Cesàro A, Paoletti S, Urbani R, Benegas J
Dipartimento BBCM, Università di Trieste, Italy.
Int J Biol Macromol. 1989 Apr;11(2):66-72. doi: 10.1016/0141-8130(89)90044-5.
A statistical model is presented in which an ionic polymer is taken as a linear arrangement of flexible segments (similar to the spring-bead model). This model is used to represent semi-flexible linear ionic polysaccharides in solution. The distribution of end-to-end distances is taken from Monte Carlo calculations of the amylosic chain conformation and combined with Manning's counterion condensation theory of linear polyelectrolytes. The excess thermodynamic properties are then calculated as a function of the degree of ionization and of a number of physical variables. The results show that the statistical average of thermodynamic functions taken over the conformational states is not equivalent to the thermodynamic function of the average conformation. This has important implications for the correct comparison of theoretical prediction with the experimental results.
提出了一种统计模型，其中离子聚合物被视为柔性链段的线性排列（类似于弹簧珠模型）。该模型用于表示溶液中的半柔性线性离子多糖。端到端距离的分布取自直链淀粉链构象的蒙特卡罗计算，并与线性聚电解质的曼宁反离子凝聚理论相结合。然后将过量热力学性质作为电离度和一些物理变量的函数进行计算。结果表明，在构象状态上取的热力学函数的统计平均值不等于平均构象的热力学函数。这对于理论预测与实验结果的正确比较具有重要意义。
