糖鎖による超分子中の水の運動性及び水素結合特性の磁気共鳴法による検出と応用研究

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1. Construction of the detection system for evaluating the dynamics and interactions of water and polysaccharides : (1) Solid echo method for detecting very short T2 (>l0μs) was combined to the usually used CPMG method to evaluate the amount of frozen water (originally free water) and un-frozen water (a portion of hydration water), differentiation between the inert protons and the labile protons in the polymer chain, and hydration properties of polysaccharides. (2) System for detecting slow motion of polymer and hydration water was constructed employing high field gradient for diffusion measurement due to the pulsed field gradient SE or STE and/or NMR microimaging for visualization. (3) Simultaneous analyzing system of T2 and Diffusion coefficient : Pulse sequence for diffusion measurement was modified to keep the fractions of species in samples constant. (4) Theoretical treatment of temperature dependence of T2 in the presence of a chemical proton exchange and a diffusive molecular exchange : differential equations for time dependence of magnetization due to water proton were numerically analyzed to obtain possible change of T2 with the temperature change under the experimental conditions.2. Water mobility in concentrated pullulan solutions : By using the established systenn 1 (1) and(3), frozen water (T2 10μs), unfrozen water (T2 100μs) and inert polymer protons (T2 1ms) at -11℃ were distinguished each other and in the temperature more than 0℃ hydration water and free water was not differentiate by rapid diffusive molecular exchange. The flexibility of pullulan chain in aqueous solution is proved.3. Uptake mechanism of divalent cation by gellan gum was analyzed by Cu(II) EPR method and the mechanisn was made clear in the molecular level.4. Kinetic studies of the gelation process of gelatin was investigated based on ^1H T_2 NMR, CD and viscoelesticity measurements. Hydrogen bonding dormation in prior to the coil formation was proved.