On the formation of carbonate adducts of fatty alcohols, sterols, and sugars in biological conditions

The formation and properties of carbonate adducts of some organic hydroxy compounds in aqueous medium were investigated. Fatty alcohols and sugars were chosen as representative classes of biological interest, and the medium was carbonated aqueous solution with pH ranging from 3.0 to 8.3. Capillary electrophoresis with two capacitively coupled contactless conductivity detectors (C4Ds) was used for quantitation and to obtain the mobility of the monoalkyl carbonates (MACs), which were used to determine the equilibrium and kinetic constants of the reaction as well as the diffusion coefficients. For increasing chain length of the alcohols, the equilibrium constant tends to the unit, which suggests that fatty alcohols can form the corresponding MACs. The formation of MACs for cyclohexanol and cyclopentanol also suggest the existence of similar species for sterols. Carbonate adducts of fructose, glucose, and sucrose were also detected, which suggests that these counterparts of the well-known phosphates can also occur in the cytosol. Our calculations suggest that one in 1000 to one in 10 000 molecules of these hydroxy compounds would be available as the corresponding MAC in such a medium. Experiments carried out at pH values less than 3.0 showed that there is a catalytic effect of hydronium on the interconversion of bicarbonate and a MAC. Taking into account the great number of hydroxy compounds similar to the ones investigated and that bicarbonate is ubiquitous in living cells, one can anticipate the existence of a whole new class of carbonate adducts of these metabolites.

Selective hydrogenation of fatty acids to alcohols over highly dispersed ReOx/TiO2 catalyst

Production of fatty alcohols through selective hydrogenation of fatty acids was studied over a 4% ReOx/TiO2 catalyst. Stearic acid was hydrogenated to octadecanol at temperatures and pressures between 180-200 degrees C and 2-4 MPa, with selectivity reaching 93%. A high yield of octadecanol was attributed to a strong adsorption of the acid compared to alcohol on the catalyst, which inhibits further alcohol transformation to alkanes. Low amounts (<7%) of alkanes (mainly octadecane) were formed during the conversion of stearic acid. However, it was found that the catalyst could be tuned for the production of alkanes. The reaction intermediates were octadecanal and stearyl stearate. Based on the reaction products analysis and catalyst characterization, a reaction mechanism and possible pathways were proposed.

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.

Fatty acid content of POM, sediment, foraminifer and peracarid samples obtained during POLARSTERN cruise ANT-XXIV/2 (PS71)

In order to investigate the diversity of diet composition in macrobenthic peracarid crustaceans from the Antarctic shelf and deep sea, the fatty acid (FA) composition of different species belonging to the orders Isopoda, Amphipoda, Cumacea and Tanaidacea was analysed. Multivariate analyses of the FA composition confirmed general differences between the orders, but also distinct differences within these orders. To gain information on the origin of the FAs found, the potential food sources sediment, POM and foraminiferans were included in the study. Most of the analysed amphipod species displayed high 18:1(n-9)-18:1(n-7) ratios, widely used as an indicator for a carnivorous component in the diet. Cumaceans were characterised by increased phytoplankton FA markers such as 20:5(n-3) (up to 29% of total FAs), suggesting a diet based on phytodetritus. High values of the FA 20:4(n-6) were found in some munnopsid isopods (up to 21% of total FAs) and some tanaidacean species (up to 19% of total FAs). 20:4(n-6) also occurred in high proportions in some foraminiferan samples (up to 21% of total fatty acids), but not in sediment and POM, possibly indicating the ingestion of foraminiferans by some peracarid crustaceans.

Occurrence of metazoans, and gut pigments and fatty acid composition of Acartia bifilosa in ice and under-ice water samples from Santala Bay

A field study was conducted in Santala Bay with weekly samplings during February and March 2000. Ice thickness was 20-28 cm, snow cover 0-1 cm. The under-ice water column was stratified with a cold (-0.3 - 0.2°C) and less saline (S = 2.1-4.9) interface layer. Concentrations of particulate organic carbon (0.5-5.8 mg POC/l) and algal pigments (0.3-18.2 µg chlorophyll a/l) were higher in the ice than in the water (0.2-0.5 mg POC/l, 1.6-7.1 µg chlorophyll a/l) and peaked mostly in the bottom part of the ice. The thin ice and almost lacking snow cover had favoured an early ice-algal and phytoplankton bloom. The diversity of metazoans was low, with six species in the ice and eight species in the under-ice water. The rotifer Synchaeta cf. littoralis dominated both in ice and water, with maximum abundances of 230 individuals/l in the bottom part of the ice. Rotifer eggs were also observed in the ice. Baltic sea ice seems to be a suitable habitat for rotifers. Nauplii and copepodids of the calanoid Acartia longiremis in the under-ice water showed some herbivorous feeding (<0.1-0.23 ng gut pigment/individual), but analysis of fatty acids, fatty alcohols and biomarker ratios indicated a more omnivorous/carnivorous diet. Despite low temperatures, this copepod showed growth and development below the ice, doubling in numbers (mainly CI, CII) from 118 to 230 individuals m during the third week of March.

Seasonal fatty acid and fatty alcohol composition of Pseudocalanus minutus and Oithona similis in Kongsfjorden (Svalbard)

Seasonal lipid dynamics of various developmental stages were investigated in Pseudocalanus minutus and Oithona similis. For P. minutus, the dominance of 16:1(n?7), 16:4(n?3) and 20:5(n?3) fatty acids indicated a diatom-based nutrition in spring, whereas 22:6(n?3), 16:0, 18:2(n?6) and 18:1(n?9) pointed to a flagellate-based diet during the rest of the year as well as omnivorous/carnivorous low-level feeding during winter. The shorter-chain fatty alcohols 14:0 and 16:0 prevailed, also reflecting biosynthetic processes typical of omnivores or carnivores. Altogether, the lipid signatures characterized P. minutus as an opportunistic feeder. In contrast, O. similis had consistently high amounts of the 18:1(n?9) fatty acid in all stages and during all seasons pointing to a generally omnivorous/carnivorous/detritivorous diet. Furthermore, the fatty alcohol 20:1(n?9) reached high percentages especially in adult females and males, and feeding on Calanus faecal pellets is suggested. Fatty alcohols, as wax ester moieties, revealed significant seasonal variations in O. similis and a seasonal trend towards wax ester accumulation in autumn in P. minutus. P. minutus utilized its lipid deposits for development in the copepodite stages III and IV and for gonad maturation in CV and females during the dark season. However, CVs and females depended on the spring phytoplankton bloom for final maturation processes and reproduction. O. similis fueled gonad maturation and egg production for reproduction in June by wax esters, whereas reproduction in August/September co-occurred with the accumulation of new depot lipids. Both species revealed significantly higher wax ester levels in deeper (>50 m) as compared to surface (0-50 m) dwelling individuals related to a descent prior to overwintering.