Mesoscopic Network Topology and Permeability of Adaptive Amphiphilic Conetworks

具有受控网格结构和网络拓扑结构的聚合物模型网络为推导这些软和自适应材料的结构和性能之间的系统关系提供了明确的基础，其主要目的是解开网络中结构缺陷和不均匀性的影响。实现明确定义且几乎无缺陷的模型网络结构的出色方法是Sakai等人于2008年提出的四PEG方法，其基于两个异源互补四臂星形PEG前体的点击化学互连。我们的研究目标是将这种方法应用于2 × 2不同类型的两亲性网络（ACN）;这些是（A）共价连接的永久性以及（B）离子连接的可逆性ACN，每一种由（1）两种单独的亲水和疏水的异源互补星形结构单元或由（2）两种均表现出亲水-疏水性的异源互补星形结构单元实现。疏水核-壳形态。为了得到这些ACN的结构-性质关系，主要考虑其潜在的纳米，微米，甚至宏观相分离域和潜在的离子簇结构，有必要在不同的相关长度尺度上进行全面的结构表征。本项目的目的是提供这样的表征散射方法，主要是静态和动态光散射，以及通过调查的扩散渗透的纳米探针通过网络探测光漂白后的荧光恢复。两者都可以导出结构图。这些图片，沿着原始数据本身（散射曲线和扩散路径）将与我们研究小组的其他子项目中相同数据的互补理论模型相关联，以将所得材料特性（主要是粘弹性和选择性和可切换的渗透性）与网络合成参数相关联。

Polymer model networks with controlled mesh structure and network topology provide a well-defined basis for derivation of systematic relations between structure and properties of these soft and adaptive materials, with a prime view to unravelling the impact of structural defects and inhomogeneities in the networks. A splendid approach of realizing well-defined and nearly defect-free model network structures is the tetra-PEG approach by Sakai et al. from 2008, which is based on click-chemical interconnection of two heterocomplementary four-arm star-shaped PEG precursors. Our research initiative targets at applying this approach to 2 × 2 different types of amphiphilic conetworks (ACN); these are (A) covalently-jointed permanent as well as (B) ionically-jointed reversible ACN, each realized either from (1) two separate hydrophilic and hydrophobic heterocomplementary star-shaped building blocks or from (2) two kinds of heterocomplementary star-shaped building blocks that both exhibit hydrophilic-hydrophobic core–shell morphologies. To derive structure-property relations of these ACN, with a prime view on their potential nano-, micro-, or even macrophase-separated domains and potential ionic cluster structures, it is necessary to conduct a comprehensive structural characterization on different relevant lengthscales. The present project aims at providing such characterization by scattering methods, predominantly static and dynamic light scattering, as well as through investigation of the diffusive penetration of nanoscopic probes through the networks probed by fluorescence recovery after photobleaching. Both allows structural pictures to be derived. These pictures, along with the primary data themselves (scattering curves and diffusive paths) will be correlated to complementary theoretical models of the same data in other sub-projects of our research group to interrelate the resulting material properties (mostly in view of viscoelasticity and selective and switchable permeability) to the network synthesis parameters.