A model for self-assembly in solution
A model for self-assembly in solution
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DOI：
10.1021/jp027833r
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发表时间：
2003-05-29
影响因子：
3.3
通讯作者：
Ercolani, G
中科院分区：
文献类型：
--
作者：
Ercolani, G
提出了在热力学控制下处理自组装和非线性随机聚合之间的竞争的模型。处理所依据的基本量是组装体的有效摩尔浓度 (EM) 和单官能反应物之间的分子间模型反应 (K-inter) 的平衡常数。了解这些量可以评估自组装复合物的分布曲线。为了发生有效的自组装，产品 KinterEM 必须不低于基于简单结构参数（例如组装中的分子数量 (N)、连接分子的键数量 (B) 以及单体中相互作用位点的数量）易于计算的极限值。该限制随着 N 的减少和 B 的增加而减小，实现此条件的最明显方法是增加组件的循环程度 (B - N + 1)。具有高度循环性的组件的成品率对于 KinterEM 关于其极限值的适度变化也非常敏感。根据单体浓度的值，组装体可能会经历急剧分解（变性）或转化为凝胶。
A model treating the competition, under thermodynamic control, between self-assembly and nonlinear random polymerization is presented. The fundamental quantities on which the treatment is based are the effective molarity (EM) of the assembly and the equilibrium constant for the intermolecular model reaction between monofunctional reactants (K-inter). Knowledge of these quantities allows the evaluation of the distribution curve of the self-assembling complex. In order for effective self-assembly to take place, the product KinterEM must be no lower than a limit value easily computable on the basis of simple structural parameters such as the number of molecules in the assembly (N), the number of bonds joining them (B), and the number of interaction sites in the monomers. This limit decreases on decreasing N and on increasing B, and the most obvious way to realize this condition is by increasing the degree of cyclicity of the assembly (B - N + 1). The yield of an assembly with a high degree of cyclicity is very sensitive also to modest changes of KinterEM about its limit value. Depending on the value of the monomers concentration, the assembly could undergo either sharp disassembly (denaturation) or conversion into gel.