Stepwise noncovalent synthesis leading to dendrimer-based assemblies in water.

We provide detailed insight into complex supramolecular assembly processes by fully characterizing a multicomponent model system using dynamic light scattering, cryogenic transmission electron microscopy, atomic force microscopy, and various NMR techniques. First, a preassembly of a host molecule (the fifth-generation urea-adamantyl poly(propylene imine) dendrimer) and 32 guest molecules (a water- and chloroform-soluble ureidoacetic acid guest) was made in chloroform. The association constant in chloroform is concealed by guest self-association and is therefore higher than 10(3) M(-1). Via the neat state the single-host complex was transferred to water, where larger dendrimer-based assemblies were formed. The core of these assemblies, consisting of multiple host molecules (on average three), is kinetically trapped upon dissolution in water, and its size is constant irrespective of the concentration. The guest molecules forming the corona of the assemblies, however, stay dynamic since they are still in rapid exchange on the NMR time scale, as they were in chloroform. A stepwise noncovalent synthesis provides a means to obtain metastable dynamic supramolecular assemblies in water, structures that cannot be formed in one step.

Anisotropic elasticity of quasi-one-component polymer nanocomposites.

The in-plane and out-of-plane elastic properties of thin films of "quasi-one-component" particle-brush-based nanocomposites are compared to those of "classical" binary particle-polymer nanocomposite systems with near identical overall composition using Brillouin light scattering. Whereas phonon propagation is found to be independent of the propagation direction for the binary particle/polymer blend systems, a pronounced splitting of the phonon propagation velocity along the in-plane and out-of-plane film direction is observed for particle-brush systems. The anisotropic elastic properties of quasi-one-component particle-brush systems are interpreted as a consequence of substrate-induced order formation into layer-type structures and the associated breaking of the symmetry of the film. The results highlight new opportunities to engineer quasi-one-component nanocomposites with advanced control of structural and physical property characteristics based on the assembly of particle-brush materials.

Self-assembly of soft nanoparticles with tunable patchiness.

Details of the forces between nanoparticles determine the ways in which the nanoparticles can self-assemble into larger structures. The use of directed interactions has led to new concepts in self-assembly such as asymmetric dendrons, Janus particles, patchy colloids and colloidal molecules. Recent models that include attractive regions or 'patches' on the surface of the nanoparticles predict a wealth of intricate modes of assembly. Interactions between such particles are also important in a range of phenomena including protein aggregation and crystallization, re-entrant phase transitions, assembly of nanoemulsions and the organization of nanoparticles into nanowires. Here, we report the synthesis of 6-nm nanoparticles with dynamic hydrophobic patches and show that they can form reversible self-assembled structures in aqueous solution that become topologically more connected upon dilution. The organization is based on guest-host supramolecular chemistry with the nanoparticles composed of a hydrophobic dendrimer host molecule and water-soluble hydrophilic guest molecules. The work demonstrates that subtle changes in hierarchal composition and/or concentration can dramatically change mesoscopic ordering.