Non-equilibrium supramolecular polymerization.
Non-equilibrium supramolecular polymerization.
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DOI：
10.1039/c7cs00121e
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发表时间：
2017-09-18
影响因子：
46.2
通讯作者：
Hermans TM
中科院分区：
文献类型：
--
作者：
Sorrenti A;Leira-Iglesias J;Markvoort AJ;de Greef TFA;Hermans TM
超分子聚合物可以处于四种不同的热力学状态。制备方案和机制见解可以识别它们中的每一个。超越平衡聚合是超分子化学领域一个令人兴奋的新方向。超分子聚合传统上关注热力学平衡状态，其中一维组装体处于吉布斯自由能的全局最小值。达到平衡状态的途径和速率是无关的，并且所得的组装体随着时间的推移保持不变。在过去的十年中，焦点已转移到动力学捕获（非耗散非平衡）结构，该结构在很大程度上取决于制备方法（即路径复杂性），并且组装速率至关重要。动力学模型极大地提高了我们对竞争途径的理解，并展示了如何将超分子聚合引导到所需的方向（即途径选择）。该领域的最新创新依赖于耗散的能量或质量输入，以使系统远离热力学平衡（或其他非耗散状态）。本教程回顾旨在为读者提供一组工具来识别迄今为止已探索的不同类型的自组装状态。特别是，我们的目标是通过将系统细分为耗散态和非耗散非平衡态来澄清术语“非平衡自组装”的经常不清楚的使用。给出了每种状态的示例，重点是一维超分子聚合中发现的非耗散非平衡状态。
Supramolecular polymers can reside in four distinct thermodynamic states. The preparation protocol and mechanistic insights allow to identify each one of them. Going beyond equilibrium polymerization is an exciting new direction in the field of supramolecular chemistry. Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term “non-equilibrium self-assembly” by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.
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影响因子：
15
作者：
Korevaar, Peter A.;Newcomb, Christina J.;Stupp, Samuel I.
通讯作者：
Stupp, Samuel I.
影响因子：
64.8
作者：
Korevaar, Peter A.;George, Subi J.;Meijer, E. W.
通讯作者：
Meijer, E. W.
DOI：
10.1073/pnas.1310092110
发表时间：
2013-10-22
影响因子：
11.1
作者：
Korevaar, Peter A.;Grenier, Christophe;Meijer, E. W.
通讯作者：
Meijer, E. W.
影响因子：
64.8
作者：
Fujita, Daishi;Ueda, Yoshihiro;Fujita, Makoto
通讯作者：
Fujita, Makoto
影响因子：
1.5
作者：
Escudero, Carlos;D'Urso, Alessandro;Purrello, Roberto
通讯作者：
Purrello, Roberto