Radical production from the interaction of ozone and PUFA as demonstrated by electron spin resonance spin-trapping techniques

Pryor, William A.; Prier, Donald G.; Church, Daniel F.

doi:10.1016/0013-9351(81)90130-4

Cited by 46 publications

(9 citation statements)

References 39 publications

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“…Our confirmation of the formation of relatively stable secondary ozonides in the reaction of ozone with an unsaturated phosphatidylcholine supports earlier hypotheses (10)(11)(12)(16)(17)(18)(19)(20)(21)(22)(49)(50)(51)(52) that these intermediates could serve as free-radical initiators in biological systems. The work reported here is particularly relevant to inhalation of ozone and its effects on pulmonary surfactant in the alveolar region of the lung.…”

Section: Discussionsupporting

confidence: 90%

Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

Finlayson-Pitts²,

Wv³

1990

Chem. Res. Toxicol.

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Phosphatidylcholines are significant components of pulmonary surfactant in the alveolar region of the lung, where they play a major role in lung function due to their surface tension reducing properties. However, separation and the direct identification of many of the primary products of reaction of phosphatidylcholines with inhaled pollutant gases has not been possible until recently due to the lack of suitable analytical techniques, so that compounds such as fatty acid methyl esters generally have been used as analogues for the phospholipids. We report here the first isolation and identification of the products of reaction of ozone with one of the unsaturated components of lung surfactant, beta-oleoyl-gamma-palmitoyl-L-alpha-phosphatidylcholine (OPPC), using a combination of high-performance liquid chromatography, fast atom bombardment mass spectrometry, and Fourier transform infrared, ultraviolet absorption, and nuclear magnetic resonance spectrometry as well as gas chromatography. The products are shown to be the cis and trans secondary ozonides of the parent phosphatidylcholine, analogous to those previously observed by other researchers in the reactions of the simple fatty acid methyl esters with ozone. This also appears to be the first report of fast atom bombardment mass spectra of these phospholipid secondary ozonides. The implications of this work for the inhalation of ozone, formed in photochemical smog, are discussed.

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Section: Discussionsupporting

confidence: 90%

Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

Finlayson-Pitts²,

Wv³

1990

Chem. Res. Toxicol.

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“…The e.p.r. hyperfine coupling constants of the epoxy radicals are very close to the values which were reported for radical adducts 1991 of 2-methyl-2-nitrosopropane (or 2-methyl-2-nitrosopropanol) with the linoleic acid radical and arachidonic acid radical (L@) in enzymic reaction systems [2,3,5,27,28] and other oxidation systems [29][30][31][32][33][34][35][36][37]. Other information, such as mass spectra and h.p.l.c.…”

Section: Discussionsupporting

confidence: 81%

Radical adducts of nitrosobenzene and 2-methyl-2-nitrosopropane with 12,13-epoxylinoleic acid radical, 12,13-epoxylinolenic acid radical and 14,15-epoxyarachidonic acid radical. Identification by h.p.l.c.-e.p.r. and liquid chromatography-thermospray-m.s

Iwahashi

Parker

Mason

et al. 1991

Biochemical Journal

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Linoleic acid-derived radicals, which are formed in the reaction of linoleic acid with soybean lipoxygenase, were trapped with nitrosobenzene and the resulting radical adducts were analysed by h.p.l.c.-e.p.r. and liquid chromatography-thermospray-m.s. Three nitrosobenzene radical adducts (peaks I, II and III) were detected; these gave the following parent ion masses: 402 for peak I, 402 for peak II, and 386 for peak III. The masses of peaks I and II correspond to the linoleic acid radicals with one more oxygen atom [L(O).]. The radicals are probably carbon-centred, because the use of 17O2 did not result in an additional hyperfine splitting. Computer simulation of the peak I radical adduct e.p.r. spectrum also suggested that the radical is carbon-centred. The peak I radical was also detected in the reaction of 13-hydroperoxylinoleic acid with FeSO4. From the above results, peak I is probably the 12,13-epoxylinoleic acid radical. An h.p.l.c.-e.p.r. experiment using [9,10,12,13-2H4]linoleic acid suggested that the 12,13-epoxylinoleic acid radical is a C-9-centred radical. Peak II is possibly an isomer of peak I. Peak III, which was observed in the reaction mixture without soybean lipoxygenase, corresponds to a linoleic acid radical (L.). The 12,13-epoxylinoleic acid radical, 12,13-epoxylinolenic acid radical and 14,15-epoxyarachidonic acid radical were also detected in the reactions of linoleic acid, linolenic acid and arachidonic acid respectively, with soybean lipoxygenase using nitrosobenzene and 2-methyl-2-nitrosopropane as spin-trapping agents.

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“…The 1-hydroxy-l-alkyl hydroperoxide is an intermediate in the production of aldehydes and hydrogen peroxide, but it hydrolyzes to the aldehyde and hydrogen peroxide under conditions that model pulmonary exposures to low concentrations of ozone (32)(33)(34). In addition to carbonyl compounds and hydrogen peroxide, peroxidic compounds (1,22,35) and/or radicals (36)(37)(38)(39) also are produced.…”

Section: Introductionmentioning

confidence: 99%

Ozonation of methyl oleate in hexane, in a thin film, in SDS micelles, and in distearoylphosphatidylcholine liposomes: yields and properties of the Criegee ozonide

Pryor¹,

Wu²

1992

Chem. Res. Toxicol.

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We here explore the use of Criegee ozonides as markers of ozone damage to lipids in systems that model pulmonary surfactant, lung lining fluids, and/or pulmonary membranes. Ozonation of methyl oleate in hexane gives an 89% yield of the Criegee ozonide. The presence of water should reduce the yield of this ozonide, and as expected, small but significant yields of Criegee ozonides are formed when the ozonation of methyl oleate is carried out as a film over phosphate buffer, in aqueous micelles of sodium dodecyl sulfate (SDS), or in distearoyl-L-alpha-phosphatidylcholine (DSPC) liposomes spiked with methyl oleate. Analysis utilizes reversed-phase HPLC and 1H NMR. The total yield of ozonides in 0.02 M SDS micelles exposed to 26 ppm ozone for 3 h at pH 7.4 and 22 degrees C is 11%; 7.5% is the normal ozonide, methyl 5-octyl-1,2,4-trioxolane-3-octanoate (MOO2) (ca. 4.2% trans and ca. 3.3% cis), and 3.5% is accounted for by the two cross ozonides, 3,5-dioctyl-1,2,4-trioxolane (MOO1) and dimethyl 1,2,4-trioxolane-3,5-dioctanoate (MOO3). No significant difference of ozonide yields is observed for ozonations with 26 ppm and 1.2% (12,000 ppm) ozone. The conversion of methyl oleate increaes with increasing SDS concentration. Approximately comparable yields of ozonides also are found in the ozonation of methyl oleate in DSPC liposomes although yields are not quantified. The ozonides slowly hydrolyze at pH 7.4 and 37 degrees C with half-lives for trans-MOO2 and cis-MOO2 in 0.10 M SDS micelles of 23 and 6 days, respectively.(ABSTRACT TRUNCATED AT 250 WORDS)

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Radical production from the interaction of ozone and PUFA as demonstrated by electron spin resonance spin-trapping techniques

Cited by 46 publications

References 39 publications

Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

Formation of secondary ozonides from the reaction of an unsaturated phosphatidylcholine with ozone

Radical adducts of nitrosobenzene and 2-methyl-2-nitrosopropane with 12,13-epoxylinoleic acid radical, 12,13-epoxylinolenic acid radical and 14,15-epoxyarachidonic acid radical. Identification by h.p.l.c.-e.p.r. and liquid chromatography-thermospray-m.s

Ozonation of methyl oleate in hexane, in a thin film, in SDS micelles, and in distearoylphosphatidylcholine liposomes: yields and properties of the Criegee ozonide

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