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

We propose to explore the influence of intrinsic molecular-level disorder on the structure and properties 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 to exploit bio-recognition mechanisms for controlled targeted 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. At the same time, 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 proposed 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.