title: Measuring silver nanoparticle dissolution in complex biological and environmental matrices using UV-visible absorbance.
abstract: Distinguishing the toxic effects of nanoparticles (NPs) themselves from the well-studied toxic effects of their ions is a critical but challenging measurement for nanotoxicity studies and regulation. This measurement is especially difficult for silver NPs (AgNPs) because in many relevant biological and environmental solutions, dissolved silver forms AgCl NPs or microparticles. Simulations predict that solid AgCl particles form at silver concentrations greater than 0.18 and 0.58 μg/mL in cell culture media and moderately hard reconstituted water (MHRW), respectively. The AgCl NPs are usually not easily separable from AgNPs. Therefore, common existing total silver techniques applied to measure AgNP dissolution, such as inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption, cannot accurately measure the amount of silver remaining in AgNP form, as they cannot distinguish Ag oxidation states. In this work, we introduce a simple localized surface plasmon resonance (LSPR) UV-visible absorbance measurement as a technique to measure the amount of silver remaining in AgNP form for AgNPs with constant agglomeration states. Unlike other existing methods, this absorbance method can be used to measure the amount of silver remaining in AgNP form even in biological and environmental solutions containing chloride because AgCl NPs do not have an associated LSPR absorbance. In addition, no separation step is required to measure the dissolution of the AgNPs. After using ICP-MS to show that the area under the absorbance curve is an accurate measure of silver in AgNP state for unagglomerating AgNPs in non-chloride-containing media, the absorbance is used to measure dissolution rates of AgNPs with different polymer coatings in biological and environmental solutions. We find that the dissolution rate decreases at high AgNP concentrations, 5 kDa polyethylene glycol thiol coatings increase the dissolution rate, and the rate is much higher in cell culture media than in MHRW.
authors.affiliation: Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA. jzook@nist.gov
authors.forename: Justin M
authors.initials: JM
authors.lastname: Zook
authors.forename: Stephen E
authors.initials: SE
authors.lastname: Long
authors.forename: Danielle
authors.initials: D
authors.lastname: Cleveland
authors.forename: Carly Lay A
authors.initials: CL
authors.lastname: Geronimo
authors.forename: Robert I
authors.initials: RI
authors.lastname: MacCuspie
mesh_terms: D000818:Animals; D002712:Chlorides / Q000737:chemistry; D004784:Environmental Monitoring / Q000379:methods; D013058:Mass Spectrometry / Q000379:methods; D053768:Metal Nanoparticles / Q000032:analysis*; D012834:Silver / Q000032:analysis*; D012995:Solubility; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D020349:Surface Plasmon Resonance / Q000379:methods*
chemical_list: D002712:Chlorides; D012834:Silver