An in-depth multi-omics analysis in RLE-6TN rat alveolar epithelial cells allows for nanomaterial categorization.

BACKGROUND: Nanomaterials (NMs) can be fine-tuned in their properties resulting in a high number of variants, each requiring a thorough safety assessment. Grouping and categorization approaches that would reduce the amount of testing are in principle existing for NMs but are still mostly conceptual. One drawback is the limited mechanistic understanding of NM toxicity. Thus, we conducted a multi-omics in vitro study in RLE-6TN rat alveolar epithelial cells involving 12 NMs covering different materials and including a systematic variation of particle size, surface charge and hydrophobicity for SiO2 NMs. Cellular responses were analyzed by global proteomics, targeted metabolomics and SH2 profiling. Results were integrated using Weighted Gene Correlation Network Analysis (WGCNA). RESULTS: Cluster analyses involving all data sets separated Graphene Oxide, TiO2_NM105, SiO2_40 and Phthalocyanine Blue from the other NMs as their cellular responses showed a high degree of similarities, although apical in vivo results may differ. SiO2_7 behaved differently but still induced significant changes. In contrast, the remaining NMs were more similar to untreated controls. WGCNA revealed correlations of specific physico-chemical properties such as agglomerate size and redox potential to cellular responses. A key driver analysis could identify biomolecules being highly correlated to the observed effects, which might be representative biomarker candidates. Key drivers in our study were mainly related to oxidative stress responses and apoptosis. CONCLUSIONS: Our multi-omics approach involving proteomics, metabolomics and SH2 profiling proved useful to obtain insights into NMs Mode of Actions. Integrating results allowed for a more robust NM categorization. Moreover, key physico-chemical properties strongly correlating with NM toxicity were identified. Finally, we suggest several key drivers of toxicity that bear the potential to improve future testing and assessment approaches.

The role of black carbon as a catalyst for environmental redox transformation.

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983-6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC--graphite, activated carbon, and diesel soot--to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H(2)S. All three types of BC enhanced DNT and DBP reduction. H(2)S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.

Comparison of epitaxial graphene on Si-face and C-face 4H SiC formed by ultrahigh vacuum and RF furnace production.

We present X-ray photoelectron spectroscopy, van der Pauw Hall mobilities, low-temperature far-infrared magneto transmission (FIR-MT), and atomic force microscopy (AFM) results from graphene films produced by radiative heating in an ultrahigh vacuum (UHV) chamber or produced by radio frequency (RF) furnace annealing in a high vacuum chemical vapor deposition system on Si- and C-face 4H SiC substrates at 1200-1600 degrees C. Although the vacuum level and heating methods are different, graphene films produced by the two methods are chemically similar with the RF furnace annealing typically producing thicker graphene films than UHV. We observe, however, that the formation of graphene on the two faces is different with the thicker graphene films on the C-face RF samples having higher mobility. The FIR-MT showed a 0(-1) --> 1(0) Landau level transition with a square root B dependence and a line width consistent with a Dirac fermion with a mobility >250,000 cm(2) x V(-1) x s(-1) at 4.2 K in a C-face RF sample having a Hall-effect carrier mobility of 425 cm(2) x V(-1) x s(-1) at 300 K. AFM shows that graphene grows continuously over the varying morphology of both Si and C-face substrates.

Thermal conductivity and thermal rectification in graphene nanoribbons: a molecular dynamics study.

We have used molecular dynamics to calculate the thermal conductivity of symmetric and asymmetric graphene nanoribbons (GNRs) of several nanometers in size (up to approximately 4 nm wide and approximately 10 nm long). For symmetric nanoribbons, the calculated thermal conductivity (e.g., approximately 2000 W/m-K at 400 K for a 1.5 nm x 5.7 nm zigzag GNR) is on the similar order of magnitude of the experimentally measured value for graphene. We have investigated the effects of edge chirality and found that nanoribbons with zigzag edges have appreciably larger thermal conductivity than nanoribbons with armchair edges. For asymmetric nanoribbons, we have found significant thermal rectification. Among various triangularly shaped GNRs we investigated, the GNR with armchair bottom edge and a vertex angle of 30 degrees gives the maximal thermal rectification. We also studied the effect of defects and found that vacancies and edge roughness in the nanoribbons can significantly decrease the thermal conductivity. However, substantial thermal rectification is observed even in the presence of edge roughness.

Electromechanical properties of suspended graphene nanoribbons.

Graphene nanoribbons present diverse electronic properties ranging from semiconducting to half-metallic, depending on their geometry, dimensions, and chemical composition. Here we present a route to control these properties via externally applied mechanical deformations. Using state-of-the-art density functional theory calculations combined with classical elasticity theory considerations, we find a remarkable Young's modulus value of approximately 7 TPa for ultranarrow graphene strips and a pronounced electromechanical response toward bending and torsional deformations. Given the current advances in the synthesis of nanoscale graphene derivatives, our predictions can be experimentally verified opening the way to the design and fabrication of miniature electromechanical sensors and devices based on ultranarrow graphene nanoribbons.

Electronic structure of few-layer epitaxial graphene on Ru(0001).

The electronic structure of epitaxial monolayer, bilayer, and trilayer graphene on Ru(0001) was determined by selected-area angle-resolved photoelectron spectroscopy (micro-ARPES). Micro-ARPES band maps provide evidence for a strong electronic coupling between monolayer graphene and the adjacent metal, which causes the complete disruption of the graphene pi-bands near the Fermi energy. However, the perturbation by the metal decreases rapidly with the addition of further graphene sheets, and already an epitaxial graphene bilayer on Ru recovers the characteristic Dirac cones of isolated monolayer graphene. A graphene trilayer on Ru behaves like free-standing bilayer graphene. Density-functional theory based calculations show that this decoupling is due to the efficient passivation of metal d-states by the interfacial graphene layer.

Chemically induced mobility gaps in graphene nanoribbons: a route for upscaling device performances.

We report a first-principles based study of mesoscopic quantum transport in chemically doped graphene nanoribbons with a width up to 10 nm. The occurrence of quasi-bound states related to boron impurities results in mobility gaps as large as 1 eV, driven by strong electron-hole asymmetrical backscattering phenomena. This phenomenon opens new ways to overcome current limitations of graphene-based devices through the fabrication of chemically doped graphene nanoribbons with sizes within the reach of conventional lithography.

Genotoxicity of nanomaterials: DNA damage and micronuclei induced by carbon nanotubes and graphite nanofibres in human bronchial epithelial cells in vitro.

Despite the increasing industrial use of different nanomaterials, data on their genotoxicity are scant. In the present study, we examined the potential genotoxic effects of carbon nanotubes (CNTs; >50% single-walled, approximately 40% other CNTs; 1.1 nm x 0.5-100 microm; Sigma-Aldrich) and graphite nanofibres (GNFs; 95%; outer diameter 80-200 nm, inner diameter 30-50 nm, length 5-20 microm; Sigma-Aldrich) in vitro. Genotoxicity was assessed by the single cell gel electrophoresis (comet) assay and the micronucleus assay (cytokinesis-block method) in human bronchial epithelial BEAS 2B cells cultured for 24h, 48h, or 72h with various doses (1-100 microg/cm(2), corresponding to 3.8-380 microg/ml) of the carbon nanomaterials. In the comet assay, CNTs induced a dose-dependent increase in DNA damage at all treatment times, with a statistically significant effect starting at the lowest dose tested. GNFs increased DNA damage at all doses in the 24-h treatment, at two doses (40 and 100 microg/cm(2)) in the 48-h treatment (dose-dependent effect) and at four doses (lowest 10 microg/cm(2)) in the 72-h treatment. In the micronucleus assay, no increase in micronucleated cells was observed with either of the nanomaterials after the 24-h treatment or with CNTs after the 72-h treatment. The 48-h treatment caused a significant increase in micronucleated cells at three doses (lowest 10 microg/cm(2)) of CNTs and at two doses (5 and 10 microg/cm(2)) of GNFs. The 72-h treatment with GNFs increased micronucleated cells at four doses (lowest 10 microg/cm(2)). No dose-dependent effects were seen in the micronucleus assay. The presence of carbon nanomaterial on the microscopic slides disturbed the micronucleus analysis and made it impossible at levels higher than 20 microg/cm(2) of GNFs in the 24-h and 48-h treatments. In conclusion, our results suggest that both CNTs and GNFs are genotoxic in human bronchial epithelial BEAS 2B cells in vitro. This activity may be due to the fibrous nature of these carbon nanomaterials with a possible contribution by catalyst metals present in the materials-Co and Mo in CNTs (<5wt.%) and Fe (<3wt.%) in GNFs.