Silver ion-imprinted magnetic adsorbent hyphenated to single particle-ICP-MS for separation and analysis of dissolved silver and silver nanoparticles in antibacterial gel extracts

Silver nanoparticles (Ag NPs) are extensively used in various applications, but their reactivity leads to oxidative dissolution into Ag(I). When dealing with real samples involving Ag NPs, it is inevitable to encounter situations where both Ag NPs and Ag(I) coexist. Single particle-inductively coupled plasma mass spectrometry (SP-ICP-MS) is a valuable technique for nanoparticle size characterization. However, the presence of coexisting dissolved ions strongly interferes with the accuracy of particle size analysis using SP-ICP-MS. Therefore, it is crucial to develop a reliable separation analysis method to accurately measure both Ag NPs and Ag(I).In this study, we synthesized a silver ion-imprinted magnetic adsorbent with high adsorption capacity (149 mg g-1) and rapid adsorption kinetics (30 min) at both μg L-1 and mg L-1 concentration. The adsorbent selectively adsorbs Ag(I) at pH 7 while hardly adsorbing Ag NPs. It is reusable for more than 5 cycles after regeneration. Using this magnetic adsorbent prior to SP-ICP-MS, we accurately determined the sizes of standard Ag NPs in agreement with the size determined by transmission electron microscopy. The detection limit of particle size and number concentrations of Ag NPs was 12.6 nm and 6.3 × 105 particles L-1. Moreover, we successfully applied the developed method to analyze Ag(I) and Ag NPs in antibacterial gel extracts and validated its accuracy through acid digestion-ICP-MS, TEM, and spiking experiments.Direct SP-ICP-MS analysis in the presence of Ag(I) led to a high baseline, obscuring signals from smaller Ag NPs. Our method of selectively removing Ag(I) substantially improves the accuracy of Ag NPs detection via SP-ICP-MS in the antibacterial gel extracts (e.g. from 48.26 to 35.67 nm). Compared to other approaches used in SP-ICP-MS, our method has a higher adsorption capacity, allowing for better tolerance of coexisting Ag(I).