Leanne M. Gilbertson

Shape-Dependent Surface Reactivity and Antimicrobial Activity of Nano-Cupric Oxide

Shape of engineered nanomaterials (ENMs) can be used as a design handle to achieve controlled manipulation of physicochemical properties. This tailored material property approach necessitates the establishment of relationships between specific ENM properties that result from such manipulations (e.g., surface area, reactivity, or charge) and the observed trend in behavior, from both a functional performance and hazard perspective. In this study, these structure-property-function (SPF) and structure-property-hazard (SPH) relationships are established for nano-cupric oxide (n-CuO) as a function of shape, including nanospheres and nanosheets. In addition to comparing these shapes at the nanoscale, bulk CuO is studied to compare across length scales. The results from comprehensive material characterization revealed correlations between CuO surface reactivity and bacterial toxicity with CuO nanosheets having the highest surface reactivity, electrochemical activity, and antimicrobial activity. While less active than the nanosheets, CuO nanoparticles (sphere-like shape) demonstrated enhanced reactivity compared to the bulk CuO. This is in agreement with previous studies investigating differences across length-scales. To elucidate the underlying mechanisms of action to further explain the shape-dependent behavior, kinetic models applied to the toxicity data. In addition to revealing different CuO material kinetics, trends in observed response cannot be explained by surface area alone. The compiled results contribute to further elucidate pathways toward controlled design of ENMs.

Life Cycle Impacts and Benefits of a Carbon Nanotube-Enabled Chemical Gas Sensor

As for any emerging technology, it is critical to assess potential life cycle impacts prior to widespread adoption to prevent future unintended consequences. The subject of this life cycle study is a carbon nanotube-enabled chemical gas sensor, which is a highly complex, low nanomaterial-concentration application with the potential to impart significant human health benefits upon implementation. Thus, the net lifecycle trade-offs are quantified using an impact-benefit ratio (IBR) approach proposed herein, where an IBR < 1 indicates that the downstream benefits outweigh the upstream impacts. The cradle-to-gate assessment results indicate that the midpoint impacts associated with producing CNTs are marginal compared with those associated with the other manufacturing stages. The cumulative upstream impacts are further aggregated to units of disability-adjusted life years (DALYs) using ReCiPe end point analysis method and quantitatively compared with the potential downstream DALY benefits, as lives saved, during the use phase. The approach presented in this study provides a guiding framework and quantitative method intended to encourage the development of nanoenabled products that have the potential to realize a net environmental, health, or societal benefit.

Life Cycle Payback Estimates of Nanosilver Enabled Textiles under Different Silver Loading, Release, And Laundering Scenarios Informed by Literature Review.

Silver was utilized throughout history to prevent the growth of bacteria in food and wounds. Recently, nanoscale silver has been applied to consumer textiles (nAg-textiles) to eliminate the prevalence of odor-causing bacteria. In turn, it is proposed that consumers will launder these items less frequently thus, reducing the life cycle impacts. While previous studies report that laundering processes are associated with the greatest environmental impacts of these textiles, there is no data available to support the proposed shift in consumer laundering behavior. Here, the results from a comprehensive literature review of nAg-textile life cycle studies are used to inform a cradle-to-grave life cycle impact assessment. Rather than assuming shifts in consumer behavior, the impact assessment is conducted in such a way that considers all laundering scenarios to elucidate the potential for reduced laundering to enable realization of a net life cycle benefit. In addition to identifying the most impactful stages of the life cycle across nine-midpoint categories, a payback period and uncertainty analysis quantifies the reduction in lifetime launderings required to recover the impacts associated with nanoenabling the textile. Reduction of nAg-textile life cycle impacts is not straightforward and depends on the impact category considered.

Toward Tailored Functional Design of Multi-Walled Carbon Nanotubes (MWNTs): Electrochemical and Antimicrobial Activity Enhancement via Oxidation and Selective Reduction

Multiwalled carbon nanotubes (MWNTs) are utilized in a number of sectors as a result of their favorable electronic properties. In addition, MWNT antimicrobial properties can be exploited or considered a potential liability depending on their intended application and handling. The ability to tailor electrochemical and antimicrobial properties using economical and conventional treatment processes introduces the potential to significantly enhance product performance. Oxygen functional groups are known to influence several MWNT properties, including redox activity. Here, MWNTs were functionalized with oxygen groups using standard acid treatments followed by selective reduction via annealing. Chemical derivatization coupled to X-ray photoelectron spectroscopy was utilized to quantify specific surface oxygen group concentration after variable treatment conditions, which were then correlated to observed trends in electrochemical and antimicrobial activities. These activities were evaluated as the potential for MWNTs to participate in the oxygen reduction reaction and to have the ability to promote the oxidation of glutathione. The compiled results strongly suggest that the reduction of surface carboxyl groups and the redox activity of carbonyl groups promote enhanced MWNT reactivity and elucidate the opportunity to design functional MWNTs for enhanced performance in their intended electrochemical or antimicrobial application.

Coordinating modeling and experimental research of engineered nanomaterials to improve life cycle assessment studies

Life cycle assessment (LCA) – a comprehensive modeling framework used to identify environmental and human health impacts associated with products, processes, and technologies – is increasingly recommended for emerging nanotechnologies. LCA applied prospectively can guide design decisions and enable reduction of future impacts. A growing literature describes the potential for LCA to inform development of safer nanotechnologies, for example by identifying the manufacturing inputs or processes with the greatest potential for improvement. However, few published studies to date include all life cycle stages in part because of uncertainty regarding engineered nanomaterial (ENM) releases and impacts, which precludes comprehensive environmental assessment of nano-enabled products. Life cycle impact assessment (LCIA) converts emissions into environmental damages through linked fate-exposure-effect models that require robust experimental data and a mechanistic understanding for each of these components. In the case of ENMs, there are pertinent knowledge gaps, high uncertainties in experimental data, and disagreement regarding the suitability of existing fate, exposure, and effect models. This frontier review summarizes recent advances in human and aquatic ecotoxicity LCIA for ENMs and calls for greater coordination between LCA modelers and experimentalists, including those that study fate and transport, environmental transformations, occupational exposure, and toxicology, to inform responsible development of nanotechnology, enabling ENMs to reach their full potential.

Toward safer multi-walled carbon nanotube design: Establishing a statistical model that relates surface charge and embryonic zebrafish mortality

Abstract Given the increased utility and lack of consensus regarding carbon nanotube (CNT) environmental and human health hazards, there is a growing demand for guidelines that inform safer CNT design. In this study, the zebrafish (Danio rerio) model is utilized as a stable, sensitive biological system to evaluate the bioactivity of systematically modified and comprehensively characterized multi-walled carbon nanotubes (MWNTs). MWNTs were treated with strong acid to introduce oxygen functional groups, which were then systematically thermally reduced and removed using an inert temperature treatment. While 25 phenotypic endpoints were evaluated at 24 and 120 hours post-fertilization (hpf), high mortality at 24 hpf prevented further resolution of the mode of toxicity leading to mortality. Advanced multivariate statistical methods are employed to establish a model that identifies those MWNT physicochemical properties that best estimate the probability of observing an adverse outcome. The physicochemical properties considered in this study include surface charge, percent surface oxygen, dispersed aggregate size and morphology and electrochemical activity. Of the five physicochemical properties, surface charge, quantified as the point of zero charge (PZC), was determined as the best predictor of mortality at 24 hpf. From a design perspective, the identification of this property–hazard relationship establishes a foundation for the development of design guidelines for MWNTs with reduced hazard.

Highly Conductive Single-Walled Carbon Nanotube Thin Film Preparation by Direct Alignment on Substrates from Water Dispersions

A safe, scalable method for producing highly conductive aligned films of single-walled carbon nanotubes (SWNTs) from water suspensions is presented. While microfluidic assembly of SWNTs has received significant attention, achieving desirable SWNT dispersion and morphology in fluids without an insulating surfactant or toxic superacid is challenging. We present a method that uniquely produces a noncorrosive ink that can be directly applied to a device in situ, which is different from previous fabrication techniques. Functionalized SWNTs (f-SWNTs) are dispersed in an aqueous urea solution to leverage binding between the amine group of urea and the carboxylic acid group of f-SWNTs and obtain urea-SWNT. Compared with SWNTs dispersed using conventional methods (e.g., superacid and surfactants), the dispersed urea-SWNT aggregates have a higher aspect ratio with a rodlike morphology as measured by light scattering. The Mayer rod technique is used to prepare urea-SWNT, highly aligned films (two-dimensional nematic order parameter of 0.6, 5 μm spot size, via polarized Raman) with resistance values as low as 15-1700 Ω/sq in a transmittance range of 2-80% at 550 nm. These values compete with the best literature values for conductivity of SWNT-enabled thin films. The findings offer promising opportunities for industrial applications relying on highly conductive thin SWNT films.

Informing rational design of graphene oxide through surface chemistry manipulations: properties governing electrochemical and biological activities

It is increasingly realized that rational design is critical to advance potential applications and proactively preclude adverse consequences of carbon nanomaterials (CNMs). Central to this approach is the establishment of parametric relationships that correlate material properties to both their functional performance and inherent hazard. This work aims to decouple the causative mechanisms of material structure and surface chemistry as it relates to the electrochemical and biological activities of graphene oxide (GO). The results are evaluated in the context of established relationships between surface chemistry and oxygen functionalized multi-walled carbon nanotubes (O-MWCNTs), a carbon allotrope. Systematic manipulation of GO surface chemistry is achieved through thermal annealing (under inert conditions, 200–900 °C). To further elucidate the contribution of several properties, chemical reduction was also used as an approach to differentially modify the surface chemistry. Physicochemical properties of GO and reduced GO (rGO) samples were comprehensively characterized using multiple techniques (AFM, TGA, XPS, ATR-FTIR, Raman, and DLS). The results indicate that surface chemistry is a viable design handle to control both activities. Rather than a single direct property (i.e., relative presence of carbonyl-containing moieties), it is a balance of multiple consequential properties, (extent of dispersion, defect density, and electrical conductivity) in combination with the relative presence of carbonyl moieties that synergistically contribute to electrochemical and biological activities. The identification of these governing physicochemical properties aims to inform the establishment of design parameters to guide the rational and safe design of CNMs.

A framework for sustainable nanomaterial selection and design based on performance, hazard, and economic considerations

Engineered nanomaterials (ENMs) and ENM-enabled products have emerged as potentially high-performance replacements to conventional materials and chemicals. As such, there is an urgent need to incorporate environmental and human health objectives into ENM selection and design processes. Here, an adapted framework based on the Ashby material selection strategy is presented as an enhanced selection and design process, which includes functional performance as well as environmental and human health considerations. The utility of this framework is demonstrated through two case studies, the design and selection of antimicrobial substances and conductive polymers, including ENMs, ENM-enabled products and their alternatives. Further, these case studies consider both the comparative efficacy and impacts at two scales: (i) a broad scale, where chemical/material classes are readily compared for primary decision-making, and (ii) within a chemical/material class, where physicochemical properties are manipulated to tailor the desired performance and environmental impact profile. Development and implementation of this framework can inform decision-making for the implementation of ENMs to facilitate promising applications and prevent unintended consequences.An adapted framework based on the Ashby material selection strategy can be used to select nanomaterials based on their functional performance and on their environmental and human health considerations.

Opportunities to advance sustainable design of nano-enabled agriculture identified through a literature review

The application of nanotechnology in agriculture and food systems is a new and rapidly evolving area of research with the potential to positively impact an industry that is experiencing increased demand under increasingly stressed resources. Given the intimate relationship between agriculture, the environment, and human health, a proactive approach to design is critical – one that is informed by considering the trade-offs between potential benefits realized by nano-enabling and potential adverse impacts imposed by their use. This tutorial review includes an overview of current and proposed nano-enabled applications that are unique to agriculture and food systems to identify, (i) the function provided and proposed benefits realized through nano-enabling, (ii) the efficiency of (nano)material use, and (iii) the proposed mechanism through which the ‘nano’ component of the design operates. It is through this review that three primary suggestions emerge, offering guidance for ongoing studies to inform design for enhanced agriculture sustainability: the need for (i) comprehensive data reporting, including material flows (input, emissions, and retention in the environment or product) of the engineered nanomaterials or active ingredient used, (ii) experimental design that includes non-nano controls, and (iii) identification and discussion of mechanisms underlying how the ‘nano’ aspect of the design enables the observed outcome. In addition to overarching guidance for continued research to inform design for enhanced agriculture sustainability, suggestions unique to each reviewed product class are also provided.