Department of Civil and Environmental Engineering and Geodetic Science, The Ohio State University, Columbus, Ohio 43210, USA.
Langmuir. 2012 Jan 17;28(2):1095-104. doi: 10.1021/la202328n. Epub 2011 Dec 22.
Determining the fate of manufactured nanomaterials in the environment is contingent upon understanding how stabilizing agents influence the stability of nanoparticles in aqueous systems. In this study, the aggregation and dissolution tendencies of uncoated silver nanoparticles and the same particles coated with three common coating agents, trisodium citrate, sodium dodecyl sulfate (SDS), and Tween 80 (Tween), were evaluated. Early stage aggregation kinetics of the uncoated and coated silver nanoparticles were assessed by dynamic light scattering over a range of electrolyte types (NaCl, NaNO(3), and CaCl(2)) and concentrations that span those observed in natural waters. Although particle dissolution was observed, aggregation of all particle types was still consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The aggregation of citrate-coated particles and SDS-coated particles were very similar to that for the uncoated particles, as the critical coagulation concentrations (CCC) of the particles in different electrolytes were all approximately the same (40 mM NaCl, 30 mM NaNO(3), and 2 mM CaCl(2)). The Tween-stabilized particles were significantly more stable than the other particles, however, and in NaNO(3) aggregation was not observed up to an electrolyte concentration of 1 M. Differences in the rate of aggregation under diffusion-limited aggregation conditions at high electrolyte concentrations for the SDS and Tween-coated particles, in combination with the moderation of their electrophoretic mobilities, suggest SDS and Tween imparted steric interactions to the particles. The dissolution of the silver nanoparticles was inhibited by the SDS and Tween coatings, but not by the citrate coating, and in chloride-containing electrolytes a secondary precipitate of AgCl was observed bridging the individual particles. These results indicate that coating agents could significant influence the fate of silver nanoparticles in aquatic systems, and in some cases these stabilizers may completely prevent particle aggregation.
确定制造的纳米材料在环境中的命运取决于了解稳定剂如何影响纳米粒子在水系统中的稳定性。在这项研究中,评估了未涂层的银纳米粒子和用三种常见涂层剂(柠檬酸钠、十二烷基硫酸钠(SDS)和吐温 80(Tween))涂覆的相同粒子的聚集和溶解趋势。通过动态光散射在一系列电解质类型(NaCl、NaNO(3)和 CaCl(2))和浓度范围内评估了未涂层和涂层银纳米粒子的早期聚集动力学,这些浓度范围涵盖了天然水中观察到的浓度。尽管观察到了颗粒溶解,但所有颗粒类型的聚集仍然符合经典的德加古因-朗道-维尔韦尔-奥弗贝克(DLVO)理论。柠檬酸钠涂层颗粒和 SDS 涂层颗粒的聚集与未涂层颗粒非常相似,因为不同电解质中颗粒的临界聚沉浓度(CCC)大致相同(40mMNaCl、30mMNaNO(3)和 2mM CaCl(2))。然而,Tween 稳定的颗粒明显更稳定,在 1M 的电解质浓度下,在高电解质浓度下在扩散限制聚集条件下的聚集速率没有观察到。SDS 和 Tween 涂层颗粒在高电解质浓度下扩散限制聚集条件下聚集速率的差异,以及它们电泳迁移率的缓和,表明 SDS 和 Tween 赋予了颗粒位阻相互作用。SDS 和 Tween 涂层抑制了银纳米粒子的溶解,但柠檬酸钠涂层没有抑制,在含氯电解质中观察到 AgCl 的二次沉淀桥接了各个颗粒。这些结果表明,涂层剂可能会显著影响银纳米粒子在水系统中的命运,在某些情况下,这些稳定剂可能会完全阻止颗粒聚集。