Smit A. Shah

Determination of uptake, accumulation, and stress effects in corn (Zea mays L.) grown in single-wall carbon nanotube contaminated soil

Single-wall carbon nanotubes (SWNTs) are projected to increase in usage across many industries. Two studies were conducted using Zea L. (corn) seeds exposed to SWNT spiked soil for 40 d. In Study 1, corn was exposed to various SWNT concentrations (0, 10, and 100 mg/kg) with different functionalities (non-functionalized, OH-functionalized, or surfactant stabilized). A microwave induced heating method was used to determine SWNTs accumulated mostly in roots (0-24 μg/g), with minimal accumulation in stems and leaves (2-10 μg/g) with a limit of detection at 0.1 μg/g. Uptake was not functional group dependent. In Study 2, corn was exposed to 10 mg/kg SWNTs (non-functionalized or COOH-functionalized) under optimally grown or water deficit conditions. Plant physiological stress was determined by the measurement of photosynthetic rate throughout Study 2. No significant differences were seen between control and SWNT treatments. Considering the amount of SWNTs accumulated in corn roots, further studies are needed to address the potential for SWNTs to enter root crop species (i.e., carrots), which could present a significant pathway for human dietary exposure.

Bioaccumulation, stress, and swimming impairment in Daphnia magna exposed to multiwalled carbon nanotubes, graphene, and graphene oxide

The use of carbon-based nanomaterials (CNMs) such as multiwalled carbon nanotubes (MWCNTs), graphene, and graphene oxide (GO) is increasing across many applications because of their unique and versatile properties. These CNMs may enter the aquatic environment through many pathways, creating the potential for organism exposure. The present study addresses the bioaccumulation and toxicity seen in Daphnia magna exposed to CNMs dispersed in sodium dodecyl benzene sulfonate (SDBS). In study I, D. magna were exposed to varying outer diameters of MWCNTs for 24 h in moderately hard or hard freshwater. Bioaccumulation of MWCNT was found in all treatments, with the highest concentrations (0.53 ± 0.27 μg/g) in D. magna exposed in hard freshwater (p < 0.005). The median lethal concentration (LC50) was determined for D. magna exposed to CNMs in moderately hard and hard freshwater. In study II, D. magna were exposed to CNMs for 72 h in moderately hard freshwater to assess swimming velocity and generation of reactive oxygen species (ROS) detected by dichlorofluorescein fluorescence. An overall decrease was seen in D. magna swimming velocity after exposure to CNMs. The generation of ROS was significantly higher (1.54 ± 0.38 dichlorofluorescein mM/mg dry wt) in D. magna exposed to MWCNTs of smaller outer diameters than in controls after 72 h (p < 0.05). These results suggest that further investigation of CNM toxicity and behavior in the aquatic environment is needed. Environ Toxicol Chem 2017;36:2199-2204.

Electrochemical etching of Ti2AlC to Ti2CTx (MXene) in low-concentration hydrochloric acid solution

In this study, we successfully demonstrate the electrochemical etching of Al from porous Ti2AlC electrodes in dilute hydrochloric acid to form a layer of Ti2CTx MXene on Ti2AlC. This is the first report on etching of the A layer from the MAX phase in a fluoride-free solution as a less hazardous method to process and handle MXenes. In addition, these MXenes possess only –Cl terminal groups, as well as the common ones, such as –O and –OH. However, electrochemical etching can also result in subsequent over-etching of parent MAX phases to carbide-derived carbon (CDC). We propose a core–shell model to explain electrochemical etching of Ti2AlC to Ti2CTx and CDC. The proposed model suggests that a careful balance in etching parameters is needed to produce MXenes while avoiding over-etching. Our electrochemical approach expands the possible range of both etching techniques and resulting MXene compositions.

Aqueous Exfoliation of Graphite into Graphene Assisted by Sulfonyl Graphene Quantum Dots for Photonic Crystal Applications

We investigate the π-π stacking of polyaromatic hydrocarbons (PAHs) with graphene surfaces, showing that such interactions are general across a wide range of PAH sizes and species, including graphene quantum dots. We synthesized a series of graphene quantum dots with sulfonyl, amino, and carboxylic functional groups and employed them to exfoliate and disperse pristine graphene in water. We observed that sulfonyl-functionalized graphene quantum dots were able to stabilize the highest concentration of graphene in comparison to other functional groups; this is consistent with prior findings by pyrene. The graphene nanosheets prepared showed excellent colloidal stability, indicating great potential for applications in electronics, solar cells, and photonic displays which was demonstrated in this work.

Surface-agnostic highly stretchable and bendable conductive MXene multilayers

Bendable, stretchable MXene multilayer coatings are deposited onto a wide variety of surfaces, rendering them conductive and responsive. Stretchable, bendable, and foldable conductive coatings are crucial for wearable electronics and biometric sensors. These coatings should maintain functionality while simultaneously interfacing with different types of surfaces undergoing mechanical deformation. MXene sheets as conductive two-dimensional nanomaterials are promising for this purpose, but it is still extremely difficult to form surface-agnostic MXene coatings that can withstand extreme mechanical deformation. We report on conductive and conformal MXene multilayer coatings that can undergo large-scale mechanical deformation while maintaining a conductivity as high as 2000 S/m. MXene multilayers are successfully deposited onto flexible polymer sheets, stretchable poly(dimethylsiloxane), nylon fiber, glass, and silicon. The coating shows a recoverable resistance response to bending (up to 2.5-mm bending radius) and stretching (up to 40% tensile strain), which was leveraged for detecting human motion and topographical scanning. We anticipate that this discovery will allow for the implementation of MXene-based coatings onto mechanically deformable objects.

Graphene reflux: improving the yield of liquid-exfoliated nanosheets through repeated separation techniques

Scalable production of graphene through liquid-phase exfoliation has been plagued by low yields. Although several recent studies have attempted to improve graphene exfoliation technology, the problem of separating colloidal nanosheets from unexfoliated parent material has received far less attention. Here we demonstrate a scalable method for improving nanosheet yield through a facile washing process. By probing the sedimentation of liquid-phase exfoliated slurries of graphene nanosheets and parent material, we found that a portion of exfoliated graphene is entrapped in the sediment, but can be recovered by repeatedly washing the slurry of nanosheet and parent material with additional solvent. We found this process to significantly increase the overall yield of graphene (graphene/parent material) and recover a roughly constant proportion of graphene with each wash. The cumulative amount of graphene recovered is only a function of total solvent volume. Moreover, we found this technique to be applicable to other types of nanosheets such as boron nitride nanosheets.

High-yield scalable graphene nanosheet production from compressed graphite using electrochemical exfoliation

Electrochemical exfoliation is a promising bulk method for producing graphene from graphite; in this method, an applied voltage drives ionic species to intercalate into graphite where they form gaseous species that expand and exfoliate individual graphene sheets. However, a number of obstacles have prevented this approach from becoming a feasible production route; the disintegration of the graphite electrode as the method progresses is the chief difficulty. Here we show that if graphite powders are contained and compressed within a permeable and expandable containment system, the graphite powders can be continuously intercalated, expanded, and exfoliated to produce graphene. Our data indicate both high yield (65%) and extraordinarily large lateral size (>30 μm) in the as-produced graphene. We also show that this process is scalable and that graphene yield efficiency depends solely on reactor geometry, graphite compression, and electrolyte transport.

Tailored Network Formation in Graphene Oxide Gels

Graphene oxide (GO)-based gels are attractive because of their ability to retain individual nanosheet properties in a three-dimensional (3D) bulk material. The final morphology and properties of these 3D gel networks depend strongly on the type and density of cross-links, and these gels can be dried and annealed to form aerogels with both high conductivity (560 S/m) and high surface area (1700 m2/g). The results show that both ammonia content and the parent nanosheet morphology (crumpled vs flat) have a strong influence on the cross-linked structure and composition; notably, nitrogen is found in the gels, suggesting that ammonia actively participates in the reaction rather than as a mere catalyst. The GO nanosheet morphology may be altered using spray-drying to obtain crumpled GO (cGO) nanosheets and form cGO gels; this allows for an additional handle in the creation of GO-based gels with tunable density, electrical conductivity, and surface area.

Trophic Transfer and Accumulation of Multiwalled Carbon Nanotubes in the Presence of Copper Ions in Daphnia magna and Fathead Minnow (Pimephales promelas)

The increase in use of nanomaterials such as multiwalled carbon nanotubes (MWCNTs) presents a need to study their interactions with the environment. Trophic transfer was measured between Daphnia magna and Pimephales promelas (fathead minnow, FHM) exposed to MWCNTs with different outer diameter (OD) sizes (MWCNT1 = 8-15 nm OD and MWCNT2 = 20-30 nm OD) in the presence and absence of copper. Pristine FHM were fed D. magna, previously exposed for 3 d to MWCNT1 or MWCNT2 (0.1 mg/L) and copper (0.01 mg/L), for 7 d. D. magna bioaccumulated less MWCNT1 (0.02 μg/g) than MWCNT2 (0.06 μg/g), whereas FHM accumulated more MWCNT1 (0.81 μg/g) than MWCNT2 (0.04 μg/g). In the presence of copper, MWCNT bioaccumulation showed an opposite trend. Mostly MWCNT1 (0.03 μg/g) bioaccumulated in D. magna, however less MWCNT1 (0.21 μg/g) than MWCNT2 (0.32 μg/g) bioaccumulated in FHM. Bioaccumulation factors were higher for MWCNT1s than MWCNT2. However, an opposite trend was observed when copper was added. Plasma metallothionein-2 was measured among treatments; however concentrations were not statistically different from the control. This study demonstrates that trophic transfer of MWCNTs is possible in the aquatic environment and further exploration with mixtures can strengthen the understanding of MWCNT environmental behavior.