Background Multi-walled carbon nanotubes (MWCNT) have received attention due to extraordinary properties, resulting in concerns for occupational health and safety. Costs and ethical concerns of animal testing drive a need for in vitro models with predictive power in respiratory toxicity. The aim of this study was to assess pro-inflammatory response (Interleukin-8 expression, IL-8) and genotoxicity (DNA strand breaks) caused by MWCNT with different physicochemical properties in different pulmonary cell models and correlate these to previously published in vivo data. Seven MWCNT were selected; two long/thick (NRCWE-006/Mitsui-7 and NM-401), two short/thin (NM-400 and NM-403), a pristine (NRCWE-040) and two surface modified; hydroxylated (NRCWE-041) and carboxylated (NRCWE-042). Carbon black Printex90 (CB) was included as benchmark material. Human alveolar epithelial cells (A549) and monocyte-derived macrophages (THP-1a) were exposed to nanomaterials (NM) in submerged conditions, and two materials (NM-400 and NM-401) in co-cultures of A549/THP-1a and lung fibroblasts (WI-38) in an air-liquid interface (ALI) system. Effective doses were quantified by thermo-gravimetric-mass spectrometry analysis (TGA-MS). To compare genotoxicity in vitro and in vivo, we developed a scoring system based on a categorization of effects into standard deviation (SD) units (< 1, 1, 2, 3 or 4 standard deviation increases) for the increasing genotoxicity. Results Effective doses were shown to be 25 to 53%, and 21 to 57% of the doses administered to A549 and THP-1a, respectively. In submerged conditions (A549 and THP-1a cells), all NM induced dose-dependent IL-8 expression. NM-401 and NRCWE-006 caused the strongest pro-inflammatory response. In the ALI-exposed co-culture, only NM-401 caused increased IL-8 expression, and no DNA strand breaks were observed. Strong correlations were found between in vitro and in vivo inflammation when doses were normalized by surface area (also proxy for diameter and length). Significantly increased DNA damage was found for all MWCNT in THP-1a cells, and for short MWCNT in A549 cells. A concordance in genotoxicity of 83% was obtained between THP-1a cells and broncho-alveolar lavaged (BAL) cells. Conclusion This study shows correlations of pro-inflammatory potential in A549 and THP-1a cells with neutrophil influx in mice, and concordance in genotoxic response between THP-1a cells and BAL cells, for seven MWCNT.
Pulmonary exposure to micro- and nanoscaled particles has been widely linked to adverse health effects and high concentrations of respirable particles are expected to occur within and around many industrial settings. In this study, a field-measurement campaign was performed at an industrial manufacturer, during the production of paints. Spatial and personal measurements were conducted and results were used to estimate the mass flows in the facility and the airborne particle release to the outdoor environment. Airborne particle number concentration (1 × 103–1.0 × 104 cm−3), respirable mass (0.06–0.6 mg m−3), and PM10 (0.3–6.5 mg m−3) were measured during pouring activities. In overall; emissions from pouring activities were found to be dominated by coarser particles >300 nm. Even though the raw materials were not identified as nanomaterials by the manufacturers, handling of TiO2 and clays resulted in release of nanometric particles to both workplace air and outdoor environment, which was confirmed by TEM analysis of indoor and stack emission samples. During the measurement period, none of the existing exposure limits in force were exceeded. Particle release to the outdoor environment varied from 6 to 20 g ton−1 at concentrations between 0.6 and 9.7 mg m−3 of total suspended dust depending on the powder. The estimated release of TiO2 to outdoors was 0.9 kg per year. Particle release to the environment is not expected to cause any major impact due to atmospheric dilution
Manufactured nanomaterials (MNMs) often have a surface-chemical modification in order to tailor their physicochemical properties, including also powder properties and miscibility. Surface-chemical modifications may influence the toxicological properties of the MNM, but the specific chemistry and extent are rarely described in detail in suppliers’ technical data sheets. Chemical and quantitative information on any surface-chemical treatment, coating and functionalization are required for chemicals registration in Europe. Currently there is no globally accepted and documented approach to generate such data. Consequently, there is a continued research need to establish a structured approach to identify and quantify surface-chemical modifications. Here we present a tiered approach starting with screening for mass-loss during heating in a furnace or thermogravimetric analysis (TGA) followed by solvent extraction, and analysis by several mass spectrometry (MS) techniques depending on the target analytes. Thermal treatment was assumed to be able to quantify the amount of organic coating and MS was used to identify the extractable organic coatings after pressurized liquid extraction (PLE) using methanol at 200 °C. Volatile organic compounds in extracts were identified with gas chromatography and MS (GC-MS), non-volatile organic compounds with liquid chromatography MS (LC-MS), and polymeric compounds with matrix-assisted laser desorption ionization time-of-flight MS (MALDI-TOF-MS). The approach was demonstrated by analysis of 24 MNM, comprising titanium dioxide, synthetic amorphous silica, graphite, zinc oxide, silver, calcium carbonate, iron oxide, nickel-zinc-iron oxide, and organoclay. In extracts of 14 MNMs a range of organic compounds were identified and the main groups were silanes/siloxanes, fatty acids, fatty acid esters, quaternary ammonium compounds and polymeric compounds. In the remaining 10 MNMs no organic compounds were detected by MS, despite the fact an organic coating was indicated by TGA.
Graphene‐derived materials are attractive components in conductive inks for printed and flexible electronics. Here, the authors report a facile and scalable synthesis of mildly oxidized graphite and its formulation into screen‐printable inks. The screen‐printed electrodes exhibit sheet‐resistance below 1 Ω/sq after rolling‐compression, with a compressed film thickness of ≈3 μm and line‐width resolution below 100 μm. The method, described herein, can be used without the need for substrate‐limiting post‐printing treatments, such as high‐temperature annealing, photonic annealing, or chemical reduction. The approach is applicable to any arbitrary and heat‐sensitive substrate, including plastic and paper, and is both highly cost‐effective and suitable for roll‐to‐roll printing of a wide range of devices.
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