Adaptive Polymergele mit kontrollierter Netzwerkstruktur

两亲网络（ACN）由疏水和亲水聚合物组成，形成一种共同的渗透网络结构，能够在水和有机介质中膨胀。这种两亲性的膨胀性导致了亲水、疏水和两亲物质对溶剂敏感的粘弹性和渗透性。两者都可以作为多功能应用的基础，如软性隐形眼镜，可切换细胞基板或抗菌涂层。然而，溶剂敏感的粘弹性和热选择性性能是由聚合物网络的纳米和微观结构决定的，而这些微观结构又因选择性介质中团簇和部分折叠畴的存在而进一步复杂化。我们的研究计划旨在提供这些结构和性质之间的定量关系。为了达到这个目标，我们从Sakai和Shibayama的四聚乙二醇方法获得的模型网络结构开始，我们将采用该方法进行ACN。为了使其真正有意义，我们将实现两种不同类型的ACN。一类由共价和永久连接的构建块组成；另一类由离子和瞬时可逆连接的构建块组成。前者的纳米和微观结构由实验中当前膨胀状态和网络形成时刻的条件决定，后者仅由测量时的条件决定。比较这两种互补的ACN类型，可以清楚地认识到网络渗透过程中形成的网络不规则性的影响。在此基础上，我们将确定网络构建块的化学和拓扑结构、它们的化学测量比以及其他反应参数（如浓度、温度、反应活性和粘度）对共价互联ACN的最终网络结构的影响，以及这种结构如何通过相反亲性部分的选择性膨胀和崩溃而进一步复杂化。特别是，我们将确定在什么样的参数空间中存在大型的、潜在的渗透域，以及在选择性介质中坍塌的构建块的聚合数是多少。在这些结构模型的基础上，我们将重点研究凝胶样品表面和体积上网络结构及其粘弹性力学和热选择性渗透率的相互作用。所有这些研究将从实验和理论两个角度进行。我们的总体目标是在实验和理论之间进行强烈的反馈，旨在推导出ACN的定量结构-性能关系，并以此为基础合理设计软质材料。

Amphiphilic conetworks (ACN) consist of hydrophobic and hydrophilic polymer building blocks that form a common percolated network structure able to swell in both water and organic media. This amphiphilic swellability leads to solvent-sensitive viscoelasticity and permeability for hydrophilic, hydrophobic, and amphiphilic substances. Both can serve as a basis for versatile applications such as soft contact lenses, switchable cell substrates, or antimicrobial coatings. The solvent-sensitive viscoelastic and perm-selective properties, however, are determined by the polymer network nano- and microstructure, which, in turn, is further complexed by the presence of clusters and partially collapsed domains in selective media. Our research initiative aims at delivering quantitative relations between these structures and properties. To reach that goal, we start from model-network structures as obtained by Sakai's and Shibayama's tetra-PEG approach, which we will adopt for ACN. To make this truly meaningful, we will realize two different classes of ACN. One class consists of covalently and permanently connected building blocks; another class consist of ionically and transient-reversibly connected building blocks. Whereas the nano-and microstructures of the first are determined by both the conditions during a current state of swelling in an experiment as well as the conditions during the moment of network formation, the latter are determined only by the conditions at measurement. Comparison of both these complementary classes of ACN allows the impact of network irregularity as formed during the network percolation to be clearly recognized. On this basis, we will determine the impact of the chemical and topological constitution of the network building blocks, their stoichiometric ratio, and further reactions parameters such as concentration, temperature, reactivity, and viscosity on the resulting network structure of covalently interlinked ACN, and how this structure is further complexed by selective swelling and collapse of their oppositely philic parts. In particular, we will determine in what parameter space large, potentially percolated domains will be present and how the aggregation number of the collapsed building blocks in selective media is. On the basis of these structural models, we will focus on the interplay of the network structures and their viscoelastic mechanics and perm-selective permeability both at the gel-specimen surface and in their bulk. All these studies will be conducted both from experimental and theoretical perspectives. It is our overall goal to undergo intense feedback between experiment and theory, with the aim to derive quantitative structure-property relations for ACN as a basis for rational design of soft materials based on them.