Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Water chemistry, and isotopic ratios and fatty acids and alcohols in Calanus finmarchicus CV, norther Mid-Atlantic Ridge

Fatty acid and alcohol profiles and stable nitrogen and carbon isotope values, d15N and d13C, of Calanus finmarchicus CV were studied in June 2004 to estimate their trophic status along the northern Mid-Atlantic Ridge i.e. the Reykjanes Ridge (RR), extending from Iceland in the north to the productive region of the Sub-Polar Front (SPF) in the south. Two main groups of stations were defined in the study area based on fatty acid (FA) and fatty alcohol compositions, the stations in the RR area constituted one group and the stations in the frontal area constituted another. The sum of relative amounts of the dietary FAs was significantly higher in the RR area than in the frontal area. Conversely, the long-chained FAs, 20:1 and 22:1, were found in significantly lower relative amounts in the RR area than in the frontal area, thus indicating later ascent of the animals in the frontal area. Further support of this is provided by the fatty alcohols ratio 20:1/22:1 which differed significantly between the two areas. The d15N values were significantly higher in the frontal area compared to the RR area indicating higher trophic position and/or different pelagic-POM baseline in these areas.

Mesoporous Metal Complex–Silica Aerogels for Environmentally Friendly Amination of Allylic Alcohols

Two series of mesoporous hybrid iron(III) complex–silica aerogels were prepared in one-pot synthesis by using the sol–gel coordination chemistry approach. The use of the ligands 3-(2-aminoethylamino)propyltrimethoxysilane and 2-(diphenylphosphino)ethyltriethoxysilane, both with terminal triethoxysilyl groups, were used to incorporate metal complexes in situ into the framework of silica, through their co-condensation with a silicon alkoxide during the aerogel formation. This methodology yielded optically translucent hybrid mesoporous gels with homogeneous metal incorporation and excellent textural properties. The catalytic performance of these materials was tested in the direct amination of allylic alcohols in water as a target reaction, with activities comparable or even higher than those corresponding to the homogeneous iron(III) complex. Furthermore, these catalysts were stable and maintained their catalytic activity after six reaction cycles.

Alcohols and other oxygenates in automotive fuels

The aim of this research was to assess the effect of oxygenated hydrocarbons on the knocking characteristics of an engine when blended with low-leaded gasoline. Alcohols, ethers, esters and ketones were tested individually and in various combinations up to an oxygen content of 4% wt/wt in a blend with Series F-7 gasoline of 90, 92, 94 and 96 RON. Tests were carried out at wide open throttle, constant speed and standard timing setting. Engine speed was varied using a dynamometer and knock was detected by two piezoelectric transducers, one on the cylinder head monitoring all four cylinders and one monitoring the cylinder most prone to knock. The engine speeds associated with trace and light knock of a continuous nature were noted. Curves were produced for each oxygenate blend of base RON used against engine speed for the two knock conditions which were compared with those produced using pure Series F-7 fuels. From this a suggested RON of the blend was derived. RON increase was less when using a higher RON base fuel in the blend. Most individual oxygenates showed similar effects in similar concentrations when their oxygen content was comparable. Blends containing more than one oxygenate showed some variation with methanol/MTBE/3 methylbutan-2-one and methanol/MTBE/4 methyl pentan-2-one knocking less than expected and methanol/MTBE/TBA also showing good knock resistance. Further tests to optimise initial findings suggested a blend of methanol and MTBE to be superior although partial replacement of MTBE by 4 methyl pentan-2-one resulted in a fuel of comparable performance. Exhaust emissions were tested for a number of oxygenated blends in 2-star gasoline. 2-star and 4-star fuels were also tested for reference. All oxygenate blends reduced carbon monoxide emissions as expected and hydrocarbon emissions were also reduced. The largest reduction in carbon monoxide occurred using a 14.5 % (1 : 1 : 1) methanol/MTBE/4 methyl pentan-2-one blend. Hydrocarbon emissions were most markedly reduced by a blend containing 25.5 % 4 methyl pentan-2-one. Power output was tested for the blends and indicated a maximum increase of about 5 % at low engine speeds. The most advantageous blends were methanol/4 methyl pentan-2-one (6 : 5) 11% in 2-star and methanol/MTBE/4 methyl pentan-2-one (6 : 3 : 2) 11% in 2-star. In conclusion methanol/MTBE (6 : 5) and (5 : 5), and various combinations of methanol/MTBE/4 methyl pentan-2-one, notably (6 : 3 : 2) gave good results in all tests conducted. CFR testing of these blends showed them to increase both RON and MON substantially.

Mesoporous silicas as versatile supports to tune the palladium-catalyzed selective aerobic oxidation of allylic alcohols

Surfactant templating offers a simple route to synthesize high-surface area silicas with ordered, tunable mesopore architectures. The use of these materials as versatile catalyst supports for palladium nanoparticles has been explored in the aerobic selective oxidation (selox) of allylic alcohols under mild conditions. Families of Pd/mesoporous silicas, synthesized through incipient wetness impregnation of SBA-15, SBA-16, and KIT-6, have been characterized by using nitrogen porosimetry, CO chemisorption, diffuse reflection infrared Fourier transform spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and high-resolution TEM and benchmarked in liquid phase allylic alcohol selox against a Pd/amorphous SiO2 standard. The transition from amorphous to two-dimensional parallel and three-dimensional interpenetrating porous silica networks conferred significant selox rate enhancements associated with higher surface densities of active palladium oxide sites. Dissolved oxygen was essential for insitu stabilization of palladium oxide, and thus maintenance of high activity on-stream, whereas selectivity to the desired aldehyde selox product over competing hydrogenolysis pathways was directed by using palladium metal. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorinated surfactants in solution: Diffusion coefficients of fluorinated alcohols in water

Intra-diffusion coefficients of three fluorinated alcohols, 2,2,3,3,3-pentafluoropropan-1-ol (PFP), 2,2,3,3,4,4,4-heptafluorobutan-1-ol (HFB) and 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol (NFP) in water have been measured by the PFG–NMR spin-echo technique as a function of temperature and composition, focusing on the alcohol dilute region. For comparison, intra-diffusion coefficients of 2,2,2- trifluoroethanol (TFE) and HFB have also been measured in heavy water using the same method and conditions. As far as we know, these are the first experimental measurements of this property for these binary systems. Intra-diffusion coefficients for NFP in water and for TFE and HFB in heavy water have also been obtained by molecular dynamics simulation, complementing those for TFE, PFP and HFB reported in a previous work. The agreement between experimental and simulated results for PFP, HFB and NFP in water is reasonable, although presenting higher deviations than for the TFE/water system. From the dependence of the intra-diffusion coefficients on temperature, diffusion activation energies were estimated for all the solutes in water and heavy water.

Speaker identification using higher order spectral phase features and their effectiveness vis-a-vis Mel-Cepstral features

The effectiveness of higher-order spectral (HOS) phase features in speaker recognition is investigated by comparison with Mel Cepstral features on the same speech data. HOS phase features retain phase information from the Fourier spectrum unlikeMel–frequency Cepstral coefficients (MFCC). Gaussian mixture models are constructed from Mel– Cepstral features and HOS features, respectively, for the same data from various speakers in the Switchboard telephone Speech Corpus. Feature clusters, model parameters and classification performance are analyzed. HOS phase features on their own provide a correct identification rate of about 97% on the chosen subset of the corpus. This is the same level of accuracy as provided by MFCCs. Cluster plots and model parameters are compared to show that HOS phase features can provide complementary information to better discriminate between speakers.