Single-Chain Nanoparticle Complexation at Interfaces

目前的建议调查的分子内光交联聚合物链，所谓的两亲性单链纳米粒子（SCNPs）作为一种新型的表面活性剂的界面性质。具体来说，我们将通过利用特定嵌段共聚物链段之间的界面增强复合来设计SCNP，例如水溶性聚（甲基丙烯酸二甲氨基乙酯）（PDMAEMA）在界面处与油溶性聚（环氧丙烷）（PPO）结合，导致形成预先排列/塌陷的三明治构象，与两个嵌段之间距离较大的经典煎饼构象截然不同。这些预先排列的三明治将通过光化学交联方法在油/水界面处保存（仅仅是嵌段间交联和统计嵌段间和嵌段内交联;后者将允许桥接嵌段共聚物的相同嵌段的不同部分，而前者仅在相同链的两个嵌段之间产生桥）。为了实现这一目标，每个嵌段和交联程序的仔细设计是至关重要的。通过改变共聚物组成和交联条件，可以改变交联度，并且在某些情况下甚至逆转。随后，聚合物将在朗缪尔槽进行系统研究。我们预期所得到的SCNP具有前所未有的两亲性，例如，即使在较高的界面浓度下，链的平行取向也会导致界面处的Janus型结构。因此，我们预计，由于减少了覆盖界面的聚合物量，所得SCNP具有用于资源高效应用的增加的表面活性剂效率。

The current proposal investigates the interfacial properties of intramolecularly photo-crosslinked polymer chains, so-called amphiphilic single-chain nanoparticles (SCNPs) as a novel type of surfactant. Specifically, we will design SCNPs by exploiting interface-enforced complexation between segments of specific block copolymers, e.g. water-soluble poly(dimethylaminoethyl methacrylate) (PDMAEMA) associating at the interface with oil-soluble poly(propylene oxide) (PPO), leading to the formation of prearranged/collapsed sandwich conformations, critically different to the classical pancake conformation with a larger distance between both blocks. These prearranged sandwiches will be conserved by photochemical crosslinking methods at the oil/water interface (mere interblock crosslinking and statistical inter- and intrablock crosslinking; the latter would allow bridging different parts of the same block of the block copolymer, while the former generates bridges only between the two blocks of the same chain). To achieve this goal, the careful design of each block and the crosslinking procedure is critical. By variation of the copolymer composition and crosslinking conditions, the crosslinking degree can be altered and, in some cases, even reversed. Subsequently, the polymers will be investigated systematically at the Langmuir trough. We expect unprecedented amphiphilic properties of the resulting SCNPs, for example a rather parallel orientation of the chains even at higher interfacial concentration leading to a Janus-type structure at the interface. Hence, we expect that the resulting SCNPs feature an increased surfactant efficiency for resource-efficient applications due to decreased polymer amounts to cover the interface.