James E. Hutchison

Greener nanoscience: a proactive approach to advancing applications and reducing implications of nanotechnology.

Nanotechnology continues to offer new materials and applications that will benefit society, yet there is growing concern about the potential health and environmental impacts of production and use of nanoscale products. Although hundreds of studies of nanomaterial hazards have been reported, due (largely) to the complexity of the nanomaterials, there is no consensus about the impact these hazards will have. This Focus describes the need for a research agenda that addresses these nanomaterial complexities through coordinated research on the applications and implications of new materials, wherein nanomaterials scientists play a central role as we move from understanding to minimizing nanomaterial hazards. Greener nanoscience is presented as an approach to determining and implementing the design rules for safer nanomaterials and safer, more efficient processes.

Generation of Metal Nanoparticles from Silver and Copper Objects: Nanoparticle Dynamics on Surfaces and Potential Sources of Nanoparticles in the Environment

The use of silver nanoparticles (AgNPs) in antimicrobial applications, including a wide range of consumer goods and apparel, has attracted attention because of the unknown health and environmental risks associated with these emerging materials. Of particular concern is whether there are new risks that are a direct consequence of their nanoscale size. Identifying those risks associated with nanoscale structure has been difficult due to the fundamental challenge of detecting and monitoring nanoparticles in products or the environment. Here, we introduce a new strategy to directly monitor nanoparticles and their transformations under a variety of environmental conditions. These studies reveal unprecedented dynamic behavior of AgNPs on surfaces. Most notably, under ambient conditions at relative humidities greater than 50%, new silver nanoparticles form in the vicinity of the parent particles. This humidity-dependent formation of new particles was broadly observed for a variety of AgNPs and substrate surface coatings. We hypothesize that nanoparticle production occurs through a process involving three stages: (i) oxidation and dissolution of silver from the surface of the particle, (ii) diffusion of silver ion across the surface in an adsorbed water layer, and (iii) formation of new, smaller particles by chemical and/or photoreduction. Guided by these findings, we investigated non-nanoscale sources of silver such as wire, jewelry, and eating utensils that are placed in contact with surfaces and found that they also formed new nanoparticles. Copper objects display similar reactivity, suggesting that this phenomenon may be more general. These findings challenge conventional thinking about nanoparticle reactivity and imply that the production of new nanoparticles is an intrinsic property of the material that is not strongly size dependent. The discovery that AgNPs and CuNPs are generated spontaneously from manmade objects implies that humans have long been in direct contact with these nanomaterials and that macroscale objects represent a potential source of incidental nanoparticles in the environment.

Interactions between natural organic matter and gold nanoparticles stabilized with different organic capping agents.

The adsorption of natural organic matter (NOM) to the surfaces of natural colloids and engineered nanoparticles is known to strongly influence, and in some cases control, their surface properties and aggregation behavior. As a result, the understanding of nanoparticle fate, transport, and toxicity in natural systems must include a fundamental framework for predicting such behavior. Using a suite of gold nanoparticles (AuNPs) with different capping agents, the impact of surface functionality, presence of natural organic matter, and aqueous chemical composition (pH, ionic strength, and background electrolytes) on the surface charge and colloidal stability of each AuNP type was investigated. Capping agents used in this study were as follows: anionic (citrate and tannic acid), neutral (2,2,2-[mercaptoethoxy(ethoxy)]ethanol and polyvinylpyrrolidone), and cationic (mercaptopentyl(trimethylammonium)). Each AuNP type appeared to adsorb Suwannee River Humic Acid (SRHA) as evidenced by measurable decreases in zeta potential in the presence of 5 mg C L(-1) SRHA. It was found that 5 mg C L(-1) SRHA provided a stabilizing effect at low ionic strength and in the presence of only monovalent ions while elevated concentrations of divalent cations lead to enhanced aggregation. The colloidal stability of the NPs in the absence of NOM is a function of capping agent, pH, ionic strength, and electrolyte valence. In the presence of NOM at the conditions examined in this study, the capping agent is a less important determinant of stability, and the adsorption of NOM is a controlling factor.

Systematic Evaluation of Nanomaterial Toxicity: Utility of Standardized Materials and Rapid Assays

The challenge of optimizing both performance and safety in nanomaterials hinges on our ability to resolve which structural features lead to desired properties. It has been difficult to draw meaningful conclusions about biological impacts from many studies of nanomaterials due to the lack of nanomaterial characterization, unknown purity, and/or alteration of the nanomaterials by the biological environment. To investigate the relative influence of core size, surface chemistry, and charge on nanomaterial toxicity, we tested the biological response of whole animals exposed to a matrix of nine structurally diverse, precision-engineered gold nanoparticles (AuNPs) of high purity and known composition. Members of the matrix include three core sizes and four unique surface coatings that include positively and negatively charged headgroups. Mortality, malformations, uptake, and elimination of AuNPs were all dependent on these parameters, showing the need for tightly controlled experimental design and nanomaterial characterization. Results presented herein illustrate the value of an integrated approach to identify design rules that minimize potential hazard.

The Nanomaterial Characterization Bottleneck

The future of nanotechnology rests upon approaches to making new, useful nanomaterials and testing them in complex systems. Currently, the advance from discovery to application is constrained in nanomaterials relative to a mature market, as seen in molecular and bulk matter. To reap the benefits of nanotechnology, improvements in characterization are needed to increase throughput as creativity outpaces our ability to confirm results. The considerations of research, commerce, and regulation are part of a larger feedback loop that illustrates a mutual need for rapid, easy, and standardized characterization of a large property matrix. Now, we have an opportunity and a need to strike a new balance that drives higher quality research, simplifies commercial exploitation, and allows reasoned regulatory approaches.

Persistent Adult Zebrafish Behavioral Deficits Results from Acute Embryonic Exposure to Gold Nanoparticles

As the number of products containing nanomaterials increase, human exposure to nanoparticles (NPs) is unavoidable. Presently, few studies focus on the potential long-term consequences of developmental NP exposure. In this study, zebrafish embryos were acutely exposed to three gold NPs that possess functional groups with differing surface charge. Embryos were exposed to 50 μg/mL of 1.5 nm gold nanoparticles (AuNPs) possessing negatively charged 2-mercaptoethanesulfonic acid (MES) or neutral 2-(2-(2-mercaptoethoxy)ethoxy)ethanol (MEEE) ligands or 10 μg/mL of the AuNPs possessing positively charged trimethylammoniumethanethiol (TMAT). Both MES- and TMAT-AuNP exposed embryos exhibited hypo-locomotor activity, while those exposed to MEEE-AuNPs did not. A subset of embryos that were exposed to 1.5 nm MES- and TMAT-AuNPs during development from 6 to 120 h post fertilization was raised to adulthood. Behavioral abnormalities and the number of survivors into adulthood were evaluated at 122 days post fertilization. We found that both treatments induced abnormal startle behavior following a tap stimulus. However, the MES-AuNPs exposed group also exhibited abnormal adult behavior in the light and had a lower survivorship into adulthood. This study demonstrates that acute, developmental exposure to 1.5 nm MES- and TMAT-AuNPs, two NPs differing only in the functional group, affects larval behavior, with behavioral effects persisting into adulthood.

In vivo biodistribution and toxicity depends on nanomaterial composition, size, surface functionalisation and route of exposure

Anticipated growth of the nanotechnology industry has motivated the development of rapid, relevant and efficient testing strategies to evaluate the biological activity and toxic potential of the growing number of novel nanoparticles. Since nanoparticles may interact with biological systems in unforeseen ways, it is important that evaluation of nanomaterial–biological interactions cover a broad range of cell types, tissues, organs and systems. Here, we use the embryonic zebrafish as a dynamic whole animal (in vivo) assay to investigate the importance of chemical composition, size, surface functionalisation and route of exposure on nanomaterial–biological interactions and delineate nanomaterials that are biologically active from those that are not. Information gained using model systems, such as the embryonic zebrafish, can be used to direct the rational development of safer, less hazardous nanoparticles. Our results demonstrate the utility of this model as an effective and accurate tool to assess the biological activity and toxic potential of nanomaterials in a short period of time with minimal cost.

Interdigitated array electrode as an alternative to the rotated ring-disk electrode for determination of the reaction products of dioxygen reduction.

Electrochemical reduction of dioxygen in aqueous media can proceed to water, hydrogen peroxide, or a mixture of the two. The production of hydrogen peroxide, classically established with the rotated ring-disk electrode, can also be quantitatively assessed at interdigitated array (IDA) electrodes, where dioxygen is reduced at the set of microband generator electrodes and any H(2)O(2) produced is detected by its oxidation (back to O(2)) at the interdigitated set of microband collector electrodes. The sensitivity of the IDA for H(2)O(2) detection is higher owing to its more complete collection, and to the ensuing regeneration of O(2), which leads to an amplification of the generator currents. The production of H(2)O(2) is thus reflected both in the ratio of collector and generator electrode currents [the collection efficiency, coll(τ)] and in the ratio of the generator current with the collector potential on to that with it off [amplification factor, ampl(τ)]. The necessary theory for interpretation of the fraction ε of H(2)O(2) produced per dioxygen reduced is presented, based on conformal mapping techniques. Explicit equations are derived for ε at long times that are independent of the IDA dimensions and that can be used with any two-product electrochemical reaction analogous to the dioxygen reduction. Experimental data are presented for dioxygen reduction in acidic and basic media to illustrate application of the theory.

Malonamide-Functionalized Gold Nanoparticles for Selective, Colorimetric Sensing of Trivalent Lanthanide Ions

A selective and sensitive molecular sensor for trivalent lanthanide (Ln(3+)) ions based upon a malonamide-functionalized gold nanoparticle was developed for colorimetric detection in water. A new synthetic approach permits nanoparticle synthesis, stabilization, and incorporation of a selective lanthanide binding site in a single, direct step. The design incorporates a specifically tailored dual function precursor ligand that bears a sodium thiosulfate (Bunte salt) group that links to the gold nanoparticle core and a tetramethylmalonamide (TMMA) group that serves as a selective Ln(3+) binding site. The sensors colorimetric response to lanthanide ions is immediate, and it is sensitive down to approximately 50 nM for Eu(3+) and Sm(3+). This study demonstrates a general strategy for direct, convenient nanoparticle synthesis that enables the incorporation of analyte binding groups directly to the nanoparticle surface, allowing colorimetric sensors to be developed for widespread use. The one-step synthesis offers uniform surface ligand composition, reduces the volume of waste generated during nanoparticle synthesis and purification, produces functionalized gold nanoparticles that are stable in nonmodified aqueous environments, and offers colorimetric detection at ambient temperature.

Selective Growth of Vertical ZnO Nanowire Arrays Using Chemically Anchored Gold Nanoparticles

A selective growth method for ZnO vertical nanowire arrays is demonstrated using self-assembled gold nanoparticles as the growth catalyst. Gold nanoparticles functionalized with bifunctional (thiol-phosphonic acid) ligands assemble rapidly and selectively onto a patterned ZnO seed layer. Vertical ZnO nanowire arrays are grown by the vapor-liquid-solid (VLS) deposition method from the ZnO seed layer through the catalytic effect of the bound gold nanoparticles. This synthesis method offers a number of advantages for producing ZnO nanowires because it permits selective placement through directed self-assembly of gold nanoparticles, enables rapid growth, eliminates vacuum deposition processing, and minimizes the amount of gold waste when compared to traditional methods that require vapor deposition of gold films.