Huiyuan Guo

Analysis of Silver Nanoparticles in Antimicrobial Products Using Surface-Enhanced Raman Spectroscopy (SERS)

Silver nanoparticles (AgNPs) are the most commonly used nanoparticles in consumer products. Concerns over human exposure to and risk from these particles have resulted in increased interest in novel strategies to detect AgNPs. This study investigated the feasibility of surface-enhanced Raman spectroscopy (SERS) as a method for the detection and quantification of AgNPs in antimicrobial products. By using ferbam (ferric dimethyl-dithiocarbamate) as an indicator molecule that binds strongly onto the nanoparticles, AgNPs detection and discrimination were achieved based on the signature SERS response of AgNPs-ferbam complexes. SERS response with ferbam was distinct for silver ions, silver chloride, silver bulk particles, and AgNPs. Two types of AgNPs with different coatings, citrate and polyvinylpirrolidone (PVP), both showed strong interactions with ferbam and induced strong SERS signals. SERS was effectively applicable for detecting Ag particles ranging from 20 to 200 nm, with the highest signal intensity in the 60-100 nm range. A linear relationship (R(2) = 0.9804) between Raman intensity and citrate-AgNPs concentrations (60 nm; 0-20 mg/L) indicates the potential for particle quantification. We also evaluated SERS detection of AgNPs in four commercially available antimicrobial products. Combined with ICP-MS and TEM data, the results indicated that the SERS response is primarily dependent on size, but also affected by AgNPs concentration. The findings demonstrate that SERS is a promising analytical platform for studying environmentally relevant levels of AgNPs in consumer products and related matrices.

Surface-enhanced Raman scattering detection of silver nanoparticles in environmental and biological samples.

Growing concerns over the potential release and threat of silver nanoparticles (AgNPs) to environmental and biological systems urge researchers to investigate their fate and behavior. However, current analytical techniques cannot meet the requirements for rapidly, sensitively and reliably probing AgNPs in complex matrices. Surface-enhanced Raman spectroscopy (SERS) has shown great capability for rapid detection of AgNPs based on an indicator molecule that can bind on the AgNP surface. The objective of this study was to exploit SERS to detect AgNPs in environmental and biological samples through optimizing the Raman indicator for SERS. Seven indicator molecules were selected and determined to obtain their SERS signals at optimal concentrations. Among them, 1,2-di(4-pyridyl)ethylene (BPE), crystal violet and ferric dimethyl-dithiocarbamate (ferbam) produced the highest SERS intensities. Further experiments on binding competition between each two of the three candidates showed that ferbam had the highest AgNPs-binding ability. The underlying mechanism lies in the strong binding affinity of ferbam with AgNPs via multiple sulfur atoms. We further validated ferbam to be an effective indicator for SERS detection of as low as 0.1mg/L AgNPs in genuine surface water and 0.57 mg/L in spinach juice. Moreover, limited interference on SERS detection of AgNPs was found from environmentally relevant inorganic ions, organic matter, inorganic particles, as well as biologically relevant components, demonstrating the ferbam-assisted SERS is an effective and sensitive method to detect AgNPs in complex environmental and biological samples.

Development of a filter-based method for detecting silver nanoparticles and their heteroaggregation in aqueous environments by surface-enhanced Raman spectroscopy

The rising application of silver nanoparticles (AgNPs) and subsequent release into aquatic systems have generated public concerns over their potential risk and harm to aquatic organisms and human health. Effective and practical analytical methods for AgNPs are urgently needed for their risk assessment. In this study we established an innovative approach to detect trace levels of AgNPs in environmental water through integrating a filtration technique into surface-enhanced Raman spectroscopy (SERS) and compared it with previously established centrifuge-based method. The purpose of filtration was to trap and enrich salt-aggregated AgNPs from water samples onto the filter membrane, through which indicator was then passed and complexed with AgNPs. The enhanced SERS signals of indicator could reflect the presence and quantity of AgNPs in the samples. The most favorable benefit of filtration is being able to process large volume samples, which is more practical for water samples, and greatly improves the sensitivity of AgNP detection. In this study, we tested 20 mL AgNPs-containing samples and the filter-based method is able to detect AgNPs as low as 5 μg/L, which is 20 folds lower than the centrifuge-based method. In addition, the speed and precision of the detection were greatly improved. This approach was used to detect trace levels of AgNPs in real environmental water successfully. Meanwhile, the heteroaggregation of AgNPs with minerals in water was reliably monitored by the new method. Overall, a combination of the filtration-SERS approach provides a rapid, simple, and sensitive way to detect AgNPs and analyze their environmental behavior.

Applications of surface-enhanced Raman spectroscopy in the analysis of nanoparticles in the environment

The rise of nanotechnology has introduced a large number of nano-enabled consumer products into the market. Stakeholders either interested in or concerned about the applications of nanoparticles (NPs) have questions on their exposure pathways, behavior and fate in the environment. Currently, detection and analysis of NPs in complex environmental samples are difficult and challenging. This review summarizes the emerging attempts to use surface-enhanced Raman spectroscopy (SERS) as a valuable tool for NP analysis. The critical factors influencing the feasibility of SERS for NP analysis are the material type, individual size, primary shape, surface chemistry and spatial arrangement of NPs. Current SERS methods for the identification, characterization and potential quantification of NPs are summarized and compared, with key limitations and issues recognized. Further, SERS applications in investigating the environmental behavior and fate of NPs are discussed. Probing and monitoring NPs using SERS yields important insights into the roles that NPs play in the environment. By studying the potential of SERS to detect NPs and track their environmental behavior and fate, environmental scientists are able to achieve an in-depth understanding of the benefits and risks of NPs. Also, knowledge from SERS can guide the nanotechnology research community to develop and apply NPs in a safe and effective manner. With an outlook on the key challenges and potential solutions in the end, this review is expected to appeal to a broad audience in the fields of nanotechnology, interfacial chemistry, analytical chemistry, soil science, environmental science, food science, and nanotoxicology.

Bioaccessibility and exposure assessment of trace metals from urban airborne particulate matter (PM10 and PM2.5) in simulated digestive fluid

We describe a batch-extraction with simulated digestive fluid (salivary fluid, gastric fluid and intestinal fluid) to estimate the bioaccessibility of inhaled trace metals (TMs) in particulate matter less than 10 and 2.5 μm in aerodynamic diameter (PM10 and PM2.5). Concentrations of the assayed TMs (As, Cd, Cr, Ni, Mn, Cu, Zn, Sb, Hg and Pb) were determined in PM10 and PM2.5 samples by inductively coupled plasma-mass spectrometry. The TMs with the largest soluble fractions for airborne PM collected from winter and summer in saliva were Mn and Sb, respectively; in seasons this became Co in gastric fluid and Cu in intestinal fluid. Clearly, bioaccessibility is strongly dependent on particle size, the component of simulated digestive fluids (e.g., pH, digestive enzymes pepsin and trypsin), and the chemical properties of metal ions. The particle size and seasonal variation affected the inhaled bioaccessible fraction of PM-bound TMs during mucociliary clearance, which transported PM from the tracheal and the bronchial region to the digestive system. This study provides direct evidence for TMs in airborne PM being bioaccessible TMs are likely to possess an enhanced digestive toxic potential due to airborne PM pollution.

Surface-Enhanced Raman Spectroscopy: A Tool for All Classes of Food Contaminants

Our food system is vulnerable and can be contaminated intentionally and unintentionally by microbes, chemicals, and engineered nanomaterials. Early-on detection of these contaminants in the food supply chain is critically important to keep our food safe. Surface-enhanced Raman spectroscopy (SERS) is, perhaps, the only technique that has been explored for detecting all three classes of contaminants that cannot be optically seen. In this short article, we will briefly summarize the current status of SERS in studying each of the three classes of contaminants, and the research challenges and opportunities.