Weathering of a carbon nanotube/epoxy nanocomposite under UV light and in water bath: impact on abraded particles.

Weathering processes can influence the surface properties of composites with incorporated nanoparticles. These changes may affect the release behavior of nanoparticles when an abrasion process is applied. Therefore, the influence of two different weathering processes, immersion in water and exposure to UV light, on the properties of abraded particles from a carbon nanotube (CNT)/epoxy nanocomposite was investigated. The investigation included the measurement of the weathering impact on the surface chemistry of the exposed samples, the particle size of abraded particles, the quantity of exposed CNTs in the respirable part of the abraded particles, and the toxicity of abraded particles, measured by in vitro toxicity tests using the THP-1 monocyte-derived macrophages. The results showed that weathering by immersion in water had no influence on the properties of abraded particles. The exposure to UV light caused a degradation of the epoxy on the surface, followed by delamination of an approx. 2.5 µm thick layer. An increased quantity of exposed CNTs in abraded particles was not found; on the contrary, longer UV exposure times decreased the released fraction of CNTs from 0.6% to 0.4%. The toxicity tests revealed that abraded particles from the nanocomposites did not induce additional acute cytotoxic effects compared to particles from the neat epoxy.

Carbon Nanotubes Released from an Epoxy-Based Nanocomposite: Quantification and Particle Toxicity.

Studies combining both the quantification of free nanoparticle release and the toxicological investigations of the released particles from actual nanoproducts in a real-life exposure scenario are urgently needed, yet very rare. Here, a new measurement method was established to quantify the amount of free-standing and protruding multiwalled carbon nanotubes (MWCNTs) in the respirable fraction of particles abraded from a MWCNT-epoxy nanocomposite. The quantification approach involves the prelabeling of MWCNTs with lead ions, nanocomposite production, abrasion and collection of the inhalable particle fraction, and quantification of free-standing and protruding MWCNTs by measuring the concentration of released lead ions. In vitro toxicity studies for genotoxicity, reactive oxygen species formation, and cell viability were performed using A549 human alveolar epithelial cells and THP-1 monocyte-derived macrophages. The quantification experiment revealed that in the respirable fraction of the abraded particles, approximately 4000 ppm of the MWCNTs were released as exposed MWCNTs (which could contact lung cells upon inhalation) and approximately 40 ppm as free-standing MWCNTs in the worst-case scenario. The release of exposed MWCNTs was lower for nanocomposites containing agglomerated MWCNTs. The toxicity tests revealed that the abraded particles did not induce any acute cytotoxic effects.

Exposure Assessment of a High-energy Tensile Test With Large Carbon Fiber Reinforced Polymer Cables.

This study investigated the particle and fiber release from two carbon fiber reinforced polymer cables that underwent high-energy tensile tests until rupture. The failing event was the source of a large amount of dust whereof a part was suspected to be containing possibly respirable fibers that could cause adverse health effects. The released fibers were suspected to migrate through small openings to the experiment control room and also to an adjacent machine hall where workers were active. To investigate the fiber release and exposure risk of the affected workers, the generated particles were measured with aerosol devices to obtain the particle size and particle concentrations. Furthermore, particles were collected on filter samples to investigate the particle shape and the fiber concentration. Three situations were monitored for the control room and the machine hall: the background concentrations, the impact of the cable failure, and the venting of the exposed rooms afterward. The results showed four important findings: The cable failure caused the release of respirable fibers with diameters below 3 µm and an average length of 13.9 µm; the released particles did migrate to the control room and to the machine hall; the measured peak fiber concentration of 0.76 fibers/cm(3) and the overall fiber concentration of 0.07 fibers/cm(3) in the control room were below the Permissible Exposure Limit (PEL) for fibers without indication of carcinogenicity; and the venting of the rooms was fast and effective. Even though respirable fibers were released, the low fiber concentration and effective venting indicated that the suspected health risks from the experiment on the affected workers was low. However, the effect of long-term exposure is not known therefore additional control measures are recommended.

Co-release of hexabromocyclododecane (HBCD) and Nano- and microparticles from thermal cutting of polystyrene foams.

Polystyrene foam is a very important insulation material, and hexabromocyclododecane (HBCD) is frequently used as its flame retardant. HBCD is persistent, bioaccumulative, and toxic, and therefore workplace exposure and environmental emission should be avoided. In this study, we investigated the co-release of HBCD and aerosol particles during the thermal cutting of expanded polystyrene foam (EPS) and extruded polystyrene foam (XPS). The generated particles were simultaneously measured by a fast mobility particle sizer (FMPS) and collected by a cascade impactor (NanoMoudi). In the breathing zone of a cutting worker, the number concentration of aerosol particles was above 1 × 10(12) particles m(-3), and the air concentration of HBCD was more than 50 µg m(-3). Most of the released HBCD was partitioned into particles with an aerodynamic diameter at the nanometer scale. The average concentrations of HBCD in these submicrometer particles generated from the thermal cutting of EPS and XPS were 13 times and 15 times higher than the concentrations in raw foams, respectively. An occupational exposure assessment indicated that more than 60% of HBCD and 70% of particles deposited in the lung of cutting worker would be allocated to the alveolar region. The potential subchronic (or chronic) toxicity jointly caused by the particles and HBCD calls for future studies.

Site-specific immobilization of enzymes on magnetic nanoparticles and their use in organic synthesis.

Magnetic nanoparticles (MNPs) are attractive materials that serve as a support for enzyme immobilization and facilitate separations by applying an external magnetic field; this could facilitate the recycling of enzymes and broaden their applications in organic synthesis. Herein, we report the methods for the immobilization of water-soluble and membrane-bound enzymes, and the activity difference between free and immobilized enzymes is discussed. Sialyltransferase (PmST1, from Pasteurella multocida ) and cytidine monophosphate (CMP)-sialic acid synthetase (CSS, from Neisseria meningitides ) were chosen as water-soluble enzymes and expressed using an intein expression system. The enzymes were site-specifically and covalently immobilized on PEGylated-N-terminal cysteine MNPs through native chemical ligation (NCL). Increasing the length of the PEG linker between the enzyme and the MNP surface increased the activity of the immobilized enzymes relative to the free parent enzymes. In addition, the use of a fluorescent acceptor tag for PmST1 affected enzyme kinetics. In contrast, sialyltransferase from Neisseria gonorrheae (NgST, a membrane-bound enzyme) was modified with a biotin-labeled cysteine at the C-terminus using NCL, and the enzyme was then assembled on streptavidin-functionalized MNPs. Using a streptavidin-biotin interaction, it was possible to immobilize NgST on a solid support under mild ligation conditions, which prevented the enzyme from high-temperature decomposition and provided an approximately 2-fold increase in activity compared to other immobilization methods on MNPs. Finally, the ganglioside GM3-derivative (sialyl-lactose derivative) was synthesized in a one-pot system by combining the use of immobilized PmST1 and CSS. The enzymes retained 50% activity after being reused ten times. Furthermore, the results obtained using the one-pot two-immobilized-enzyme system demonstrated that it can be applied to large-scale reactions with acceptable yields and purity. These features make enzyme-immobilized MNPs applicable to organic synthesis.

Synthesis and characterisation of group nine transition metal complexes containing new mesityl and naphthyl based azaindole scorpionate ligands.

Two novel boron-based flexible scorpionate ligands based on 7-azaindole, Li[HB(azaindolyl)(2)(1-naphthyl)] and Li[HB(azaindolyl)(2)(mesityl)] {Li[(Naphth)Bai] and Li[(Mes)Bai] respectively}, have been prepared (mesityl = 2,4,6-trimethylphenyl). These salts have been isolated in two forms, either as dimeric structures which contain bridging hydride interactions with the lithium centres or as crystalline material containing mono nuclear bis-acetonitrile solvates. The newly formed ligands have been utilised to prepare a range of group nine transition metal complexes with the general formula [M(COD){κ(3)-NNH-HB (azaindolyl)(2)(Ar)}] (where M = rhodium, iridium; Ar = 1-naphthyl, mesityl; COD = 1,5-cyclooctadiene) and [Rh(NBD){κ(3)-NNH-HB (azaindolyl)(2)(Ar)}] (where NBD = 2,5-norbornadiene; Ar = 1-naphthyl, mesityl). These new complexes have been compared to the previously reported compounds which contain the related scorpionate ligands Li[HB(azaindolyl)(2)(phenyl)] and K[HB(azaindolyl)(3)] {Li[(Ph)Bai] and K[Tai] respectively}. Structural characterisation of the complexes [Rh(COD){κ(3)-NNH-HB (azaindolyl)(2)(mesityl)}], [Ir(COD){κ(3)-NNH-HB (azaindolyl)(2)(mesityl)}] and [Rh(NBD){κ(3)-NNH-HB (azaindolyl)(2)(naphthyl)}] confirm the expected κ(3)-NNH coordination mode for these new ligands. Spectroscopic analysis suggests strong interactions of the B-H functional group with the metal centres in all cases.

Double addition of H2 to transition metal-borane complexes: a 'hydride shuttle' process between boron and transition metal centres.

The addition of H(2) across a transition metal-borane bond is reported for the first time providing a mechanism for recharging borane functional groups to borohydride.

Rhodium and iridium complexes containing diphenyl-2-(3-methyl)indolylphosphine: synthesis, structure and application in the catalytic transfer hydrogenation of ketones.

The synthesis and characterisation of a number of group nine complexes containing the recently reported ligand, diphenyl-2-(3-methyl)indolylphosphine, is presented herein. The complexes [RhCl(COD){PPh(2)(C(9)H(8)N)}] (1), [IrCl(COD){PPh(2)(C(9)H(8)N)}] (2), [RhCl(NBD){PPh(2)(C(9)H(8)N)}] (3) and [Rh(COD)(MeCN){PPh(2)(C(9)H(8)N)}]BF(4) (4) (where COD = 1,5-cyclooctadiene, NBD = 2,5- norbornadiene) have been structurally characterised by X-ray crystallography. The complex [Rh(2)(COD)(2){N(Me)[double bond, length as m-dash]C(H)Ph)}{PPh(2)(C(9)H(8)N)}][BF(4)](2) (8) was also isolated and structurally characterised. Complex 8 contains a '[Rh(COD)]' fragment coordinated to the aromatic ring of the indolyl group, providing the first example of a eta(6) coordination mode for this ligand. The synthesised complexes were investigated for their activity in the catalytic transfer hydrogenation of ketones and found to be moderately active catalysts.