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

我们提出探索分子水平的内在无序性对嵌段共聚物自组装胶体纳米结构和性能的影响。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，作为药物和遗传材料的纳米级载体，因为它们的尺寸、装载能力和货物释放轮廓可以通过适当设计组成共聚物进行微调。树枝状支链共聚物是特别感兴趣的，因为大量的末端基团可以与靶向配体功能化。这使得人们可以有效地在一个分子上连接不同的官能团，并利用生物识别机制将药物靶向递送到特定的组织或细胞。最新的关于共聚物自组装的实验大多是在完美单分散线性嵌段共聚物的理论基础上进行的。然而，新型药物的工业制造需要应用稳健的合成方案，这不可避免地导致产物（即嵌段共聚物）的分子质量多分散性和结构（拓扑）紊乱。对pi的初步研究表明，这并不一定是一个缺点：一定数量的分子无序甚至可以稳定自组装的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分支结构（拓扑多样性）的综合影响。特别是，我们将研究这种分子无序可以在多大程度上被利用来优化和调整纳米聚集体的结构和性质。为此，我们将结合分析热力学方法，导致精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.