A series of gold nanoparticles stabilised by 'Newkome-type' dendritic branching has been synthesised and fully characterised. In particular, the properties and behaviour of these hybrid materials are compared with those of a previously reported set of nanoparticles stabilised by dendrons constructed using L-lysine building blocks. The rates of cyanide-induced nanoparticle decomposition were determined, and it was found that the rate of decomposition increased on the introduction of dendritic branching. Furthermore, 'Newkome-type' dendrons were significantly more effective at protecting the encapsulated gold nanoparticle than the L-lysine based dendrons. It is proposed that this observation can be explained on the basis of more effective packing and surface coverage by the 'Newkome-type' dendrons. Importantly, this study therefore demonstrates that the organic chemical structure of dendritic ligands plays a crucial role in controlling the reactivity of self-assembled hybrid nanostructures. (c) 2006 Elsevier Inc. All rights reserved.