Desorption electrospray ionisation mass spectrometry reveals in situ modification of a hindered amine light stabiliser resulting from direct N–OR bond cleavage

Detection and characterisation of structural modifications of a hindered amine light stabiliser (HALS) directly from a polyester-based coil coating have been achieved by desorption electrospray ionisation mass spectrometry (DESI-MS) for the first time. In situ detection is made possible by exposing the coating to an acetone vapour atmosphere prior to analysis. This is a gentle and non-destructive treatment that allows diffusion of analyte to the surface without promoting lateral migration. Using this approach a major structural modification of the HALS TINUVIN®123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate) was discovered where one N-ether piperidine moiety (N-OC8H17) is converted to a secondary piperidine (N–H). With the use of 2-dimensional DESI-MS imaging the modification was observed to arise during high curing temperatures (ca. 260 °C) and under simulated physiological conditions (80 °C, full solar spectrum). It is proposed that the secondary piperidine derivative is a result of a highly reactive aminyl radical intermediate produced by N–O homolytic bond cleavage. The nature of the bond cleavage is also suggested by ESR spin-trapping experiments employing α-phenyl-N-tert-butyl nitrone (PBN) in toluene at 80 °C. The presence of a secondary piperidine derivative in situ and the implication of N–OR competing with NO–R bond cleavage suggest an alternative pathway for generation of the nitroxyl radical—an essential requirement in anti-oxidant activity that has not previously been described for the N-ether sub-class of HALS.

Antibodies mediate formation of neutrophil extracellular traps in the middle ear and facilitate secondary pneumococcal otitis media

Otitis media (OM) (a middle ear infection) is a common childhood illness that can leave some children with permanent hearing loss. OM can arise following infection with a variety of different pathogens, including a coinfection with influenza A virus (IAV) and Streptococcus pneumoniae (the pneumococcus). We and others have demonstrated that coinfection with IAV facilitates the replication of pneumococci in the middle ear. Specifically, we used a mouse model of OM to show that IAV facilitates the outgrowth of S. pneumoniae in the middle ear by inducing middle ear inflammation. Here, we seek to understand how the host inflammatory response facilitates bacterial outgrowth in the middle ear. Using B cell-deficient infant mice, we show that antibodies play a crucial role in facilitating pneumococcal replication. We subsequently show that this is due to antibody-dependent neutrophil extracellular trap (NET) formation in the middle ear, which, instead of clearing the infection, allows the bacteria to replicate. We further demonstrate the importance of these NETs as a potential therapeutic target through the transtympanic administration of a DNase, which effectively reduces the bacterial load in the middle ear. Taken together, these data provide novel insight into how pneumococci are able to replicate in the middle ear cavity and induce disease.

Painting anatase (TiO2) nanocrystals on long nanofibers to prepare photocatalysts with large active surface for dye degradation and organic synthesis

Anatase TiO2 nanocrystals were painted on H-titanate nanofibers by using an aqueous solution of titanyl sulfate. The anatase nanocrystals were bonded solidly onto the titanate fibers through formation of coherent interfaces at which the oxygen atoms were shared by the nanocrystals and the fiber. This approach allowed us to create large anatase surfaces on the nanofibers, which are active in photocatalytic reactions. This method was also applied successfully to coat anatase nanocrystals on surfaces of fly ash and layered clay. The painted nanofibers exhibited a much higher catalytic activity for the photocatalytic degradation of sulforhodamine B and the selective oxidation of benzylamine to the corresponding imine (with a product selectivity >99%) under UV irradiation than both the parent H-titanate nanofibers and a commercial TiO2 powder, P25. We found that gold nanoparticles supported on H-titanate nanofibers showed no catalytic activity for the reduction of nitrobenzene to azoxybenzene, whereas the gold nanoparticles supported on the painted nanofibers and P25 could efficiently reduce nitrobenzene to azoxybenzene as the sole product under visible light irradiation. These results were different from those from the reduction on the gold nanoparticles photocatalyst on ZrO2, in which the azoxybenzene was the intermediate and converted to azobenzene quickly. Evidently, the support materials significantly affect the product selectivity of the nitrobenzene reduction. Finally, the new photocatalysts could be easily dispersed into and separated from a liquid because of their fibril morphology, which is an important advantage for practical applications.

Oxidation of 4-substituted TEMPO derivatives reveals modifications at the 1-and 4-positions

Potenital pathways for the deactivation of hindered amine light stabilisers (HALS) have been investigated by observing reactions of model compounds-based on 4-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-with hydroxyl radicals. In these reactions, dilute aqueous suspensions of photocatalytic nanoparticulate titanium dioxide were irradiated with UV light in the presence of water-soluble TEMPO derivatives. Electron spin resonance (ESR) and electrospray ionisation mass-spectrometry (ESI-MS) data were acquired to provide complementary structural elucidation of the odd-and even-electron products of these reactions and both techniques show evidence for the formation of 4-oxo-TEMPO (TEMPONE). TEMPONE formation from the 4-substituted TEMPO compounds is proposed to be initiated by hydrogen abstraction at the 4-position by hydroxyl radical. High-level ab initio calculations reveal a thermodynamic preference for abstraction of this hydrogen but computed activation barriers indicate that, although viable, it is less favoured than hydrogen abstraction from elsewhere on the TEMPO scaffold. If a radical is formed at the 4-position however, calculations elucidate two reaction pathways leading to TEMPONE following combination with either a second hydroxyl radical or dioxygen. An alternate mechanism for conversion of TEMPOL to TEMPONE via an alkoxyl radical intermediate is also considered and found to be competitive with the other pathways. ESI-MS analysis also shows an increased abundance of analogous 4-substituted piperidines during the course of irradiation, suggesting competitive modification at the 1-position to produce a secondary amine. This modification is confirmed by characteristic fragmentation patterns of the ionised piperidines obtained by tandem mass spectrometry. The conclusions describe how reaction at the 4-position could be responsible for the gradual depletion of HALS in pigmented surface coatings and secondly, that modification at nitrogen to form the corresponding secondary amine species may play a greater role in the stabilisation mechanisms of HALS than previously considered.

Transfection of MDA-MB-231 human breast carcinoma cells with bone sialoprotein (BSP) stimulates migration and invasion in vitro and growth of primary and secondary tumors in nude mice

We have investigated the role of bone sialoprotein (BSP), a secreted glycoprotein normally found in bone, in breast cancer progression. To explore functions for BSP in human breast cancer invasion and metastasis, the full-length BSP cDNA was transfected into the MDA-MB-231-BAG human breast cancer cell line under the control of the CMV promoter. Clones expressing BSP and vector control clones were isolated. BSP producing clones showed increased monolayer wound healing, a faster rate of stellate outgrowth in Matrigel and increased rate of invasion into a collagen matrix when compared to control clones. Clones were also examined in models of breast cancer growth and metastasis in vivo. BSP transfected clones showed an increased rate of primary tumor growth following mammary fat pad injection of nude mice. BSP transfected clones and vector control clones metastasized to soft organs and bone at a similar rate after intra-cardiac injection as determined by real-time PCR and X-ray analysis. Although these organs were targets for both BSP transfected and non-transfected cells, the size of the metastatic lesion was shown to be significantly larger for BSP expressing clones. This was determined by real-time PCR analysis for soft organs and by X-ray analysis of bone lesions. For bone this was confirmed by intra-tibial injections of cells in nude mice. We conclude that BSP acts to drive primary and secondary tumor growth of breast cancers in vivo.

Impact of the piston secondary motion on its slap force

A theoretical model is developed for the analysis of piston secondary motion. Based on this model, the slap force of a specific L6 diesel engine was compared when considering different boundary conditions, such as lubricating oil on cylinder liner, surface roughness, deformation of cylinder liner and piston skirt. It is concluded that it is necessary to consider the secondary motion of piston in the analysis of the inner excitation for an internal combustion engine. A more comprehensive consideration of the boundary condition (i.e., more close to the actual condition) will lead to a smaller maximum slap force, and among all boundary conditions considered in this paper, the structural deformation of the piston skirt and cylinder liner is the most influential factor. The theoretical model developed and findings obtained in this study will benefit the future analysis and design of advanced internal combustion engine structures.

High-voltage insulation organic-inorganic nanocomposites by plasma polymerization

In organic-inorganic nanocomposites, interfacial regions are primarily influenced by the dispersion uniformity of nanoparticles and the strength of interfacial bonds between the nanoparticles and the polymer matrix. The insulating performance of organic-inorganic dielectric nanocomposites is highly influenced by the characteristics of interfacial regions. In this study, we prepare polyethylene oxide (PEO)-like functional layers on silica nanoparticles through plasma polymerization. Epoxy resin/silica nanocomposites are subsequently synthesized with these plasma-polymerized nanoparticles. It is found that plasma at a low power (i.e., 10 W) can significantly increase the concentration of C-O bonds on the surface of silica nanoparticles. This plasma polymerized thin layer can not only improve the dispersion uniformity by increasing the hydrophilicity of the nanoparticles, but also provide anchoring sites to enable the formation of covalent bonds between the organic and inorganic phases. Furthermore, electrical tests reveal improved electrical treeing resistance and decreased dielectric constant of the synthesized nanocomposites, while the dielectric loss of the nanocomposites remains unchanged as compared to the pure epoxy resin.

Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Observations on the formation, growth and chemical composition of aerosols in an urban environment

The charge and chemical composition of ambient particles in an urban environment were determined using a Neutral Particle and Air Ion Spectrometer and an Aerodyne compact Time-Of-Flight Aerosol Mass Spectrometer. Particle formation and growth events were observed on 20 of the 36 days of sampling, with eight of these events classified as strong. During these events, peaks in the concentration of intermediate and large ions were followed by peaks in the concentration of ammonium and sulphate, which were not observed in the organic fraction. Comparison of days with and without particle formation events revealed that ammonium and sulphate were the dominant species on particle formation days while high concentrations of biomass burning OA inhibited particle growth. Analyses of the degree of particle neutralisation lead us to conclude that an excess of ammonium enabled particle formation and growth. In addition, the large ion concentration increased sharply during particle growth, suggesting that during nucleation the neutral gaseous species ammonia and sulphuric acid react to form ammonium and sulphate ions. Overall, we conclude that the mechanism of particle formation and growth involved ammonia and sulphuric acid, with limited input from organics.

Chemical and bioanalytical assessment of coal seam gas associated water

A comprehensive study was undertaken involving chemical (inorganic and organic) and bioanalytical (a suite of 14 in vitro bioassays) assessments of coal seam gas (coal bed methane) associated water (CSGW) in Queensland, Australia. CSGW is a by-product of the gas extraction process and is generally considered as water of poor quality. This was done to better understand what is known about the potential biological and environmental effects associated with the organic constituents of CSGW in Australia. In Queensland, large amounts of associated water must be withdrawn from coal seams to allow extraction of the gas. CSGW is disposed of via release to surface water, reinjected to groundwater or reused for irrigation of crops or pasture, supplied for power station cooling and or reinjected specifically to augment drinking water aquifers. Groundwater samples were collected from private wells tapping into the Walloon Coal Measures, the same coal aquifer exploited for coal seam gas production in the Surat Basin, Australia. The inorganic characteristics of these water samples were almost identical to the CSGW entering the nearby gas company operated Talinga-Condabri Water Treatment Facility. The water is brackish with a pH of 8 to 9, high sodium, bicarbonate and chloride concentrations but low calcium, magnesium and negligible sulphate concentrations. Only low levels of polyaromatic hydrocarbons (PAHs) were detected in the water samples, and neither phenols nor volatile organic compounds were found. Results from the bioassays showed no genotoxicity, protein damage, or activation of hormone receptors (with the exception of the estrogen receptor). However, five of the 14 bioassays gave positive responses: an arylhydrocarbon-receptor gene activation assay (AhR-CAFLUX), estrogenic endocrine activity (ERα-CALUX), oxidative stress response (AREc32), interference with cytokine production (THP1-CPA) and non-specific toxicity (Microtox). The observed effects were benchmarked against known water sources and were similar to secondary treated wastewater effluent, stormwater and surface water. As mixture toxicity modelling demonstrated, the detected PAHs explained less than 5% of the observed biological effects.

Changes in teachers’ behaviour in secondary science education : implementing a standards-referenced national curriculum

There is substantial attention worldwide to the quality of secondary school teaching in STEM in Education. This paper reports on the use of Outcome Mapping (OM) as an approach to guide and monitor change in teacher practice and a visual tool, shaped as a Star, to benchmark and monitor this behaviour. OM and the visual tool were employed to guide and document three secondary teachers’ behaviour as they planned, implemented and assessed a science unit in the new Australian standards-referenced curriculum. Five key outcome markers in the teachers’ behaviour were identified together with progress markers — cumulative qualitative indicators — leading to these outcomes. The use of a Star to benchmark and track teachers’ behaviours was particularly useful because it showed teacher behaviour on multiple dimensions simultaneously at various points in time. It also highlighted priorities in need of further attention and provided a pathway to achievement. Hence, OM and the Star representation provide both theoretical and pragmatic approaches to enhancing quality in STEM teaching.

Spectroscopic vibrations of austinite (CaZnAsO4⋅OH) and its mineral structure : Implications for identification of secondary arsenic-containing mineral

Austinite (CaZnAsO4⋅OH) is a unique secondary mineral in arsenic-contaminated mine wastes. The infrared and Raman spectroscopies were used to characterize the austenite vibrations. The IR bands at 369, 790 and 416 cm−1 are assigned to the ν2, ν3 and ν4 vibrations of AsO43− unit, respectively. The Raman bands at 814, 779 and 403 cm−1 correspond to the ν1, ν3 and ν4 vibrations of AsO43− unit respectively. The sharp bands at 3265 cm−1 for IR and 3270 cm−1 both reveals that the structural hydroxyl units exist in the austenite structure. The IR and Raman spectra both show that some SO4 units isomorphically replace AsO4 in austinite. X-ray single crystal diffraction provides the arrangement of each atom in the mineral structure, and also confirms that the conclusions made from the vibrational spectra. Micro-powder diffraction was used to confirm our mineral identification due to the small quantity of the austenite crystals.

Using informative priors in the estimation of mixtures over time with application to aerosol particle size distributions

The issue of using informative priors for estimation of mixtures at multiple time points is examined. Several different informative priors and an independent prior are compared using samples of actual and simulated aerosol particle size distribution (PSD) data. Measurements of aerosol PSDs refer to the concentration of aerosol particles in terms of their size, which is typically multimodal in nature and collected at frequent time intervals. The use of informative priors is found to better identify component parameters at each time point and more clearly establish patterns in the parameters over time. Some caveats to this finding are discussed.

Colloidal semiconductor nanocrystals : controlled synthesis and surface chemistry in organic media

Colloidal semiconductor nanocrystals (CS-NCs) possess compelling benefits of low-cost, large-scale solution processing, and tunable optoelectronic properties through controlled synthesis and surface chemistry engineering. These merits make them promising candidates for a variety of applications. This review focuses on the general strategies and recent developments of the controlled synthesis of CS-NCs in terms of crystalline structure, particle size, dominant exposed facet, and their surface passivation. Highlighted are the organic-media based synthesis of metal chalcogenide (including cadmium, lead, and copper chalcogenide) and metal oxide (including titanium oxide and zinc oxide) nanocrystals. Current challenges and thus future opportunities are also pointed out in this review.