Multicore Unimolecular Structure Formation in Single Dendritic–Linear Copolymers under Selective Solvent Conditions

The
conformational and thermodynamic properties of single dendritic–linear
copolymers are investigated by analytical models and computer simulations.
Applying poor solvent conditions on the dendritic part, these molecules
are known to form single unimolecular micelle-like structures. A mean-field
model applying the Daoud–Cotton approach and a surface tension
argument is presented and suggests the splitting of the unimolecular
single-core structure into a multicore structure with increasing dendrimers
generation and decreasing solvent selectivity. Monte Carlo simulations
utilizing the bond fluctuation model with explicit solvent are performed
which show the formation of multicore structures for trifunctional
codendrimers of different generations and spacer lengths with linear
chains attached to the terminal groups. These findings are aimed to
understand the physics of spontaneous self-assembly of codendrimers
in various well-defined macro-conformations under change of environmental
conditions with potential applications such as drug delivery systems.