Aqueous Dilution of Noble NPs Bulk Dispersions: Modeling Instability due to Dissolution by AF4 and Stablishing Considerations for Plasmonic Assays.

Among different nanomaterials, gold and silver nanoparticles (AuNPs and AgNPs) have become useful tools for a wide variety of applications in general, and particularly for plasmonic assays. Particle size and stability analysis are key elements for their practical applications since the NPs properties depend on these parameters. Hence, in the present work, asymmetrical flow field flow fractionation (AF4) coupled to UV-Vis and dynamic light scattering (DLS) detectors in series, has been evaluated for stability studies of citrate-capped AuNPs and AgNPs aqueous dispersions. First, experimental parameters, such as mobile phase or cross-flow rate were optimized. Sodium azide to pH 7 for AuNPs and pH 9.2 for AgNPs were selected as the optimum mobile phase. The analytical response of bulk dispersions of AuNPs (20, 40, 60 and 80 nm) and AgNPs (20, 40 and 60 nm) and their dilutions have been studied. Fractograms showed a decrease on the absorbance signal in diluted dispersions as a function of time and particle size for the diluted dispersions that can be explained by dissolution in diluted dispersion since hydrodynamic diameter was constant. The results indicated that the dependence of the signal with time was more intense for AgNPs than for AuNPs, which can be correlated with its lower stability. These findings should be considered when plasmonic assays are realized. Here, assays involving non-oxidant acidic acids as use cases, were tested for several batches of NPs and considerations about their stability and operability stablished.