997 .

[22]  Malgorzata Ciszkowska and,et al.  Conductometric Detection of Coil-to-Helix Transition of Anionic Polysaccharides. κ-Carrageenan , 1999 .

[23]  H. Ohshima,et al.  Design of a rate- and time-programming drug release device using a hydrogel: pulsatile drug release from kappa-carrageenan hydrogel device by surface erosion of the hydrogel. , 2001, Colloids and surfaces. B, Biointerfaces.

[24]  A. Imamura,et al.  Observation of the Molecular Weight Change during the Helix−Coil Transition of κ-Carrageenan Measured by the SEC−LALLS Method , 1998 .