The impact of capping agents and environmental conditions (pH, ionic strength, and background electrolytes) on surface charge and aggregation potential of silver nanoparticles (AgNPs) suspensions were investigated. Capping agents are chemicals used in the synthesis of nanoparticles to prevent aggregation. The AgNPs examined in the study were as follows: (a) uncoated AgNPs (H(2)-AgNPs), (b) electrostatically stabilized (citrate and NaBH(4)-AgNPs), (c) sterically stabilized (polyvinylpyrrolidone (PVP)-AgNPs), and (d) electrosterically stabilized (branched polyethyleneimine (BPEI)-AgNPs)). The uncoated (H(2)-AgNPs), the citrate, and NaBH(4)-coated AgNPs aggregated at higher ionic strengths (100 mM NaNO(3)) and/or acidic pH (3.0). For these three nanomaterials, chloride (Cl(-), 10 mM), as a background electrolyte, resulted in a minimal change in the hydrodynamic diameter even at low pH (3.0). This was limited by the presence of residual silver ions, which resulted in the formation of stable negatively charged AgCl colloids. Furthermore, the presence of Ca(2+) (10 mM) resulted in aggregation of the three previously identified AgNPs regardless of the pH. As for PVP coated AgNPs, the ionic strength, pH and electrolyte type had no impact on the aggregation of the sterically stabilized AgNPs. The surface charge and aggregation of the BPEI coated AgNPs varied according to the solution pH.

As a result of the extensive number of applications of silver nanoparticles (AgNPs), their potential impacts, once released into the environment, are of concern. The toxicity of AgNPs was reported to be dependent on various factors such as particle size, shape and capping agent. Although these factors may play a role in AgNPs toxicity, the results presented herein suggest that surface charge is one of the most important factors that govern the toxicity of AgNPs. In the current study, the toxicity of four AgNPs representing various surface charging scenarios ranging from highly negative to highly positive was investigated. These AgNPs were (1) uncoated H(2)-AgNPs, (2) citrate coated AgNPs (Citrate-AgNPs), (3) polyvinylpyrrolidone coated AgNPs (PVP-AgNPs), and (4) branched polyethyleneimine coated AgNPs (BPEI-AgNPs). Our results clearly demonstrate that the AgNPs exhibited surface charge-dependent toxicity on the bacillus species investigated. Furthermore, ultrafiltration membranes were utilized to purify the AgNPs suspensions from residual impurities prior to the introduction to the microbes. This step was crucial in determining the true AgNPs toxicity and is either missing or not explicitly mentioned in most of the reported toxicity studies.

It is expected that the antibacterial property of bulk silver is carried over and perhaps enhanced, to silver nanoparticles. Therefore, when one examines the environmental issues associated with the manufacture and use of silver nanoparticle-based products, the antibacterial effects should always be taken into account particularly at the different stages of the product lifecycle. Currently, there are two arguments in the scientific literature about the mechanisms of antimicrobial properties of silver nanoparticles as they relate to colloidal silver particles and inonic silver. Methodologies of risk assessment and control have to account for both arguments.