Facile generation of surface diversity in gold nanoparticles.

Surface chemistry is a key determinant of the physico-chemical and biological properties of gold nanoparticles (AuNPs). The introduction of chemical diversity in the surface of AuNPs is usually accomplished by place-exchange reactions using incoming ligands containing the desired terminal functional groups. As an alternative approach, we present here a simple, practical methodology to modify the surface of gold nanoparticles that allows the preparation of AuNPs stabilized with polyethyleneglycol (PEG) ligands with different surface chemistries using AuNPs stabilized with thiol-PEG-amino ligands as starting material. The surface modification reaction involves the acylation of the terminal amino groups in the ligand with an organic acid anhydride in an aqueous buffer. In addition to a full surface modification, this method also allows the synthesis of AuNPs with tailored mixed surfaces, containing two or more different functional groups, each of them at the desired extent. The ease of the experimental conditions for the reaction, purification, and for determining the level of surface modification makes this strategy an attractive alternative to current methods for the preparation of AuNPs with diverse surface chemistry.

Ag5 nanoclusters with dual catalytic antiradical activities.

Silver nanoclusters of five atoms (Ag5) display outstanding catalytic activities for the deactivation of radicals. Using 2,2-diphenyl-1­picrylhydrazyl (DPPH) radical as a model system, we observed a fast radical reduction to DPPH anions using only [Ag5] 3 to 4 orders of magnitude less than [DPPH]. Moreover, nanoclusters remain stable at the end of the reaction, and can deactivate again DPPH radicals at the same rate, indicating that they act as anti-radical catalysts. The radical scavenger catalytic activity of Ag5 proceeds selectively through the oxidation of methanol (used to dissolve the radical) to formaldehyde, which is supported by DFT calculations. The obtained catalytic rate constants are almost 2 orders of magnitude higher than oxidases, and more than 4 orders of magnitude larger than graphene quantum dots. We also show that Ag5 not only catalyze the reduction of radicals but also their oxidation, promoting the inhibition of the autoxidation mechanisms of hydrocarbon polymers, which are very sensitive to the presence of radicals. For this purpose, thin films of two industrially relevant polymers (polyisoprene and acrylonitrile-butadienestyrene copolymer), were exposed to standard simulated photo-ageing conditions in the presence of Ag5. Using Attenuated Total Reflection-FTIR and DFT modeling we observed that, although Ag5 nanoclusters, with ≈ 15% surface coverage, do not totally inhibit the oxidation, they favour a decomposition that yields inactive products, in contrast with the more detrimental ketone formation pathway. These results not only open new possibilities for developing a post-process inhibition of polymer degradation, for which nowadays there are no efficient procedures, but also, they could be used as very efficient dual-redox catalytic radical scavengers for different industrial or biomedical purposes.