Characterizing the Interplay between Polymer Solvation and Conformation
Characterizing the Interplay between Polymer Solvation and Conformation
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DOI：
10.1021/acs.jpcb.1c02191
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发表时间：
2021-05-12
影响因子：
3.3
通讯作者：
Patel, Amish J.
中科院分区：
文献类型：
--
作者：
Dhabal, Debdas;Jiang, Zhitong;Patel, Amish J.
柔性分子的构象转变，特别是那些由疏水效应驱动的构象转变，往往会受到去溶剂化障碍的阻碍。对于这样的转变，因此重要的是表征和理解溶剂化和构象之间的相互作用。使用专门的分子模拟，在这里，我们进行这样的表征在水中溶解的疏水性聚合物。我们发现，一个外部的潜在的，这不利于扰动的聚合物水化沃茨，可以触发线圈到球或崩溃过渡，和崩溃和扩展状态的相对稳定性可以量化的强度所需的潜力。我们的研究结果还提供了机制的崩溃过渡的见解，突出了聚合物崩溃的瓶颈是一个足够大的集群的形成，和集体去湿这样的集群。我们还研究了在辛烷，一种非极性溶剂中的疏水聚合物的崩溃，有趣的是，我们发现，过渡的机械细节是定性类似于在水中。
Conformational transitions of flexible molecules, especially those driven by hydrophobic effects, tend to be hindered by desolvation barriers. For such transitions, it is thus important to characterize and understand the interplay between solvation and conformation. Using specialized molecular simulations, here we perform such a characterization for a hydrophobic polymer solvated in water. We find that an external potential, which unfavorably perturbs the polymer hydration waters, can trigger a coil-to-globule or collapse transition, and that the relative stabilities of the collapsed and extended states can be quantified by the strength of the requisite potential. Our results also provide mechanistic insights into the collapse transition, highlighting that the bottleneck to polymer collapse is the formation of a sufficiently large cluster, and the collective dewetting of such a cluster. We also study the collapse of the hydrophobic polymer in octane, a nonpolar solvent, and interestingly, we find that the mechanistic details of the transition are qualitatively similar to that in water.