Balancing Segregation and Complexation in Amphiphilic Copolymers by Architecture and Confinement
Balancing Segregation and Complexation in Amphiphilic Copolymers by Architecture and Confinement
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DOI：
10.1021/acs.langmuir.6b04602
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发表时间：
2017-05-02
期刊：
影响因子：
3.9
通讯作者：
Plamper, Felix A.
中科院分区：
文献类型：
--
作者：
Hebbeker, Pascal;Steinschulte, Alexander A.;Plamper, Felix A.
分离是胶束化的众所周知的原理，因为疏溶剂组分试图通过自组装使与其他实体（如溶剂）的相互作用最小化。相反的原理是基于复合（或凝聚），导致不同成分的共组装/结合。在文献中的大多数情况下，依赖于这些模式中的一个，虽然经典的胶束化方案（如球形胶束，蠕虫状胶束，囊泡）可以通过分离和络合的微妙平衡来丰富。由于它们的相互作用，可以获得具有前所未有的结构和行为的胶束结构。在这个功能中，系统被突出显示，这是两种机制之间，我们研究浓度，架构和约束效应。提出了具有分子间和分子内相互作用的体系，并讨论了聚合物拓扑结构和单体序列对所得结构的影响。结果表明，络合可以导致改变胶束化行为的一个疏水性和一个亲水性组分的复合物可以有一个非常低的表面张力对溶剂。然后，更可溶的组分在复合物的表面富集，并作为微表面活性剂。尽管溶液中两亲共聚物的分离占主导地位，但络合作用的效果可以通过支化（结构的改变）来增强。增强络合的另一种可能性是通过将共聚物限制在（伪）2D环境（如在液-液界面处可用的环境）中。这些观察结果显示了如何通过调整分离和络合/溶解之间的微妙平衡来实现新的结构特征。
Segregation is a well-known principle for micellization, as solvophobic components try to,minimize interactions with other entities (such as solvent) by self-assembly. An opposite principle is based on complexation (or coacervation), leading to the coassembly/association of different components. Most cases in the literature rely on only one of these modes, though the classical micellization scheme (such as spherical micelles, wormlike micelles, and vesicles) can be enriched by a subtle balance of segregation and complexation. Because of their counteraction, micellar constructs with unprecedented structure,and behavior could be obtained. In this feature, systems are highlighted, which are between both mechanisms, and we study concentration, architecture, and confinement effects. Systems with inter-and intramolecular interactions are presented, and the effects of polymer topology and monomer sequence on the resulting structures are discussed. It is shown that complexation can lead to altered micellization behavior as the complex of one hydrophobic and one hydrophilic component can have a very low surface tension toward the solvent. Then, the more soluble component is enriched at the surface of the complex and acts as a microsurfactant. Although segregation dominates for amphiphilic Copolymers in solution, the effect of the complexation can be enhanced by branching (change of architecture). Another possibility to enhance the complexation is by confining copolymers in a (pseudo-) 2D environment (like the one available at liquid-liquid interfaces). These observations show how new structural features can be achieved by tuning the subtle balance between segregation and complexation/solubilization.