链刚度对盐溶液中单个聚电解质构象的作用
Role of chain stiffness on the conformation of single polyelectrolytes in salt solutions.
作者信息
Wei Yu-Fu, Hsiao Pai-Yi
机构信息
Department of Engineering and System Science, National Tsing Hua University, Hsinchu, Taiwan 300, Republic of China.
出版信息
J Chem Phys. 2007 Aug 14;127(6):064901. doi: 10.1063/1.2751195.
Conformation of single polyelectrolytes in tetravalent salt solutions is investigated under the framework of a coarse-grained model, using Langevin dynamics simulations. The chain size, studied by the radius of gyration, shows three different variational behaviors with salt concentration, depending on the chain stiffness. According to the size variations, polyelectrolytes of fixed chain length are classified into three categories: (1) flexible chain, for which the variation shows a curve similar to a tilted L, (2) semiflexible chain, whose curve resembles U, and (3) rigid chain, for which the curve is a straight line. The wormlike chain model with persistence length predicted by the Odijk-Skolnick-Fixman theory is found to be able to qualitatively describe the end-to-end distance at low salt concentration not only for semiflexible and rigid chains but also for flexible chain. In a low salt region, a flexible polyelectrolyte extends more significantly than a semiflexible chain, in reference of the size of their uncharged counterparts, and in a high salt region, regardless of chain stiffness, a chain attains a dimension comparable to that of its neutral polymer. The chain stiffness influences both the local and the global chain structures. A flexible chain exhibits a zigzagged local structure in the presence of salt ions, and the condensed structure is a disordered, random globule. A semiflexible chain is locally smooth, and the condensed structure is orderly packed, taking a form such as hairpin or toroid. Moreover, the chain stiffness can also affect the nature of the coil-globule transition. The transition occurred in a discrete manner for semiflexible chain, whereas it occurred in a continuous way for flexible chain. This discrete feature happened not only at low salt concentration when a semiflexible chain collapsed but also at high salt concentration when the collapsed chain is reexpanded. At the end, the effects of chain stiffness and salt concentration on the conformation of single polyelectrolytes are summarized in a schematic state diagram.
在粗粒化模型框架下,利用朗之万动力学模拟研究了四价盐溶液中单个聚电解质的构象。通过回转半径研究的链尺寸,根据链的刚度,随盐浓度呈现出三种不同的变化行为。根据尺寸变化,固定链长的聚电解质可分为三类:(1)柔性链,其变化呈现出类似于倾斜L的曲线;(2)半柔性链,其曲线类似U形;(3)刚性链,其曲线为直线。发现由奥迪克 - 斯科尔尼 - 菲克斯曼理论预测的具有持久长度的蠕虫状链模型不仅能够定性描述低盐浓度下半柔性和刚性链以及柔性链的端到端距离。在低盐区域,参考其不带电对应物的尺寸,柔性聚电解质比半柔性链伸展得更显著,而在高盐区域,无论链的刚度如何,链达到与其中性聚合物相当的尺寸。链的刚度影响局部和全局链结构。柔性链在存在盐离子时呈现出锯齿状局部结构,凝聚结构是无序的随机球状体。半柔性链局部平滑,凝聚结构有序堆积,呈发夹或环形等形式。此外,链的刚度还会影响线团 - 球状体转变的性质。半柔性链的转变以离散方式发生,而柔性链的转变以连续方式发生。这种离散特征不仅在低盐浓度下半柔性链塌陷时出现,而且在高盐浓度下塌陷链重新伸展时也会出现。最后,在一个示意性状态图中总结了链刚度和盐浓度对单个聚电解质构象的影响。