Core-size regulated aggregation/disaggregation of citrate-coated gold nanoparticles (5–50 nm) and dissolved organic matter: Extinction, emission, and scattering evidence

Abstract

Knowledge of the interactions between gold nanoparticles (GNPs) and dissolved organic matter (DOM) is significant in the development of detection devices for environmental sensing, studies of environmental fate and transport, and advances in antifouling water treatment membranes. The specific objective of this research was to spectroscopically investigate the fundamental interactions between citrate-stabilized gold nanoparticles (CT-GNPs) and DOM. Studies indicated that 30 and 50nm diameter GNPs promoted disaggregation of the DOM. This result—disaggregation of an environmentally important polyelectrolyte—will be quite useful regarding antifouling properties in water treatment and water-based sensing applications. Furthermore, resonance Rayleigh scattering results showed significant enhancement in the UV range which can be useful to characterize DOM and can be exploited as an analytical tool to better sense and improve our comprehension of nanomaterial interactions with environmental systems. CT-GNPs having core size diameters of 5, 10, 30, and 50nm were studied in the absence and presence of added DOM at 2 and 8 ppm at low ionic strength and near neutral pH (6.0–6.5) approximating surface water conditions. Interactions were monitored by cross-interpretation among ultraviolet (UV)-visible extinction spectroscopy, excitation-emission matrix (EEM) spectroscopy (emission and Rayleigh scattering), and dynamic light scattering (DLS). This comprehensive combination of spectroscopic analyses lends new insights into the antifouling behavior of GNPs. The CT-GNP-5 and -10 controls emitted light and aggregated. In contrast, the CT-GNP-30 and CT-GNP-50 controls scattered light intensely, but did not aggregate and did not emit light. The presence of any CT-GNP did not affect the extinction spectra of DOM, and the presence of DOM did not affect the extinction spectra of the CT-GNPs. The emission spectra (visible range) differed only slightly between calculated and actual mixtures of CT-GNP-5 or -10 with DOM, whereas emissions for mixtures of CT-GNP-30 or -50 with DOM were enhanced at the surface plasmon resonance (SPR) wavelength. The emission spectra (ultraviolet range) for protein-like constituents of DOM were quenched. Resonance Rayleigh scattering (RRS) was more intense for the CT-GNP-30 and -50 than for the CT-GNP-5 and -10 controls. Intensity-based DLS particle size distributions (PSDs) of DOM controls, CT-GNP-5 and -10nm controls, and 5- and 10nm GNP-DOM mixtures exhibited multimodal aggregation. Analyses of CT-GNP-5 and CT-GNP-10nm mixtures with DOM indicated overcoating of DOM molecules occurred in close proximity (<10nm) to GNPs, whereas similar overcoating was not supported for the CT-GNP-30 or -50 mixtures with DOM. These fundamental observations can be exploited to improve our comprehension of nanomaterial interactions with environmental systems.