Theory and computer modelling of self-organization of linear-dendritic macromolecules into colloidal nano-structures: impacts of topological and molecular mass polydispersity

我们打算探索本征分子水平无序对嵌段共聚物自组装胶体纳米结构的结构和性质的影响。这种结构被认为在(生物)纳米技术和医学中具有巨大的潜力，例如作为药物和遗传物质的纳米级载体，因为它们的尺寸、载荷量和货物释放曲线可以通过适当的组成共聚物的设计来微调。树枝状支化的共聚物特别令人感兴趣，因为大量的末端基团可以被靶向配体官能化。这使得人们能够有效地将不同的官能团连接到一个分子上，并利用生物识别机制来控制药物的靶向传递到特定的组织或细胞。迄今为止，关于共聚物自组装的实验大多是基于为完全单分散的线性嵌段共聚而发展的理论。然而，新型药物的工业生产需要应用强大的合成协议，这不可避免地导致产品的分子质量多分散性和结构(拓扑)无序，即嵌段共聚物。对PI的初步研究表明，这并不一定是一个缺点：一定量的分子无序甚至可以稳定自组装纳米结构并改善其性能。该项目的目的是将我们的理论知识扩展到传统的理想化体系之外，并研究自组装嵌段共聚物的分子质量分布和不规则支化结构(拓扑多样性)的综合影响。特别是，我们将研究这种分子无序在多大程度上可以被用来优化和调节纳米聚集体的结构和性能。为此，我们将结合分析热力学方法，以获得准确的结果和数值模拟。

We propose to explore the influence of intrinsic molecular-level disorder on the structure andproperties of self-assembled colloidal nanostructures made of block copolymers . Such structures are considered to have a huge potential in (bio)nanotechnology and medicine, e.g., as nano-scale carriers for drugs and genetic materials because their size, loading capacity and cargo release profiles can be fine-tuned by proper design of constituent copolymers. Dendritically branched copolymers are of particular interest, because of the large number of terminal groups that can be functionalized with targetable ligands. This allows one to efficiently connect different functional groups on one molecule and exploit bio-recognition mechanisms for controlled targetted delivery of the drugs to specific tissues or cells.Up-to-date experiments on the copolymer self-assembly were mostly rationalized on the basis of theories developed for perfectly monodisperse linear block copolymers.However, industrial manufacturing of novel pharmaceuticals requires the application of robust synthetic protocols that unavoidably result in molecular mass polydispersity and structural (topological) disorder of the products, i.e., the block copolymers. Preliminary studies of the PIs indicate that this is not necessarily a drawback: A certain amount of molecular disorder can even stabilize self-assembled nanostructures and improve their properties.The aim of the project is to extend our theoretical knowledge beyond traditional“idealized” systems and investigate the combined effects of molecular mass distribution and irregular branched structure (topological diversity) of self-assembling block-copolymers. In particular, we will investigate to which extent such molecular disorder can be exploited to optimize and tune the structure and properties of the nano-aggregates. To this end, we will combine analytical thermodynamic approaches that lead to exact results and numerical simulations.