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. Oxidation products of these PUFA could not be detected, but monounsaturated fatty acids proved to be good indicators of oxidative processes. The presence (after NaBH(4)-reduction) of a high proportion of 11-hydroxyoctadec-cis-9-enoic and 8-hydroxyoctadec-cis-9-enoic acids showed that the degradation of oleic acid involved mainly free radical oxidation processes (70-75% autoxidation and 20-25% photooxidation). We also detected large amounts of degradation products of the oxidation product 9,10-epoxyoctadecanoic acid including diols, methoxyhydrins and chlorohydrins. These oxidative effects were found in all the lipid classes examined. Products included significant amounts of chlorophyll side-chain autooxidation products Z- and E-3,7,11,15-tetramethylhexadec-3-ene-1,2-diols and Z-and E-3,7,11,15-tetramethylhexadec-2-ene-1,4-diols, while phytyldiol was present in relatively low proportions. Delta(5)-3beta,7-epimeric unsaturated steroidal diols arising from the autooxidation of the Delta(5) double bond of epi-brassicasterol and minor amounts of Delta(4)-3beta,6-diols were also detected. Long-chain unsaturated ketone (alkenone) content per cell was much higher in the presence of 0.5% CO(2) likely due to carbon storage under these conditions. The proportions of di- and tri-unsaturated alkenones was relatively stable throughout the growth cycle in the absence of additional CO(2), but not when grown with 0.5% CO(2). The detection of characteristic alkenone autoxidation products in cells grown under these latter conditions allowed us to attribute the significant increase in index observed to the involvement of free radical oxidation processes.
Rontani
Jean-François
JF
Laboratoire de Microbiologie Géochimie et Ecologie Marines (UMR 6117), Centre d'Océanologie de Marseille (OSU), Campus de Luminy, case 901, 13288 Marseille, France. jean-francois.rontani@com.univmed.fr
Jameson
Ian
I
Christodoulou
Stéphane
S
Volkman
John K
JK
D001881:Borates / Q000737:chemistry; D056890:Eukaryota / Q000378:metabolism*; D005227:Fatty Acids / Q000737:chemistry / Q000378:metabolism; D005231:Fatty Acids, Unsaturated / Q000737:chemistry / Q000378:metabolism; D005609:Free Radicals / Q000737:chemistry* / Q000378:metabolism; D008401:Gas Chromatography-Mass Spectrometry; D008055:Lipids / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013261:Sterols / Q000737:chemistry / Q000378:metabolism
D001881:Borates; D005227:Fatty Acids; D005231:Fatty Acids, Unsaturated; D005609:Free Radicals; D008055:Lipids; D013261:Sterols; C010634:sodium borate