Silver nanoparticles or free silver ions work? An enantioselective phytotoxicity study with a chiral tool

Nowadays, silver nanoparticles (AgNP) have been widely used and there are raising concerns about their potential adverse effects on organism. As for the exact toxicity mechanism of AgNP, opinions still vary and whether the released silver ions (Ag⁺) or AgNP themselves are responsible for the toxicity remains debatable. In the present study, we have designed two exposure systems where Ag⁺ and AgNP coexisted but differed in quantification by using photo-reduced method with cysteine enantiomers, and their toxicities to freshwater microalgae Scenedesmus obliquus and model plant Arabidopsis thaliana were determined. In the results, Ag⁺ was in suit photo-reduced by cysteine enantiomers, and the UV-Vis and circular dichroism spectrum evidence confirmed the quantification difference between Ag-l-cysteine (Ag-l-Cys) and Ag-d-cysteine (Ag-d-Cys), where there was more AgNP and less Ag⁺ in Ag-l-Cys. Furthermore, the toxicity assay data revealed that Ag-d-Cys was more toxic to S. obliquus but A. thaliana was more susceptible to Ag-l-Cys. The metal element distribution in Arabidopsis leaves was also influenced in an enantioselective manner, which was related to the oxidative stress. Considering the quantification difference between Ag-l-Cys and Ag-d-Cys, it can be concluded that AgNP exhibited their toxicity to S. obliquus by the action of Ag⁺, but toxicity brought to A. thaliana was attributed to AgNP themselves rather than Ag⁺. The results of the present study help to better clarify the role of Ag⁺ in AgNP toxicity and offer a chiral tool and a new sight to investigate the toxicity mechanism of AgNP.