Structure of micelles formed by highly asymmetric polystyrene-b-polydimethylsiloxane and polystyrene-b-poly[5-(N,N-diethylamino)isoprene] diblock copolymers.

The internal structure of polystyrene(PS)-shell micelles having core-forming blocks consisting of polydimethylsiloxane (PDMS) or poly[5-(N,N-diethylamino)isoprene] (PAI) was determined in detail by accessing the multilevel structural organization using static and dynamic light scattering and small-angle X-ray scattering techniques. Well-defined PS-b-PDMS and PS-b-PAI diblock copolymers with molar masses in the range of 12.0k-18.2k g/mol were dispersed in cyclohexane, dimethylacetamide, or dimethylformamide. Colloidal nanoparticles exhibiting either swollen core with a large surface area per corona chain that enables the PS chains to assume a random coil conformation with gaussian statistics, or compact core and slightly stretched PS chains in the corona were obtained. Therefore, the results of this study provide an interesting alternative allowing for precise control of the core and corona properties of PS-b-PDMS and PS-b-PAI micelles in selective solvents. Admittedly, such differences in terms of micellar properties can dictate the potential of block copolymer micelles for generating thin films from preformed nano-objects, as well as the capability to function as nanoreactors in organic medium.