Positional distribution of Δ5-acids in triacylglycerols from conifer seeds as determined by partial chemical cleavage

The positional distribution of various Δ5-acids in the seed triacylglycerols from several conifer species has been established after partial chemical degradation with Grignard reagent. The species studied were representative of four conifer families and were specially selected for their particularly high Δ5-acid contents. These species were Taxus baccata (Taxaceae; 5,9-18:2 acid, 11.9%), Larix decidua (Pinaceae; 5,9,12-18:3 acid, 28.5%), Sciadopytis verticillata (Taxodiaceae; 5,11,14-20:3 acid, 16.7%), and Juniperus communis (Cupressaceae; 5,11,14,17-20:4 acid, 19.8%). Calculations from the fatty acid compositions of triacylglycerols and of the mixture of 1,2- and 2,3-diacylglycerols generated by the Grignard reagent indicated that, for the four species, there was a considerable enrichment of Δ5-acids (generally more than ten times) in the 1,3-positions as compared to the 2-position, where Δ5-acids represented always less than 2% of total fatty acids esterified to triacylglycerols. This distribution was practically independent from the species (four families studied), the chainlength (18 or 20 carbon atoms), and the number of ethylenic bonds (two to four) in the Δ5-acids. Similar distributions were established for triacylglycerols from the seeds of three pine species that are available on a ton-scale: Pinus pinea, P. koraiensis, and P. pinaster. These observations confirm and extend previous studies conducted with other conifer species by similar techniques or by ¹³C-nuclear magnetic resonance spectroscopy. Consequently, the almost exclusive location of Δ5-acids in the external positions of triacylglycerols is now well established and appears to be a general feature of conifer seed oils.     

Mechanisms of Enzyme-Catalyzed Reduction of Two Carcinogenic Nitro-Aromatics, 3-Nitrobenzanthrone and Aristolochic Acid I: Experimental and Theoretical Approaches

This review summarizes the results found in studies investigating the enzymatic activation of two genotoxic nitro-aromatics, an environmental pollutant and carcinogen 3-nitrobenzanthrone (3-NBA) and a natural plant nephrotoxin and carcinogen aristolochic acid I (AAI), to reactive species forming covalent DNA adducts. Experimental and theoretical approaches determined the reasons why human NAD(P)H:quinone oxidoreductase (NQO1) and cytochromes P450 (CYP) 1A1 and 1A2 have the potential to reductively activate both nitro-aromatics. The results also contributed to the elucidation of the molecular mechanisms of these reactions. The contribution of conjugation enzymes such as N,O-acetyltransferases (NATs) and sulfotransferases (SULTs) to the activation of 3-NBA and AAI was also examined. The results indicated differences in the abilities of 3-NBA and AAI metabolites to be further activated by these conjugation enzymes. The formation of DNA adducts generated by both carcinogens during their reductive activation by the NOQ1 and CYP1A1/2 enzymes was investigated with pure enzymes, enzymes present in subcellular cytosolic and microsomal fractions, selective inhibitors, and animal models (including knock-out and humanized animals). For the theoretical approaches, flexible in silico docking methods as well as ab initio calculations were employed. The results summarized in this review demonstrate that a combination of experimental and theoretical approaches is a useful tool to study the enzyme-mediated reaction mechanisms of 3-NBA and AAI reduction.     

Biodiesel compatibility with carbon steel and HDPE parts

Compatibility of the new environmentally-friendly alternative of diesel engine fuels, biodiesel, with storage and engine part materials, is still an open issue. In this work, the interaction between three fuels (petroleum diesel and two types of biodiesel — soybean and sunflower) and two materials (carbon steel and high density polyethylene) used in storage and automotive tanks, is analyzed in detail. A wide set of characterization techniques was used to evaluate the changes in both solid and fluid materials, as weight change measurement, optical, scanning electron and atomic force (AFM) microscopies, Raman and FTIR spectroscopies, and differential scanning calorimetry. The AFM technique allowed detecting surface roughness and morphology changes in the metallic material following the trends in the weight losses. In the case of polymeric material, weight gain by fluid absorption occurred, being detected by the spectroscopic techniques. The biodiesel fuels underwent some ageing however this phenomenon did not affect the interaction between the biodiesel fuels and the substrates. The petrodiesel, which did not age, caused more significant degradation of the substrates.     

The Change of X‐ray Diffraction Peak Width During in situ Conventional Sintering of Nanoscale Powders

Diffraction peaks of nanoscale particles of 3 mol% yttria‐stabilized zirconia become sharper as the powder sinters. The reduction in the peak width is correlated with the increase in density. The sharpening of the peak agrees reasonably well with the remaining free surface area as the sample sinters. Therefore, high curvature of the free surface of the pores is assumed to lead to peak broadening (the grain boundaries that grow at the expense of the free surfaces of the pores do not have this curvature). The change in the grain size during sintering does not make a significant contribution to peak width.     

RTD studies in a falling film graphite evaporator with internal spiral fins: Influence of the geometry

A hydrodynamic study of a new graphite evaporator has been performed. In this exchanger the fluid flows as a thin film on a spirally wound fin which forms a spiral staircase inside a tube. The slope θ_m of the spirally wound fin is modifiable. The residence time distribution (RTD) of the film was measured for different fin slopes θ_m and several film flowrates m_f. The flow pattern was then modelled thanks to the DTS software as a cascade of perfect mixed cells and the mean residence time τ_m was calculated. The evolution of τ_m as a function of θ_m and m_f is accurately represented by a power law relation.