Double bond migration to methylidene positions during electron ionization mass spectrometry of branched monounsaturated fatty acid derivatives.

Electron ionization mass spectra of several monounsaturated methyl-branched fatty acid methyl and trimethylsilyl esters were examined. These spectra exhibited some intensive fragment ions, whose formation could be explained after double-bond migration to methylidene position. This preferential migration (substantiated by deuterium labeling) acts significantly in the case of monounsaturated fatty acid methyl and trimethylsilyl esters possessing a methyl branch localized between the penultimate and the C(4) positions (relative to the ester group), whatever the position of the double-bond.

Hydrogen and trimethylsilyl transfers during EI mass spectral fragmentation of hydroxycarboxylic and oxocarboxylic acid trimethylsilyl derivatives.

This paper, describing electron ionization mass spectral fragmentation of some hydroxycarboxylic and oxocarboxylic acid trimethylsilyl derivatives, focuses on the formation of fragment ions resulting from the interactions between the two functionalities of these compounds. These interactions result in the formation of fragment ions at [CH2=C(OTMS)2]+., [CH2=CHC(OTMS)=OTMS]+, [M-31]+, [M-105]+, and [M-RCHO]+.

A new method for nanomolar determination of silicic acid in seawater.

A novel method is proposed to determine concentrations of silicic acid in seawater in the nanomolar range of 3-500 nM. It preconcentrates silicic acid through a "Magnesium Induced Co-precipitation" (MAGIC) step before a classical spectrophotometric measurement. The detection limit (3+/-2 nM) is improved by a factor 10 in comparison to the conventional colorimetric methods.

Free radical oxidation (autoxidation) of alkenones and other lipids in cells of Emiliania huxleyi.

Cells of the coccolithophorid Emiliania huxleyi strain CS-57 grown under an atmosphere of air+0.5% CO(2) showed oxidative damage after 10 days growth with concomitant and major changes to the lipid composition. The fatty acid profile was strongly altered and lacked appreciable amounts of the polyunsaturated fatty acids (PUFA: C(18:5), C(18:3) and C(22:6)) typical of healthy cells.

Anaerobic Degradation of Hexadecan-2-one by a Microbial Enrichment Culture under Sulfate-Reducing Conditions.

A microbial enrichment culture from marine sediment was able to grow on hexadecan-2-one as the sole source of carbon and energy under sulfate-reducing conditions. Oxidation of the ketone involved carboxylation reactions and was coupled to sulfide production. This enrichment culture also grew on 6,10,14-trimethylpentadecan-2-one.

Anaerobic n-alkane metabolism by a sulfate-reducing bacterium, Desulfatibacillum aliphaticivorans strain CV2803T.

The alkane-degrading, sulfate-reducing bacterium Desulfatibacillum aliphaticivorans strain CV2803T, recently isolated from marine sediments, was investigated for n-alkane metabolism. The total cellular fatty acids of this strain had predominantly odd numbers of carbon atoms (C odd) when the strain was grown on a C-odd alkane (pentadecane) and even numbers of carbon atoms (C even) when it was grown on a C-even alkane (hexadecane). Detailed analyses of those fatty acids by gas chromatography/mass spectrometry allowed us to identify saturated 2-, 4-, 6-, and 8-methyl- and monounsaturated 6-methyl-branched fatty acids, with chain lengths that specifically correlated with those of the alkane.

Electron ionization mass spectral fragmentation of cholestane-3beta,4alpha,5alpha-triol and cholestane-3beta,5alpha,6alpha/beta-triol bis- and tris-trimethylsilyl derivatives.

The electron ionization (EI) mass spectral fragmentation of the bis- and tris-trimethylsilyl derivatives of cholestane-3beta,4alpha,5alpha-triol, cholestane-3beta,5alpha,6beta-triol and cholestane-3beta,5alpha,6alpha-triol was investigated. The EI mass spectrum of the 3beta,4alpha-bis-trimethylsilyl derivative of cholestane-3beta,4alpha,5alpha-triol exhibits interesting fragment ions at m/z 142 and 332 resulting from the initial loss of TMSOH between the carbons 2 and 3 and subsequent retro-Diels-Alder (RDA) cleavage of the ring A. Trimethylsilyl transfer between the 4alpha- and the 5alpha-hydroxy groups acts significantly before RDA cleavage affording an ion at m/z 404.

Visible light-induced oxidation of unsaturated components of cutins: a significant process during the senescence of higher plants.

9-Hydroperoxy-18-hydroxyoctadec-10(trans)-enoic and 10-hydroperoxy-18-hydroxyoctadec-8(trans)-enoic acids deriving from type II (i.e. involving 1O2) photooxidation of 18-hydroxyoleic acid were detected after visible light-induced senescence experiments carried out with Petroselinum sativum and subsequent cutin depolymerisation.

Regiospecific oxygenation of alkenones in the benthic haptophyte Chrysotila lamellosa Anand HAP 17.

Two groups of previously unidentified C37-C39 epoxyalkenones and alkenediones were detected in late stationary phase cultures of the haptophyte microalga Chrysotila lamellosa. The formation of these compounds is attributed to the involvement of enzymatic processes acting specifically on the C-21 or C-22 allylic carbon and the omega15 double bond of methyl and ethyl alkenones respectively. Thus, the epoxyalkenones appear to be derivatives of alkenones where the omega15 double bond is oxidized to the epoxide.

Trimethylsilyl transfer during electron ionization mass spectral fragmentation of some omega-hydroxycarboxylic and omega-dicarboxylic acid trimethylsilyl derivatives and the effect of chain length.

The electron ionization (EI) mass spectral fragmentation of omega-hydroxycarboxylic and omega-dicarboxylic acid trimethylsilyl derivatives was investigated. The mass spectra of these compounds exhibited fragment ions resulting from classical fragmentation of the trimethylsilyl ether and ester groups, and others resulting from the interactions between the two functionalities (m/z 147, 204, 217, [M-31](+) and [M-105](+) in the case of omega-hydroxycarboxylic acid derivatives and m/z 147, 204, 217 and [M-131](+) in the case of omega-dicarboxylic acid derivatives). Several fragmentation pathways were proposed to explain the formation of these different fragment ions.

Electron ionization mass spectral fragmentation of derivatized 4,5- and 5,6-epoxysterols.

The electron ionization (EI) mass spectral fragmentation of derivatized 4,5- and 5,6-epoxysterols was investigated. Interesting fragmentation processes involving a transannular cleavage of the epoxide ring after transfer of the trimethylsilyl group are significant in the case of 4,5-epoxysterol trimethylsilyl ethers (affording abundant fragment ions at m/z 403 and 404). Different pathways, which have been substantiated by deuterium labelling, are proposed in order to explain the formation of these ions.

Long-chain alkenones and related compounds in the benthic haptophyte Chrysotila lamellosa Anand HAP 17.

The neutral lipid compositions of the coastal haptophyte Chrysotila lamellosa HAP 17 grown in batch culture at 10 and 20 degrees C have been determined. A comparison was also made between the lipid compositions of cells harvested in early and late stationary phase. This species contains a suite of very long-chain C(37)-C(40) alkenones and alkenoates as found in a few microalgae from the Haptophyta.

Long-chain (C19-C29) 1-chloro-n-alkanes in leaf waxes of halophytes of the Chenopodiaceae.

The hydrocarbon fraction of leaf waxes of three halophytes of the Chenopodiaceae common to Mediterranean salt marshes (Suaeda vera, Sarcocornia fruticosa and Halimione portulacoides) revealed the presence of a minor series of odd and even chains 1-chloro-n-alkanes ranging from C(19) to C(29). The identification of these new chlorinated plant constituents was based on a combination of mass spectrometry data with selective chlorine detection (CPG-AED) and was confirmed by comparison with authentic standards. The qualitative and quantitative distributions of these 1-chloro-n-alkanes varied inter-specifically.

Production of a polyunsaturated isoprenoid wax ester during aerobic metabolism of squalene by Marinobacter squalenivorans sp. nov.

This paper describes the production of 5,9,13-trimethyltetradeca-4E,8E,12-trienyl-5,9,13-trimethyltetradeca-4E,8E,12-trienoate during the aerobic degradation of squalene by a Marinobacter strain, 2Asq64, isolated from the marine environment. A pathway involving initial cleavage of the C(10)-C(11) or C(14)-C(15) double bonds of the squalene molecule is proposed to explain the formation of this polyunsaturated isoprenoid wax ester. The isoprenoid wax ester content reached 1.

Electron ionization mass spectral fragmentation of C19 isoprenoid aldehydes and carboxylic acid methyl and trimethylsilyl esters.

The electron ionization (EI) mass spectra of saturated and alpha,beta-unsaturated C(19) isoprenoid aldehydes and carboxylic acid methyl and trimethylsilyl esters are reported. Different pathways are proposed in order to explain the main fragmentations observed. The conjugated double bond migrates more or less readily before gamma-hydrogen rearrangement according to the structure of the considered compound.

Aerobic and anaerobic metabolism of squalene by a denitrifying bacterium isolated from marine sediment.

The aerobic and anaerobic metabolism of the isoprenoid alkene squalene was investigated in a new type of marine denitrifying bacterium, strain 2sq31, isolated from marine sediment. Strain 2sq31 was identified as a species of Marinobacter. Under denitrifying conditions, the strain efficiently degraded squalene; of 0.

Visible light-dependent degradation of lipidic phytoplanktonic components during senescence: a review.

Though most of the organic components of phytoplankton are susceptible to being photodegraded during senescence, until recent years there has been very little research in this area. Recently, however, there have been a renewal of interest, and the heterogeneous visible light-induced degradative reactions of lipidic compounds associated with phytodetritus have been studied. The present paper reviews the results obtained in the course of these studies.

Aerobic and anaerobic abiotic oxidation of squalene in the presence of hydroperoxides.

Abiotic oxidation of squalene in the presence of hydroperoxysterols was studied in seawater under aerobic and anaerobic conditions. This ubiquitous isoprenoid alkene is quickly degraded in the presence of oxygen and its oxidation results mainly in the production of tertiary alcohols and to a lesser extent of epoxides and secondary alcohols. Although the degradation of squalene logically slows down under anaerobic conditions, a significant oxidation affording similar products than in the case of aerobic degradation has been observed.

Visible light-dependent degradation of long-chain alkenes in killed cells of Emiliania huxleyi and Nannochloropsis salina.

Photosensitized degradation rates of phytoplanktonic n-alkenes under visible light exposure were determined in laboratory experiments. Killed cells of Emiliania huxleyi and Nannochloropsis salina were used as source of biogenic alkenes. In E.

Influence of oxygen supply on heptadecane mineralization by Pseudomonas nautica.

The influence of different states of oxygen supply on heptadecane mineralization has been investigated in resting cell suspensions of Pseudomonas nautica. The rate of heptadecane biodegraded was constant for oxygen concentrations between 21% and 10% (v/v) (about 100% and 50% of air saturation, 230 and 110 microM, respectively). A decline in biodegradation rates occurred for oxygen concentrations below 10% (about 50% of air saturation, 110 microM) and biodegradation stopped with 0.

The effect of growth temperature on the long-chain alkenes composition in the marine coccolithophorid Emiliania huxleyi.

The hydrocarbon fraction of a pure culture of Emiliania huxleyi, composed of a mixture of C31, C33, C37 and C38 polyunsaturated n-alkenes, appeared strongly dependent on the growth temperature of the alga between 8 degrees C and 25 degrees C. The total hydrocarbon content increased linearly with decreasing temperatures. C37 and C38 alkenes (which accounted for more than 90% of the total hydrocarbons) showed distinct changes in distribution compared to C31 and C33 alkenes, suggesting different biological syntheses and/or functions for these two groups of compounds.

Biodegradation of free phytol by bacterial communities isolated from marine sediments under aerobic and denitrifying conditions.

Biodegradation of (E)-phytol [3,7,11, 15-tetramethylhexadec-2(E)-en-1-ol] by two bacterial communities isolated from recent marine sediments under aerobic and denitrifying conditions was studied at 20 degrees C. This isoprenoid alcohol is metabolized efficiently by these two bacterial communities via 6,10, 14-trimethylpentadecan-2-one and (E)-phytenic acid. The first step in both aerobic and anaerobic bacterial degradation of (E)-phytol involves the transient production of (E)-phytenal, which in turn can be abiotically converted to 6,10,14-trimethylpentadecan-2-one.

In-vitro study of interaction between photooxidation and biodegradation of 2-methylphenanthrene by Sphingomonas SP. 2MPII.

This work reports a study of interactions between reactions of photooxidation and reactions of bacterial degradation of an alkylated polyaromatic hydrocarbon (2-methylphenanthrene). Bacterial growth was carried out using artificial sunlight as light source. Among the various products detected, the major product was identified as the 2-methylphenanthrene aldehyde.

Involvement of bioemulsifier in heptadecane uptake in Pseudomonas nautica.

A microbial surfactant was investigated for its potential to enhance the biodegradation of heptadecane. The bioemulsifier used in this study was extracted from culture supernatants of Pseudomonas nautica after growth on heptadecane. The heptadecane uptake rate-could be increased 15-fold by the addition of 1.