Interplay of Supramolecular and Macromolecular Dynamics in Transient Polymer Networks

该项目的目的是得到一个一致的图片上的超分子聚合物网络的动力学。 这将通过研究微观链的流动性和时间依赖性的微观网络拓扑结构在两个超分子聚合物网络模型工具箱建立从相同的前体聚合物，分别，但表现出极大的变化类型和强度的超分子链互连。 一个工具箱将这样做，以满足凯茨“活爬行”模型的结构基础，这是扩散，打破，并重新融合的遥爪链的低聚物末端连接的可逆键，其强度将在这项工作中系统地变化。 另一个工具箱将这样做，以满足Rubinstein-Semenov“粘性劳斯”和“粘性爬行”模型的结构基础，这是扩散聚合物，经历相互瞬时结合沿着其主链介导的缔合侧基，其瞬时结合强度也将在本项目中系统地变化。 这两个工具箱将与精致的控制积木链的长度，单分散性，和替代模式。 与此同时，它的目标是获得一个一致的图片上的瞬时链互连的强度如何与固有的大分子松弛动力学相互作用，以评估所产生的整体网络动态的高分子物理和超分子化学弧。 最重要的是，这种相互作用将进一步评估，通过系统地研究这些网络中的超分子结合基序的聚类和协同效应。 所有这些实验工作都将得到理论评估的补充。 该项目中使用的主要技术是流变学，光漂白后的荧光恢复，荧光相关光谱，静态和动态光散射，以及小角度X射线散射，部分在基于液滴的微流体环境中进行。 该项目预计将与两个特权合作伙伴进行密切合作：Evelyne货车Ruymbeke（比利时鲁汶天主教大学）和布拉德利D。Olsen（马萨诸塞州理工学院，美国）。 这项工作将与目前正在运行的姐妹项目（DFG编号SE 1888/5-1）相结合，该项目侧重于从星形构建块构建的不同类别的瞬态模型网络中的动力学和纳米拓扑学演化，拟议的研究将协同互补，但仍针对其自己的独立方向。

This project aims to derive a consistent picture on the dynamics of supramolecular polymer networks. This will be done by studying the microscopic chain mobility and the time-dependent microscopic network topology in two supramolecular polymer-network model toolboxes built from the same precursor polymers, respectively, yet exhibiting greatly varying type and strength of supramolecular chain interlinking. One toolbox will be made such to meet the structural basis of the Cates "living reptation" model, which is that of diffusing, breaking, and re-fusing telechelic chains of oligomers end-linked by reversible bonds, whose strength will be varied systematically in this work. Another toolbox will be made such to meet the structural basis of the Rubinstein-Semenov "sticky Rouse" and "sticky reptation" models, which is that of diffusing polymers that undergo mutual transient binding along their backbones mediated by associative sidegroups, whose transient binding strength will also be varied systematically in this project. Both toolboxes will be made with exquisite control of the building-block chain length, monodispersity, and substitution pattern. With that, it is targeted at obtaining a consistent picture on how the strength of transient chain interlinking interplays with the inherent macromolecular relaxation kinetics to assess the resulting overall network dynamics in an arc of polymer physics and supramolecular chemistry. On top of that, this interplay will be further assessed by systematically studying the effect of clustering and cooperativity of the supramolecular binding motifs in these networks. All this experimental effort will be supplemented by theoretical assessment. The prime techniques to be used in this project are rheology, fluorescence recovery after photobleaching, fluorescence correlation spectroscopy, static and dynamic light scattering, and small-angle x-ray scattering, partially conducted in a droplet-based microfluidic environment. The project anticipates strong collaboration with two privileged partners: Evelyne van Ruymbeke (Université Catholique Louvain, Belgium) and Bradley D. Olsen (Massachusetts Institute of Technology, U.S.A.). The work will tie in to a presently running sister project (DFG number SE 1888/5-1) that focuses on dynamics and nanotopological evolution in a different class of transient model networks built from star-shaped building blocks, to which the proposed research will be synergistically complementary, but yet targeted at its own independent direction.