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Gas-phase microwave plasma-assisted synthesis of freestanding graphene is a promising route to produce high-quality graphene flakes. However, a comprehensive understanding of the gas-phase kinetics that is required to advance production rates and yields is still lacking. Here, we use line-of-sight Fourier-transform infrared (FTIR) absorption spectroscopy as an in situ diagnostic to measure gaseous species formed during graphene synthesis, thereby elucidating the chemical kinetics mechanism. Different carbonaceous precursors that lead to the formation of either few-layer graphene flakes or soot-like particles are examined, and the results are compared with numerical simulations and mass spectrometry measurements. Quantitative FTIR measurements show a correlation between concentration of atomic carbon and hydrogen in the post-plasma region and particle morphology. Lower carbon and higher hydrogen concentrations lead to graphene formation, while higher carbon and lower hydrogen concentrations shift the reaction toward soot-like particles. We also investigate how the precursor chemical composition, precursor flowrate, and delivered microwave power affect the carbon concentration in the post-plasma region, thus enabling to control particle morphology. [Display omitted] [ABSTRACT FROM AUTHOR]

Objective Cryopyrin-associated periodic syndromes ( CAPS) result from gain-of-function mutations in the NLRP3 gene, which causes excessive release of interleukin-1β ( IL-1β) and systemic inflammation. While pathogenetic NLRP3 variant phenotypes are well-characterized, low-penetrance NLRP3 variants represent a significant clinical challenge. The aims of this study were to determine the clinical phenotype, the in vitro biologic phenotype, and the effect of anti- IL-1 treatment in patients with low-penetrance NLRP3 variants. Methods A multicenter study of consecutive symptomatic patients with low-penetrance NLRP3 variants recruited from 7 centers between May 2012 and May 2013 was performed. The observed findings were transferred into a study database, from which they were extracted for analysis. Controls were patients with a known pathogenetic NLRP3 variant. Clinical presentation and CAPS markers of inflammation were captured. Functional assays of inflammasome activation, including caspase 1 activity, NF-κB release, cell death, and IL-1β release, were performed. Treatment effects of IL-1 were determined. Comparisons between low-penetrance and pathogenetic NLRP3 variants were performed. Results The study included 45 patients, 21 of which were female (47%); 26 of the patients (58%) were children. NLRP3 low-penetrance variants identified in the patients were Q703K (n = 19), R488K (n = 6), and V198M (n = 20). In the controls, 28 had pathogenetic NLRP3 variants. Patients with low-penetrance NLRP3 variants had significantly more fever (76%) and gastrointestinal symptoms (73%); eye disease, hearing loss, and renal involvement were less common. Functional inflammasome testing identified an intermediate phenotype in low-penetrance NLRP3 variants as compared to wild-type and pathogenetic NLRP3 variants. All treated patients responded to IL-1 inhibition, with complete response documented in 50% of patients. Conclusion Patients with low-penetrance NLRP3 variants display a distinct clinical phenotype and an intermediate biologic phenotype, including IL-1β and non- IL-1β-mediated inflammatory pathway activation. [ABSTRACT FROM AUTHOR]

Fluorescence spectra and lifetimes of anisole and toluene vapor in nitrogen have been measured at conditions below ambient (257–293 K and 100–2000 mbar) upon excitation with 266-nm laser light to expand the applicable range of anisole and toluene laser-induced fluorescence (LIF) for conditions below room temperature that occur in expanding flows and cases with strong evaporative cooling. Anisole fluorescence spectra broaden with decreasing pressure while fluorescence lifetimes decrease simultaneously. This is consistent with a more pronounced effect of internal vibrational redistribution on the overall fluorescence signal and can be explained by significantly reduced collision rates. In the case of toluene, the transition from photo-induced heating to photo-induced cooling was observed for the first time for 266 nm. The data confirm predictions of earlier work and is particularly important for the advancement of the available photo-physical (step-ladder) models: since those transitions mark points where the molecules are already thermalized after excitation (i.e., no vibrational relaxation occurs during deactivation), they are important support points for fitting empirical parameters and allow analytical determination of the ground state energy transferred to the excited state. The data enable temperature and/or pressure sensing, e.g., in accelerating cold flows using laser-induced fluorescence of both tracers. [ABSTRACT FROM AUTHOR]

Fresh volcanic glasses from the extrusive section of the Troodos Ophiolite in Akaki Canyon are tholeiitic and basaltic to dacitic in composition. Compared to normal MORB they have extremely low fractionation corrected Na 8 , Fe 8 and Ti 8 and are enriched in fluid-mobile trace elements, including U, Ba, Rb, Sr and Pb, relative to non-fluid mobile elements of similar incompatibility. Trace element compositions of Akaki lavas define an array extending between ‘back-arc lava’-like compositions, and the field defined by Troodos boninites from the upper part of the lava sequence. Troodos lavas were derived from a mantle source that underwent early melt depletion, and later enrichment by both fluids and small degree melts. These processes can explain the unusual negative correlation of Pb/Ce with Zr/Nb and Ba/Nb in Troodos extrusives. Although some Troodos lavas are similar in composition to lavas from back-arc spreading centres, the boninites from the upper parts of the lava pile do not appear to have exact compositional equivalents among lavas from fore-arcs, back-arcs or other tectonic settings where similar rocktypes have been recovered. We suggest that the geochemical evolution inferred for the mantle source of Troodos lavas, together with geological evidence is most consistent with an origin for the Troodos Ophiolite at a spreading centre close to a ridge–trench–trench, or ridge–trench–transform triple junction, where highly depleted, subduction-modified, fluid-enriched mantle wedge material was able to upwell and decompress to shallow depths in a ‘fore-arc’ location. In such a tectonic setting, arc volcanism is captured by the spreading centre, explaining the lack of evidence for subaerial arc magmatism in Troodos. Rapid lateral migration of the triple junction could account for the similar ages of other Tethyan supra-subduction zone ophiolites. [ABSTRACT FROM AUTHOR]