Effect of Orientational Specificity of Complexation on the Behavior of Supramolecular Polymers: Theory and Simulation
Effect of Orientational Specificity of Complexation on the Behavior of Supramolecular Polymers: Theory and Simulation
复制标题
络合定向特异性对超分子聚合物行为的影响：理论与模拟
DOI：
10.1021/ma062146
复制
发表时间：
2007
期刊：
影响因子：
5.5
通讯作者：
E. Dormidontova
中科院分区：
文献类型：
--
作者：
Matthew C. Hagy;Chun;E. Dormidontova
使用蒙特卡罗模拟，我们研究了由能够定向特异性可逆键合的供体和受体基团封端的柔性低聚物的缔合。根据模拟结果，我们获得了链增长和闭环的平衡常数。这些常数被用于分析模型中，该模型很好地再现了大规模模拟结果。我们还提出了一种分析方法，可用于分析实验数据或预测难以通过实验获得的分子量、链/环分布等。我们的模拟和分析结果表明，可逆键合定向特异性的增加降低了缔合度和分子量，并导致小环的抑制。结果，环-链交叉浓度（即链和环中可逆键数量重合的浓度）降低并呈现出作为寡聚物函数的最大值...
Using Monte Carlo simulations we study the association of flexible oligomers terminated by a donor and an acceptor group capable of orientationally specific reversible bonding. On the basis of simulation results, we have obtained equilibrium constants for chain growth and ring closure. These constants were employed in an analytical model, which reproduces the large-scale simulation results very well. We also propose an analytical approach which can be used to analyze experimental data or make predictions of molecular weight, chain/ring distributions, etc., which are hard to obtain experimentally. Our simulation and analytical results show that an increase of orientational specificity of reversible bonding decreases the degree of association and molecular weight and leads to the suppression of small rings. As a result the ring−chain crossover concentration (i.e., the concentration at which the number of reversible bonds in chains and rings coincide) decreases and exhibits a maximum as a function of oligome...