Autoxidative and Photooxidative Reactivity of Highly Branched Isoprenoid (HBI) Alkenes

Autoxidation of several mono-, di-, tri- and tetra-unsaturated highly branched isoprenoid (HBI) alkenes was induced in organic solvents using a radical initiator and enhancer, and their degradation rates were compared to those of classical phytoplanktonic lipids (mono-unsaturated fatty acids, sterol...

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Bibliographic Details
Published in:Lipids
Main Authors: Rontani, Jean-Francois, Belt, S. T., Vaultier, Frederic, Brown, T. A., Masse, G.
Other Authors: Institut méditerranéen d'océanologie (MIO), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Toulon (UTLN)-Centre National de la Recherche Scientifique (CNRS)
Format: Article in Journal/Newspaper
Language:English
Published: HAL CCSD 2014
Subjects:
HBI alkenes
Autoxidation
Photooxidation
Kinetic
Senescent diatom cells
Specific tracers
[CHIM.ORGA]Chemical Sciences/Organic chemistry
[SDU.OCEAN]Sciences of the Universe [physics]/Ocean
Atmosphere
Antarc*
Antarctic
Online Access:https://hal.science/hal-01308379
https://doi.org/10.1007/s11745-014-3891-x
Description
Summary:Autoxidation of several mono-, di-, tri- and tetra-unsaturated highly branched isoprenoid (HBI) alkenes was induced in organic solvents using a radical initiator and enhancer, and their degradation rates were compared to those of classical phytoplanktonic lipids (mono-unsaturated fatty acids, sterols and chlorophyll phytyl side-chain). Autoxidation of two HBI trienes was also investigated in senescent and highly photodegraded diatom cells, collected in the Antarctic, using Fe2+ ions as radical inducers. Autoxidation rates of HBI alkenes were found to increase with the number of tri-substituted double bonds, as expected. Further, HBI trienes possessing one bis-allylic position (where hydrogen abstraction is highly favoured) were found to be particularly reactive towards autoxidation and degraded at similar rates compared to polyunsaturated fatty acids in diatom cells. By comparison of the autoxidation products of the most reactive tri-unsaturated HBI with the corresponding photooxidation products, some specific tracers of these two types of abiotic degradation processes were identified. The lack of reactivity of the mono-unsaturated HBI IP25 and a structurally similar di-unsaturated HBI towards autoxidative degradation supports the good preservation of these biomarkers in marine sediments.

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