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

1.用于评估水和多糖的动力学和相互作用的检测系统的构建：（1）将固体回波法检测极短T_2（> 10 μs）的方法与常用的CPMG法相结合，（原自由水）和未冻水（水合水的一部分）、聚合物链中惰性质子和不稳定质子之间的区别以及多糖的水合性质。(2)由于脉冲场梯度SE或STE和/或NMR显微成像用于可视化，因此构建了用于检测聚合物和水合水的慢运动的系统，其采用高场梯度用于扩散测量。(3)T2和扩散系数的同时分析系统：对扩散测量的脉冲序列进行了改进，使样品中的物种分数保持恒定。(4)质子化学交换和分子扩散交换条件下T2随温度变化的理论处理：对水质子磁化强度随时间变化的微分方程进行数值分析，得到实验条件下T2随温度变化的可能规律.普鲁兰多糖浓溶液中的水迁移率：利用所建立的系统1（1）和（3），在-11℃下，冻结水（T2 10μs）、未冻结水（T2 100μs）和惰性聚合物质子（T2 1 ms）可相互区分，而在0℃以上，通过快速扩散分子交换，不能区分水合水和自由水。证明了普鲁兰多糖分子链在水溶液中的柔性.采用Cu（II）EPR方法分析结冷胶对二价阳离子的吸收机理，从分子水平上阐明其吸收机理.本文用核磁共振、圆二色谱和粘弹性等方法研究了明胶凝胶化过程的动力学。证明了在螺旋形成之前存在氢键。

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.