Kim R. Rogers

Analysis of engineered nanomaterials in complex matrices (environment and biota): general considerations and conceptual case studies.

Advances in the study of the environmental fate, transport, and ecotoxicological effects of engineered nanomaterials (ENMs) have been hampered by a lack of adequate techniques for the detection and quantification of ENMs at environmentally relevant concentrations in complex media. Analysis of ENMs differs from traditional chemical analysis because both chemical and physical forms must be considered. Because ENMs are present as colloidal systems, their physicochemical properties are dependent on their surroundings. Therefore, the simple act of trying to isolate, observe, and quantify ENMs may change their physicochemical properties, making analysis extremely susceptible to artifacts. Many analytical techniques applied in materials science and other chemical/biological/physical disciplines may be applied to ENM analysis as well; however, environmental and biological studies may require that methods be adapted to work at low concentrations in complex matrices. The most pressing research needs are the development of techniques for extraction, cleanup, separation, and sample storage that introduce minimal artifacts to increase the speed, sensitivity, and specificity of analytical techniques, as well as the development of techniques that can differentiate between abundant, naturally occurring particles, and manufactured nanoparticles.

Biosensors for direct determination of organophosphate pesticides.

Direct, selective, rapid and simple determination of organophosphate pesticides has been achieved by integrating organophosphorus hydrolase with electrochemical and opitical transducers. Organophosphorus hydrolase catalyzes the hydrolysis of a wide range of organophosphate compounds, releasing an acid and an alcohol that can be detected directly. This article reviews development, characterization and applications of organophosphorus hydrolase-based potentiometric, amperometric and optical biosensors.

Biosensors for environmental applications

Abstract The high cost and slow turnaround times typically associated with the measurement of regulated pollutants clearly indicates a need for environmental screening and monitoring methods which are fast, portable, and cost-effective. To meet this need, a variety of field analytical methods have been introduced, a number of which are commercially available or under development. Because of their unique characteristics, however, technologies such as biosensors might be exploited to fill specific niche applications in the environmental monitoring area. Although the potential environmental market is large, there are a number of technical and commercial obstacles which must be addressed before biosensors or other field analytical technologies have a significant impact on environmental monitoring. Some of these obstacles include the large number of potential pollutants and broad range of their chemical classes; the broad range and complexity of environmental matrices; the variety of possible co-contaminants; the wide dynamic range of pollutant concentrations; lack of well-established data quality expectations by potential users; lack of sufficient markets for specific applications; and regulatory acceptance requirements. This paper will focus primarily on challenges and possible opportunities for the development of biosensors for environmental monitoring applications.

A review of environmental applications of bioluminescence measurements

This review of the recent literature on environmental applications of bioluminescence systems will focus on in vivo and in vitro bioluminescence methods that have been utilized to elucidate properties of chemicals, toxic and mutagenic effects, and to estimate biomass. The unifying theme was the applications of bioluminescence to environmental monitoring, remedial investigations, toxicity assessments, and field methods. In addition to standard analytical laboratory methods and emerging field methods used for environmental monitoring, there currently exist a need for rapid and cost-effective methods to determine toxicity and bioavailability of pollutants in contaminated environmental samples. The U. S. Environmental Protection Agency (EPA) has continuing interest in innovative technologies for environmental monitoring applications such as those provided by bioluminescence methods.

Differential Gene Expression in Daphnia magna Suggests Distinct Modes of Action and Bioavailability for ZnO Nanoparticles and Zn Ions

Zinc oxide nanoparticles (ZnO NPs) are being rapidly developed for use in consumer products, wastewater treatment, and chemotherapy providing several possible routes for ZnO NP exposure to humans and aquatic organisms. Recent studies have shown that ZnO NPs undergo rapid dissolution to Zn(2+), but the relative contribution of Zn(2+) to ZnO NP bioavailability and toxicity is not clear. We show that a fraction of the ZnO NPs in suspension dissolves, and this fraction cannot account for the toxicity of the ZnO NP suspensions to Daphnia magna. Gene expression profiling of D. magna exposed to ZnO NPs or ZnSO(4) at sublethal concentrations revealed distinct modes of toxicity. There was also little overlap in gene expression between ZnO NPs and SiO(x) NPs, suggesting specificity for the ZnO NP expression profile. ZnO NPs effected expression of genes involved in cytoskeletal transport, cellular respiration, and reproduction. A specific pattern of differential expression of three biomarker genes including a multicystatin, ferritin, and C1q containing gene were confirmed for ZnO NP exposure and provide a suite of biomarkers for identifying environmental exposure to ZnO NPs and differentiating between NP and ionic exposure.

Toxicogenomic responses of nanotoxicity in Daphnia magna exposed to silver nitrate and coated silver nanoparticles.

Applications for silver nanomaterials in consumer products are rapidly expanding, creating an urgent need for toxicological examination of the exposure potential and ecological effects of silver nanoparticles (AgNPs). The integration of genomic techniques into environmental toxicology has presented new avenues to develop exposure biomarkers and investigate the mode of toxicity of novel chemicals. In the present study we used a 15k oligonucleotide microarray for Daphnia magna, a freshwater crustacean and common indicator species for toxicity, to differentiate between particle specific and ionic silver toxicity and to develop exposure biomarkers for citrate-coated and PVP-coated AgNPs. Gene expression profiles revealed that AgNO(3) and AgNPs have distinct expression profiles suggesting different modes of toxicity. Major biological processes disrupted by the AgNPs include protein metabolism and signal transduction. In contrast, AgNO(3) caused a downregulation of developmental processes, particularly in sensory development. Metal responsive and DNA damage repair genes were induced by the PVP AgNPs, but not the other treatments. In addition, two specific biomarkers were developed for the environmental detection of PVP AgNPs; although further verification under different environmental conditions is needed.

Principles of affinity-based biosensors.

Despite the amount of resources that have been invested by national and international academic, government, and commercial sectors to develop affinity-based biosensor products, little obvious success has been realized through commercialization of these devices for specific applications (such as the enzyme biosensors for blood glucose analysis). Nevertheless, the fastest growing area in the biosensors research literature continues to involve advances in affinity-based biosensors and biosensor-related methods. Numerous biosensor techniques have been reported that allow researchers to better study the kinetics, structure, and (solid/liquid) interface phenomena associated with protein-ligand binding interactions. In addition, potential application areas for which affinity-based biosensor techniques show promise include clinical/diagnostics, food processing, military/antiterrorism, and environmental monitoring. The design and structural features of these devices—composed of a biological affinity element interfaced to a signal transducer—primarily determine their operational characteristics. This paper although not intended as a comprehensive review, will outline the principles of affinity biosensors with respect to potential application areas.

Release of Silver from Nanotechnology-Based Consumer Products for Children

We assessed the potential for childrens exposure to bioavailable silver during the realistic use of selected nanotechnology-based consumer products (plush toy, fabric products, breast milk storage bags, sippy cups, cleaning products, humidifiers, and humidifier accessory). We measured the release of ionic and particulate silver from products into water, orange juice, milk formula, synthetic saliva, sweat, and urine (1:50 product to liquid mass ratio); into air; and onto dermal wipes. Of the liquid media, sweat and urine yielded the highest amount of silver release, up to 38% of the silver mass in products; tap water yielded the lowest amount, ≤1.5%. Leaching from a blanket into sweat plateaued within 5 min, with less silver released after washing. Between 0.3 and 23 μg m(-2) of silver transferred from products to wipes. Aerosol concentrations were not significantly elevated during product use. Fabrics, a plush toy, and cleaning products were most likely to release silver. Silver leached mainly via dissolution and was facilitated in media with high salt concentrations. Levels of silver to which children may potentially be exposed during the normal use of these consumer products is predicted to be low, and bioavailable silver is expected to be in ionic rather than particulate form.

Changes in silver nanoparticles exposed to human synthetic stomach fluid: Effects of particle size and surface chemistry

The significant rise in consumer products and applications utilizing the antibacterial properties of silver nanoparticles (AgNPs) has increased the possibility of human exposure. The mobility and bioavailability of AgNPs through the ingestion pathway will depend, in part, on properties such as particle size and the surface chemistries that will influence their physical and chemical reactivities during transit through the gastrointestinal tract. This study investigates the interactions between synthetic stomach fluid and AgNPs of different sizes and with different capping agents. Changes in morphology, size and chemical composition were determined during a 30 min exposure to synthetic human stomach fluid (SSF) using Absorbance Spectroscopy, High Resolution Transmission Electron and Scanning Electron Microscopy (TEM/SEM), Dynamic Light Scattering (DLS), and Nanoparticle Tracking Analysis (NTA). AgNPs exposed to SSF were found to aggregate significantly and also released ionic silver which physically associated with the particle aggregates as silver chloride. Generally, the smaller sized AgNPs (<10nm) showed higher rates of aggregation and physical transformation than larger particles (75 nm). Polyvinylpyrrolidone (pvp)-stabilized AgNPs prepared in house behaved differently in SSF than particles obtained from a commercial source despite having similar surface coating and size distribution characteristics.

Organophosphorus Hydrolase‐Based Assay for Organophosphate Pesticides

We report a rapid and versatile organophosphorus hydrolase (OPH) ‐based method for measurement of organophosphates. This assay is based on a substrate‐dependent change in pH at the local vicinity of the enzyme. The pH change is monitored using fluorescein isothiocyanate (FITC), which is covalently immobilized to the enzyme. This method employs the use of poly(methyl methacrylate) beads to which the FITC‐labeled enzyme is adsorbed. Analytes were then measured using a microbead fluorescence analyzer. The dynamic concentration range for the assay extends from 25 to 400 μM for paraoxon with a detection limit of 8 μM. Organophosphorus insecticides measured using this technique included ethylparathion, methylparathion, dursban, fensulfothion, crotoxyphos, diazinon, mevinphos, dichlorvos, and coumaphos. This technique was used to measure coumaphos in biodegradation samples of cattle dip wastes and showed a high correlation (r2 = 0.998) to an HPLC method.