Determination of the vapor pressures of select polychlorinated dibenzo-p-dioxins and dibenzofurans at 75-275 °C

Vapor pressures were determined for several polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at 75-275 °C, extending the available literature data to more relevant temperature regions and providing the first experimental data for 2,3,7-trichlorodibenzo-p-dioxin (2,3,7-TriCD). A modification of the effusion technique, based upon controlling the diffusion of the target compound and subsequent high resolution gas chromatography/low resolution mass spectrometry (HRGC/LRMS) analysis, was proven comparable to other accepted methods for determining the vapor pressures of semi-volatile organic compounds (SVOCs). Vapor pressures for octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) were in excellent agreement with those reported in literature. The application of the current method for the vapor pressure determinations of eight polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/PCDFs) in the extended temperature range (up to 275 °C) is reported. The extension of the vapor pressures to such temperatures, unprecedented for the PCDDs/Fs, is important for vapor-particle partitioning modeling in regions relevant to PCDD/F formation and control. Estimates for the melting temperatures and enthalpies of sublimation and vaporization are also reported, the latter for which no experimentally determined values have been found in the literature. The use of the method to deliver reproducible, trace concentrations (ppt-ppb) of targets was applied to the calibration of the jet-REMPI/TOFMS as an online detector for low chlorinated PCDDs/Fs.     

Paf-acether in human skin

Paf is a phospholipid mediator present in human skin which induces inflammatory events such as neutrophil infiltration and increased vascular permeability. Recent data suggest that cutaneous cells, such as fibroblasts and keratinocytes, produce paf and that paf is released during allergic cutaneous reactions. It is tempting to speculate that paf may contribute to the development of various skin disorders with acute and chronic skin inflammation. Paf antagonists may help in bringing answers to this hypothesis and may offer new prospects for the treatment of cutaneous inflammatory diseases. Based on a paper presented at the Third International Conference on Platelet-Activating Factor and Structurally Related Alkyl Ether Lipids, Tokyo, Japan, May 1989.     

A fuzzy constraint-based approach to data reconciliation in material flow analysis

Data reconciliation consists in modifying noisy or unreliable data in order to make them consistent with a mathematical model (herein a material flow network). The conventional approach relies on least-squares minimization. Here, we use a fuzzy set-based approach, replacing Gaussian likelihood functions by fuzzy intervals, and a leximin criterion. We show that the setting of fuzzy sets provides a generalized approach to the choice of estimated values, that is more flexible and less dependent on oftentimes debatable probabilistic justifications. It potentially encompasses interval-based formulations and the least squares method, by choosing appropriate membership functions and aggregation operations. This paper also lays bare the fact that data reconciliation under the fuzzy set approach is viewed as an information fusion problem, as opposed to the statistical tradition which solves an estimation problem.     

Joint routing and location-based service in VANETs

Geographic routing protocols use location information when they need to route packets. In the meantime, location information are maintained by location-based services provided by network nodes in a distributed manner. Routing and location services are very related but are used separately. Therefore, the overhead of the location-based service is not considered when we evaluate the geographic routing overhead. Our aim is to combine routing protocols with location-based services in order to reduce communication establishment latency and routing overhead.     

Modelling of the Nonlinear Behavior of Compatibilized Polyethylene/Polyamide Blends in Shear and Extensional Flows

We have studied the effect of the amount Φ_c of a reactive compatibilizer on the rheological properties of a polyethylene/polyamide blend, under steady shear and transient extensional flows. Here, we propose to describe the viscosity η(γ) and the first normal stress coefficient γ₁(γ) using a Carreau‐type power‐law model, which is a three‐parameter model. A single model is sufficient to express the behavior of γ₁(γ) On the other hand, the complete η(γ) curve is described by the superposition of two Carreau models, in relation to the presence of two relaxation mechanisms. Moreover, the extentional viscosity η_E(?), estimated using the end pressure drop observed in capillary flow experiments, is expressed by a two‐parameter power‐law model.     

Stability of ruthenium catalysts supported on TiO2 or ZrO2 in catalytic wet air oxidation

The stability of ruthenium catalysts supported on TiO₂ and ZrO₂ were studied in the wet air oxidation of aqueous solution of succinic and p-hydroxybenzoic acids taken as model effluent and on real effluents from the paper-pulp industry. Catalyst recycling experiments were conducted in batch reactor and long-term stability tests were conducted in trickle-bed reactor. In all experiments, ruthenium and support materials were perfectly stable to leaching, sintering and fouling. Ruthenium catalysts experienced a weak deactivation as they were exposed to air, e.g., in recycling experiments however the loss of activity occurred only after the first exposure and was completely reversible upon catalyst reduction. The deactivation was attributed to an over-oxidation of the catalyst surface particularly noticeable in the case of very small Ru-clusters (1 nm).     

Molecular analysis of intact preen waxes of Calidris canutus (Aves: Scolopacidae) by gas chromatography/mass spectrometry

The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing additional resolution to the analysis of wax esters. The C₂₁−C₃₂ wax esters are composed of complex mixtures of hundreds of individual isomers. The odd carbon-numbered wax esters are predominantly composed of even carbon-numbered n-alcohols (C₁₄, C₁₆, and C₁₈) esterified predominantly with odd carbon-numbered 2-methyl fatty acids (C₇, C₉, C₁₁, and C₁₃), resulting in relatively simple distributions. The even carbon-numbered wax esters show a far more complex distribution due to a number of factors: (i) Their n-alcohol moieties are not dominated by even carbon-numbered n-alcohol moieties are not dominated by even carbon-numbered n-alcohols esterified with odd carbon-numbered 2-methyl fatty acids, but odd and even carbon-numbered n-alcohols participate in approximately equal amounts; (ii) odd carbon-numbered methyl-branched alcohols participate abundantly in these wax ester clusters; and (iii) with increasing molecular weight, various isomers of the 2,6-, 2,8-, and 2,10-dimethyl branched fatty acids also participate in the even carbon-numbered wax esters. The data demonstrate that there is a clear biosynthetic control on the wax ester composition although the reasons for the complex chemistry of the waxes are not yet understood.     

Alternative technologies for biotechnological fuel ethanol manufacturing

The challenges of implementing biorefineries on a global scale include socioeconomic, financial, and technological constraints. In particular, the development of biorefineries is tightly linked to the continued availability of fermentation raw materials. These constraints can be relaxed by the use of diverse raw materials, while advances that confer higher flexibility would enable biotechnological plant managers to swiftly react to volatile markets. In conventional processes, Saccharomyces cerevisiae grows on a relatively limited range of substrates, and produces only a single product—ethanol. Given the observed maturity of the S. cerevisiae fermentation technology, alternatives to baker's yeast may be needed to tip the economic balance in favour of biotechnological ethanol. These alternative fermentation technologies may allow a greater diversity of substrates to be used to produce an individually tailored mix of ethanol and other chemicals. Copyright © 2007 Society of Chemical Industry     

New phospholipid fatty acids from the marine spongeCinachyrella alloclada uliczka

The fatty acid composition of phospholipids from the Senegalese spongeCinachyrella alloclada was examined. Two new fatty acids not hitherto found in nature, namely 10,13-octadecadienoic acid and 16-tricosenoic acid, were identified. 8-Hexadecenoic, 13-nonadecenoic and 5,9,13-trimethyltretradecanoic fatty acids were also found for the first time in sponges. The latter compound (1.4% of the total fatty acid mixture), an isoprenoid fatty acid, accompanies the major fatty acid 4,8,12-trimethyltridecanoic acid (19.7%). The monomethyl branched fatty acids (22%) identified include 23-methylpentacosanoic acid (anteiso-26∶0), not previously observed in sponged. The major long-chain fatty acids encountered were the known 17-tetracosenoic 19-heptacosadienoic and 5,9,23-tricontatrienoic acid. Some sixty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry.