Supramoleculare Polymer Brushes as Drug Carrier Systems – Design of defined and reactive systems

超分子相互作用是自然界中可逆地产生分级有序纤维结构的关键驱动力。目前的Emmy Noether项目采用了这一概念，目的是控制聚合物自组装成超分子纤维，也称为聚合物刷。由于其刚性的圆柱形形状，不同功能聚合物的集成及其模块化设计，相应的结构对于生物医学应用具有高度吸引力。迄今为止获得的结果表明，明确的结构-性能之间的关系的化学结构的超分子积木和它们的聚集。在这个项目的延续，扩大的目标是一个显着改善的控制聚集过程和由此产生的结构形成和反应性组装和分解过程的集成。首先，在继续以前的实验的全面调查将确定一个确定的增长动力学控制组件的基础上，合适的条件。理想地，可以鉴定亚稳区域，其在添加合适的核时启动活性生长过程。或者，在微流体装置中产生的限定的相变诱导更均匀的聚集过程并改善结构控制。与此同时，该延续项目旨在开发合适的积木，分别促进反应驱动的组装或组装结构的相应分解。聚集可以示例性地通过原位形成必要的疏水屏蔽来诱导。另一方面，疏水元件中的反应性基团打开了反应性裂解或转化的可能性，这随后导致结构的分解。在这些过程之后，可以产生对不同刺激非常特异性地反应的瞬时聚合物刷。类似于自然界中已知的纤维状结构的能量驱动材料的开发代表了该项目的后续步骤。因此，需要通过化学燃料可逆地激活并因此触发能量依赖性聚集的构建块。在聚合物链处与互补反应性的组合扩展了控制这种方法的机会，例如通过结构的可逆固定。从长远来看，该项目可能是开发智能和最重要的自适应合成材料的基石，这些材料可以对其环境的变化做出特异性和选择性反应，并在生物医学应用方面开辟新的方法，例如在药物运输或组织结构方面。

Supramolecular interactions are a key driving force in nature for reversible creation of hierarchically ordered fibrous structures. The current Emmy Noether project takes up this concept with the aim of controlling the self-assembly of polymers into supramolecular fibers, also called polymer brushes. Due to their rigid, cylindrical shape, the integration of different functional polymers, and their modular design, the corresponding structures are highly attractive for biomedical applications. The results obtained so far show clear structure-property relationships between the chemical structure of the supramolecular building blocks and their aggregation. In continuation of this project, the expanded goal is a significant improvement of the control over the aggregation process and the resulting structure formation and an integration of reactive assembly and disintegration processes. First, comprehensive investigations in continuation of previous experiments will determine suitable conditions for a defined growth based on a kinetically controlled assembly. Ideally, a metastable region can be identified that initiates a living growth process upon addition of suitable nuclei. Alternatively, defined phase transitions generated in microfluidic devices induce a more uniform aggregation process and improve structural control. In parallel, this continuation project aims to develop suitable building blocks that facilitate a reaction-driven assembly or a corresponding disintegration of the assembled structures, respectively. The aggregation can exemplarily be induced by the in-situ formation of the necessary hydrophobic shielding. On the other hand, reactive groups in the hydrophobic elements open up the potential for reactive cleavage or transformation, which subsequently leads to disintegration of the structures. Following these processes, transient polymer brushes can be created that react very specifically to different stimuli. The development of energy-driven materials analogous to known fiber-like structures in nature represents a subsequent step in this project. Therefore, building blocks are required that are reversibly activated by a chemical fuel and consequently trigger an energy-dependent aggregation. The combination with complementary reactivities at the polymer chains extends the opportunities to control this approach, e.g. by reversible fixation of the structures. In the long term, this project might represent a cornerstone for the development of intelligent and, above all, adaptive synthetic materials that can react specifically and selectively to changes in their environment and, with regard to biomedical applications, open up new approaches, e.g. in drug transport or the structuring of tissue.