Abstract
The autoxidation of polyunsaturated fatty acids is initiated bothin vivo andin vitro by nitrogen dioxide. The mechanism of the initiation process is believed to involve both addition reactions and hydrogen atom abstraction reactions, with hydrogen abstraction predominating at low levels of nitrogen dioxide. Therefore low levels of nitrogen dioxide should react with polyunsaturated fatty acids to give allylic derivatives; in an anaerobic system these derivations should be allylic nitro and nitrite compounds. Using negative methane chemical ionization mass spectrometry and other analytical techniques, we have identified these allylic nitrite and nitro compounds from the reactions of low levels of nitrogen dioxide with methyl linoleate and methyl linolenate in the absence of oxygen.
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Abbreviations
- AN:
-
allylic nitro or nitrite compounds
- c :
-
cis double bond
- DTPA:
-
diethylenetriaminepentaacetic acid
- GC:
-
gas chromatography
- HPLC:
-
high-performance liquid chromatography
- IR:
-
infrared
- M:
-
parent ion
- m/z :
-
mass/charge
- NCI:
-
negative chemical ionization
- NMR:
-
nuclear magnetic resonance
- HP:
-
hydroperoxide
- t :
-
trans double bond
- TLC:
-
thin-layer chromatography
- UV:
-
ultraviolet
- 9c, 11t, 15c-13AN:
-
methyl 13-nitrito-cis-9,trans-11,cis-15-octadecatrienoate and methyl 13-nitro-trans-9,trans-11,cis-15-octadecatrienoate
- 9t, 11t, 15c-13AN:
-
methyl 13-nitrito-trans-9,trans-11,cis-15-octadecatrienoate and methyl 13-nitro-trans-9,trans-11,cis-15-octadecatrienoate
- 9t, 11t, 15c-13HP:
-
methyl 13-hydrperoxy-cis-9,trans-11cis-15-octadecatrienoate
- 9t, 11t, 15c-13HP:
-
methyl 13-hydroperoxy-trans-9,trans-11,cis-15-octadecatrienoate
- 9c, 12c, 14t-16AN:
-
methyl 16-nitrito-cis-9,cis-12,trans-14-octadecatrienoate and methyl 16-nitro-cis-9,cis-12,trans-14-octadecatrienoate
- 9c, 12c, 14t-16HP:
-
methyl 16-hydroperoxy-cis-9,cis-12,trans-14-octadecatrienoate
- 9c, 12t, 14t-16HP:
-
methyl 16-hydroperoxy-cis-9,trans-12,trans-14-octadecatrienoate
- 9c, 13t, 15c-12AN:
-
methyl 12-nitrito-cis-9,trans-13,cis-15-octadecatrienoate and methyl 12-nitro-cis-9,trans-13,cis-15-octadecatrienoate
- 9c, 13t, 15t-12AN:
-
methyl 12-nitrito-cis-9,trans-13,trans-15-octadecatrienoate and methyl 12-nitro-cis-9,trans-12,trans-15-octadecatrienoate
- 9c, 13t, 15c-12HP:
-
methyl 12-hydroperoxy-cis-9,trans-13,cis-15-octadecatrienoate
- 9c, 13t, 15t-12HP:
-
methyl 12-hydroperoxy-cis-9,trans-13,trans-15-octadecatrienoate 10t, 12c, 15c-9AN, methyl 9-nitrito-trans-10,cis-12,cis-15-octadecatrienoate and methyl 9-nitro-trans-10,cis-12,cis-15-octadecatrienoate
- 10t, 12t, 15c-9AN:
-
methyl 9-nitrito-trans-10,trans-12,cis-15-octadecatrienoate and methyl 9-nitro-trans-10,trans-12,cis-15-octadecatrienoate
- 10t, 12c, 15c-9HP:
-
methyl 9-hydroperoxy-trans-10,cis-12,cis-15-octadecatrienoate
- 10t, 12t, 15c-9HP:
-
methyl 9-hydroperoxy-trans-10,trans-12,cis-15-octadecatrienoate
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Gallon, A.A., Pryor, W.A. The identification of the allylic nitrite and nitro derivatives of methyl linoleate and methyl linolenate by negative chemical ionization mass spectroscopy. Lipids 28, 125–133 (1993). https://doi.org/10.1007/BF02535776
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DOI: https://doi.org/10.1007/BF02535776