Journal of Colloid and Interface Science, Vol.479, 173-181, 2016
Sub-monolayer silver loss from large gold nanospheres detected by surface plasmon resonance in the sigmoidal region
Nanosilver becomes labile upon entering the human body or the environment. This lability creates silver species with antimicrobial properties that make nanosilver attractive as active components in many consumer products, wound dressings, and agricultural applications. Because lability depends strongly on morphology, it is imperative to use a material with constant lability throughout kinetic studies so that accurate lability data can be acquired with efficient detection. Here 2.5 nm thick silver was coated onto 90-nm diameter gold nanosphere cores and this surface silver layer was gradually removed by either chemical or X-ray radiation etching. The most sensitive region of a sigmoidal surface plasmon resonance (SPR) response as a function of silver thickness was found for the first time between 0.9- and 1.6-nm thick silver, revealing a new nanosilver standard for lability studies. The SPR peak position detection sensitivity is 8 nm (SPR peak shift)/nm (silver thickness change) within this steepest region of the plasmon response curve whereas outside, sensitivity drops to 1 nm/nm. Since the centroid of SPR profiles can be discerned with 0.25 nm precision, the 8-nm/nm sensitivity means it is possible to detect a 0.3-angstrom or sub-monolayer change in silver thickness. The SPR response simulated by discrete dipole approximation (DDA) was an identical sigmoidal function between 0 and 2 nm of silver coating. These findings were supported by several other analytical measurements, which confirmed no silver recoating during these etching processes. (C) 2016 Elsevier Inc. All rights reserved.
Keywords:Nanosilver;Surface silver;Core-shell nanoparticles;Surface plasmon resonance (SPR);Sigmoidal response;SPR-thickness response;SPR sensing;Exponential phase;Thin silver shell