title: Molecular mobility and microscopic structure changes in κ-carrageenan solutions studied by gradient NMR.
abstract: Changes in the molecular mobility of κ-carrageenan were observed by the pulsed field gradient stimulated echo (PGSTE) and Carr-Purcell-Meiboom-Gill (CPMG) methods for elucidating the molecular aspect of the sol-to-gel transition. The echo signal intensity of κ-carrageenan without a gradient, Ikap(0), decreased steeply near the sol-to-gel temperature (Tsg), suggesting that κ-carrageenan chains formed aggregates and a network structure. Below Tsg, the spin-spin relaxation time T2 and the diffusion coefficient of κ-carrageenan (Dkap) increased with decreasing temperature, indicating that the solute κ-carrageenan chains have a lower molecular weight Mw than chains involved in the aggregation. The diffusion coefficient of pullulan (Dpul) added as a probe molecule in κ-carrageenan solutions was measured, and the characteristic hydrodynamic screening length, ξ, was then estimated from the degree of diffusion restriction. Below a certain temperature, Dkap reached a higher value than that of Dpul, suggesting that the Mw of solute κ-carrageenan became lower than that of pullulan. GPC measurements confirmed the presence of κ-carrageenan chains with a lower Mw than that of pullulan. A simple physical model of the structural change in κ-carrageenan solution was proposed with a bimodal distribution of κ-carrageenan with higher and lower Mw than the pullulan probe. The higher Mw chains form the gel network restricting the probe's diffusion, and the lower Mw chains increase the effective viscosity. The concentration of the high Mw solute κ-carrageenan chains in 1%, 2% and 4% κ-carrageenan solutions was estimated from Ikap(0) and the total κ-carrageenan concentration, and the relation with pullulan diffusion was studied.
authors.affiliation: Department of Food Science and Technology, Tokyo University of Marine Science and Technology, 4-5-7 Konan, Tokyo 108-8477, Japan.
authors.forename: Qiuhua
authors.initials: Q
authors.lastname: Zhao
authors.forename: Tom
authors.initials: T
authors.lastname: Brenner
authors.forename: Shingo
authors.initials: S
authors.lastname: Matsukawa
mesh_terms: D002351:Carrageenan / Q000737:chemistry*; D002850:Chromatography, Gel; D009682:Magnetic Resonance Spectroscopy; D012996:Solutions
chemical_list: D012996:Solutions; D002351:Carrageenan