title: The disordered conformation of kappa-carrageenan in solution as determined by NMR experiments and molecular modeling.
abstract: The conformation of kappa-carrageenan in solution was studied combining 1H and 13C NMR with molecular mechanics. The experimental conditions were chosen to characterize the disordered conformation of the polymer. Particular attention has been given to explore a wide range of experimental conditions as to the dependence on solvent (water and Me2SO), polymer concentration, temperature, pH, presence of a denaturing agent (guanidinium chloride), and of ions otherwise able to induce conformational order of the carrageenan chains, either in solution (I-) or in the gel state (Rb+). Two-dimensional NOE experiments were analyzed to obtain information on internuclear distances, and molecular mechanics provided the range of energetically accessible conformations. Two inter-residue topological constraints were clearly identified: their combination is rather restricting for the chain and suggests that the disordered conformation of kappa-carrageenan is characterized by an intrinsic stiffness with high values of persistent length and characteristic ratio. They also rule out any postulated interchain hydrogen bonds. In contrast, experiments on the temperature dependence of the chemical shift in Me2SO reveal the existence of two inter-residue intramolecular H-bonds which might contribute positively to the rigidity of the polymer chain. The overall picture emerging from the present results is that of a locally elongated 'loose single helix'.
authors.affiliation: POLY-biós Research Center, AREA Science Park, Padriciano 99, I-34012 Trieste, Italy.
authors.forename: Marco
authors.initials: M
authors.lastname: Bosco
authors.forename: Annalaura
authors.initials: A
authors.lastname: Segre
authors.forename: Stanislav
authors.initials: S
authors.lastname: Miertus
authors.forename: Attilio
authors.initials: A
authors.lastname: Cesàro
authors.forename: Sergio
authors.initials: S
authors.lastname: Paoletti
mesh_terms: D002236:Carbohydrate Conformation; D002247:Carbon Isotopes; D002351:Carrageenan / Q000737:chemistry*; D003198:Computer Simulation; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D006859:Hydrogen / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D019906:Nuclear Magnetic Resonance, Biomolecular
chemical_list: D002247:Carbon Isotopes; D006859:Hydrogen; D002351:Carrageenan; D004121:Dimethyl Sulfoxide