5859-00-7Relevant articles and documents
Molecular structure encodes nanoscale assemblies: Understanding driving forces in electrostatic self-assembly
Willerich, Immanuel,Groehn, Franziska
, p. 20341 - 20356 (2011)
Supramolecular nanoparticles represent a key field in recent research as their synthesis through self-assembly is straightforward and they often can respond to external triggers. A fundamental understanding of structure-directing factors is highly desirable for a targeted structure design. This contribution demonstrates a quantitative relation between the size of supramolecular self-assembled nanoparticles and the free energy of association. Nanoparticles are prepared by electrostatic self-assembly of cationic polyelectrolyte dendrimers as model macroions and oppositely charged di- and trivalent organic dye molecules relying on the combination of electrostatic and π-π-interactions. A systematic set of sulfonate-group carrying azo-dyes was synthesized. Light scattering and ζ-potential measurements on the resulting nanoparticles yield hydrodynamic radii between 20 nm H -1 is necessary to induce dendrimer interconnection. Structural features of the azo dyes causing these to favor or prevent nanoparticle formation have been identified. The dye-dye-interaction was found to be the key factor in particle size control. A simple model yields a quantitative relation between the free energy and the particle sizes, allowing for predicting the latter based on thermodynamic measurements. Hence, a set of different molecular "building bricks" can be defined where the choice of building block determines the resulting assembly size.
