title: Molecular structure encodes nanoscale assemblies: understanding driving forces in electrostatic self-assembly.
abstract: 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 < R(H) < 50 nm and positive ζ-potential values indicating a positive particle charge. Studies on dye self-aggregation and dendrimer-dye association by isothermal titration calorimetry (ITC) and UV-vis spectroscopy allow for the correlation of the thermodynamic parameters of dendrimer-dye association with the size of the particles, showing that at least a free energy gain of ΔG ≈ - 32 kJ mol(-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.
authors: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-University Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen, Germany.
authors: Immanuel
authors: I
authors: Willerich
authors: Franziska
authors: F
authors: Gröhn
mesh_terms: D002151:Calorimetry / Q000379:methods; D015394:Molecular Structure; D036103:Nanotechnology; D013056:Spectrophotometry, Ultraviolet; D055672:Static Electricity; D013816:Thermodynamics