Understanding the mechanism of nanoparticle self-assembly is of critical significance for developing synthetic strategies for complex nanostructures. By encapsulating aggregates of Au nanospheres in shells of polystyrene-block-poly(acrylic acid), we prevent the dissociation and aggregation typically associated with the drying of solution samples on TEM/SEM substrates. In our study of the salt-induced aggregation of 2-naphthalenethiol-functionalized Au nanospheres in DMF, the trapping of the solution species under various experimental conditions permits new insights in the mechanism thereof. We provide evidence that the spontaneous linear aggregation in this system is a kinetically controlled process and hence the long-range charge repulsion at the "transition state" before the actual contact of the Au nanospheres is the key factor. Thus, the charge repulsion potential (i.e. the activation energy) a nanosphere must overcome before attaching to either end of a nanochain is smaller than attaching on its sides, which has been previously established. This factor alone could give rise to the selective end-on attachment and lead to the linear assembly of originally isotropic Au nanospheres.
A central theme in nanotechnology is to advance the fundamental understanding of nanoscale component assembly, thereby allowing rational structural design that may lead to materials with novel properties and functions. nanoparticles (nPs) are often regarded as 'artificial atoms', but their 'reactions' are not readily controllable. Here, we demonstrate a complete nanoreaction system whereby colloidal nPs are rationally assembled and purified. Two types of functionalized gold nPs (A and B) are bonded to give specific products AB, AB 2 , AB 3 and AB 4 . The stoichiometry control is realized by fine-tuning the charge repulsion among the B-nPs. The products are protected by a polymer, which allows their isolation in high purity. The integration of hetero-assembly, stoichiometry control, protection scheme and separation method may provide a scalable way to fabricate sophisticated nanostructures.
A templated fabrication of open nanocavities is reported, where rational control of partial polymer attachment on sacrificial metal cores introduces openings in the polymer shells. This approach provides a facile means to modify the structural features of polymer nanocavities by manipulating the surface chemistry of colloidal nanoparticles. In particular, the anisotropic geometry of gold nanorods is exploited to promote the anisotropic polymer attachment, such that two diametric openings occurred in the polymer shell. After etching the gold nanorods, this approach yields open nanochannels that are tunable in both diameter and length. The synthetic scope of the anisotropic core/shell nanoparticles is expanded, supporting the previously proposed mechanism. We demonstrate that reducing the symmetry of nano-objects could open up new ways to create structural features using simple assembly and etching techniques. The thermostability of the open polymer nanostructures is also investigated.
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