Dihydroperoxidation facilitates the conversion of lipids to aldehydic products via alkoxyl radicals

Onyango, Arnold N.; Kumura, Naokazu; Tominaga, Hiroko; Baba, Naomichi

doi:10.1016/j.foodres.2009.12.011

Cited by 10 publications

(15 citation statements)

References 17 publications

(27 reference statements)

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“…The peaks in these spectra are parents of m/z 184 (corresponding to the phosphocholine ion) in the parent ion scan mode, confirming that they are all oxidatively modified phosphatidylcholines. Since the parent hydroperoxide PC-9-LAOOH is of known structure, and its common decomposition products are known [ 14 ], most of the peaks in Figure 1 can be easily assigned.…”

Section: Resultsmentioning

confidence: 99%

“…1-Stearoyl-2-(9′-hydroperoxy-10′,12′-octadecadienoyl)- sn -glycero-3-phosphocholine (PC-9-LA-OOH) was prepared as previously described [ 14 ]. Briefly, the 9-hydroperoxide of linoleic acid (9-LA-OOH) was prepared by oxidation of linoleic acid with a crude homogenate of tomato fruit as described by Schneider et al [ 4 ].…”

Section: Methodsmentioning

confidence: 99%

“…Briefly, the 9-hydroperoxide of linoleic acid (9-LA-OOH) was prepared by oxidation of linoleic acid with a crude homogenate of tomato fruit as described by Schneider et al [ 4 ]. 9-LA-OOH was protected as a peracetal and esterified to lyso-PC, after which the peracetal group was hydrolysed [ 14 , 17 ]. After column chromatography, PC-9-LA-OOH was obtained as a resinous solid, and its structure was confirmed by 1 H NMR and ESI-MS. 1 H NMR (500 MHz, CDCl 3 ) δ 0.87 (6H, m, CH 3 ×2), 1.28 (44H, m, CH 2 ×22), 1.58 (4H, m, OCOCH 2 CH 2 in each chain), 2.15 (2H, m, 8′-H), 2.28 (4H, t, OCOCH 2 in each chain), 3.30 (9H, s, NMe 3 ), 3.75 (2H, m, CH 2 N), 3.98 (2H, m, OCH 2 -CH-CH 2 O), 4.14 (1H, m, one proton of OCH 2 -CH-CH 2 O), 4.34 (4H, one proton of OCH 2 -CH-CH 2 O, OPOCH 2 , 13′-H), 5.22 (1H, m, CO-CH-CO), 5.44 (1H, m, 9-H), 5.57 (1H, dd, H-12), 5.97 (1H, t, 10-H), 6.46 (1H, dd, 11-H).…”

Section: Methodsmentioning

confidence: 99%

“…However, it was previously found that decomposition of a phosphatidylcholine bearing the 13-hydroperoxide of linoleic acid (PC-13-LA-OOH) under anaerobic conditions led to the formation of 9-oxononanoyl-PC as the major aldehydic PC even though the latter cannot be directly formed by β -scission of the alkoxyl radical derived from PC-13-LA-OOH [ 16 ]. In the present study, a phosphatidylcholine bearing 9-LA-OOH 2 was decomposed under anaerobic conditions (nitrogen atmosphere) and the decomposition products analysed by electrospray ionization mass spectroscopy (ESI-MS), which readily gives molecular ion peaks of oxidatively modified phospholipids without the need for prior separation [ 14 ]. Peaks for various well-known aldehydic phospholipid products were detected, and their structures were confirmed by GC-MS with electron impact ionization.…”

Section: Introductionmentioning

confidence: 99%

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Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid

Onyango

2016

BioMed Research International

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Lipid oxidation-derived carbonyl compounds are associated with the development of various physiological disorders. Formation of most of these products has recently been suggested to require further reactions of oxygen with lipid hydroperoxides. However, in rat and human tissues, the formation of 4-hydroxy-2-nonenal is greatly elevated during hypoxic/ischemic conditions. Furthermore, a previous study found an unexpected result that the decomposition of a phosphatidylcholine (PC) bearing the 13-hydroperoxide of linoleic acid under a nitrogen atmosphere afforded 9-oxononanoyl-PC rather than 13-oxo-9,11-tridecadienoyl-PC as the main aldehydic PC. In the present study, products of the anaerobic decomposition of a PC bearing the 9-hydroperoxide of linoleic acid were analysed by electrospray ionization mass spectrometry. 9-Oxononanoyl-PC (ONA-PC) and several well-known bioactive aldehydes including 12-oxo-9-hydroperoxy-(or oxo or hydroxy)-10-dodecenoyl-PCs were detected. Hydrolysis of the oxidized PC products, methylation of the acids obtained thereby, and subsequent gas chromatography-mass spectroscopy with electron impact ionization further confirmed structures of some of the key aldehydic PCs. Novel, hydroxyl radical-dependent mechanisms of formation of ONA-PC and peroxyl-radical dependent mechanisms of formation of the rest of the aldehydes are proposed. The latter mechanisms will mainly be relevant to tissue injury under hypoxic/anoxic conditions, while the former are relevant under both normoxia and hypoxia/anoxia.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid

Onyango

2016

BioMed Research International

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“…This metabolite may be formed from 3 via the corresponding alkoxyl radical and a hydroperoxy-epoxide. Aldehydes such as 9 are known to undergo further non-enzymatic oxidation to their corresponding carboxylic acids [21,23]. Therefore, the molecular species that has m/z 669.8 was deduced to be an acid species PC-COOH/D 3 10 (Scheme 3) since this molecular mass is bigger than that of aldehyde PC-CHO/D 3 9 by 16 mu.…”

Section: Mass Spectrometry-assisted Tracing Of Chemical Changes In Phmentioning

confidence: 99%

Molecular Probes in Tandem Electrospray Ionization Mass Spectrometry: Application to Tracing Chemical Changes of Specific Phospholipid Molecular Species

Tominaga¹,

Ishihara²,

Shah³

et al. 2013

AJAC

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New ionization and detection techniques in mass spectrometry have been successfully applied for efficient analyses of complex biological systems. It is, however, still difficult to trace structural changes of a specific molecular species in such systems. In the present study, a molecular probe strategy in combination with tandem electrospray ionization mass spectrometry has been examined using synthetic deuterium-labeled phosphatidylcholine hydroperoxide (PC-OOH/D3) and ethyl-labeled phosphatidylcholine having docosahexaenoic acid side chain (DHA-PC/Et). Administration of a mixture of PC-OOH/D3 and DHA-PC/Et to human blood and human skin surface, followed by extraction and analysis with collision-induced tandem electrospray ionization mass spectrometry demonstrated that metabolites of both molecular probes can be detected simultaneously with strict selectivity. The present method is also found to be useful in tracing chemical changes of the unstable docosahexaenoyl group on the surface of processed fish. The activity of phospholipase A2 can also be assessed using a phospholipid molecular probe with a linoleoyl and a deuteriomethyl group via selective detection of the lyso-phospholipid product by mass spectrometry. The advantage of the present method is that no chromatographic separation is required and analysis can be performed under strictly the same condition for different molecular probes, affording multiple data by one experiment. The present strategy may be useful for tracing time-dependent phenomena in dynamic phospholipid biochemistry, and can be widely used for any biological and food systems.

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Endogenous ozone as a regular reactive oxygen species in (patho) physiology

Onyango

2023

Advances in Redox Research

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Dihydroperoxidation facilitates the conversion of lipids to aldehydic products via alkoxyl radicals

Cited by 10 publications

References 17 publications

Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid

Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid

Molecular Probes in Tandem Electrospray Ionization Mass Spectrometry: Application to Tracing Chemical Changes of Specific Phospholipid Molecular Species

Endogenous ozone as a regular reactive oxygen species in (patho) physiology

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