Abstract
Negative ion mass spectrometric techniques, for compounds having good ionization properties, such as pentafluorobenzyl derivatives, are believed to be more sensitive than positive ion methods. Preparation of PFB oximes of fatty aldehydes from crude lipid extracts is problematic due to the release of free aldehydes from plasmalogens during derivatization. Accordingly, in these studies plasmalogens were removed by silicic acid column chromatography prior to pentafluorobenzyl derivatization. This simple purification step to remove plasmalogens is shown to facilitate the quantification of long-chain aldehydes by analysis of their pentafluorobenzyl oxime derivatives utilizing gas chromatography–mass spectrometry in the negative ion chemical ionization mode. The limit of detection for long chain fatty aldehydes using this method is 0.5 pmol and it is linear over two orders of magnitude. Silicic acid column chromatography followed by electrospray ionization mass spectrometry demonstrated that plasmalogens were removed (the detection limit for this analyses was ≤0.3 pmol). Furthermore, we have exploited the utility and sensitivity of this method to identify increases in hexadecanal and octadecanal in 3-amino-1,2,4-triazole treated human neutrophils.
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Abbreviations
- AAG :
-
1-O-alk-1′-enyl-2-acyl-sn-glycerol
- di-16:0 GPC:
-
1,2-Dihexadecanoyl-sn-glycero-3-phosphocholine
- di-20:0 GPC:
-
1,2-Diicosanoyl-sn-glycero-3-phosphocholine
- 16:0-18:1 pPC:
-
1-O-hexadec-1′-enyl-2-octadec-9′-enoyl-sn-glycero-3-phosphocholine
- 2-ClHDA:
-
2-Chlorohexadecanal
- ATZ:
-
3-Amino-1,2,4-triazole
- DAG:
-
Diacylglycerol
- DI-ESI-MS/MS:
-
Direct-infusion electrospray ionization tandem mass spectrometry
- GC–MS:
-
Gas chromatography–mass spectrometry
- HCAEC:
-
Human coronary artery endothelial cells
- HNE:
-
4-Hydroxynonenal
- MDA:
-
Malondialdehyde
- NICI:
-
Negative ion chemical ionization
- 18:0 SM:
-
N-octadecanoyl sphingosylphosphorylcholine
- PFB:
-
Pentafluorobenzyl
- PC:
-
Phosphatidylcholine
- SIM:
-
Selected ion monitoring
- TLC:
-
Thin layer chromatography
References
O’Brien PJ, Siraki AG, Shangari N (2005) Aldehyde sources, metabolism, molecular toxicity mechanisms, and possible effects on human health. Crit Rev Toxicol 35:609–662
Uchida K (2000) Role of reactive aldehyde in cardiovascular diseases. Free Radic Biol Med 28:1685–1696
Esterbauer H, Jurgens G, Quehenberger O, Koller E (1987) Autoxidation of human low density lipoprotein: loss of polyunsaturated fatty acids and vitamin E and generation of aldehydes. J Lipid Res 28:495–509
Porter NA, Caldwell SE, Mills KA (1995) Mechanisms of free radical oxidation of unsaturated lipids. Lipids 30:277–290
Yin H, Porter NA (2005) New insights regarding the autoxidation of polyunsaturated fatty acids. Antioxid Redox Signal 7:170–184
Esterbauer H, Schaur RJ, Zollner H (1991) Chemistry and biochemistry of 4-hydroxynonenal, malonaldehyde and related aldehydes. Free Radic Biol Med 11:81–128
Albert CJ, Crowley JR, Hsu FF, Thukkani AK, Ford DA (2001) Reactive chlorinating species produced by myeloperoxidase target the vinyl ether bond of plasmalogens: identification of 2-chlorohexadecanal. J Biol Chem 276:23733–23741
Brahmbhatt VV, Hsu FF, Kao JL, Frank EC, Ford DA (2007) Novel carbonyl and nitrile products from reactive chlorinating species attack of lysosphingolipid. Chem Phys Lipids 145:72–84
Thukkani AK, Hsu FF, Crowley JR, Wysolmerski RB, Albert CJ, Ford DA (2002) Reactive chlorinating species produced during neutrophil activation target tissue plasmalogens: production of the chemoattractant, 2-chlorohexadecanal. J Biol Chem 277:3842–3849
Marsche G, Heller R, Fauler G, Kovacevic A, Nuszkowski A, Graier W, Sattler W, Malle E (2004) 2-chlorohexadecanal derived from hypochlorite-modified high-density lipoprotein-associated plasmalogen is a natural inhibitor of endothelial nitric oxide biosynthesis. Arterioscler Thromb Vasc Biol 24:2302–2306
Kim SS, Gallaher DD, Csallany AS (1999) Lipophilic aldehydes and related carbonyl compounds in rat and human urine. Lipids 34:489–496
Csallany AS, Kim SS, Gallaher DD (2000) Response of urinary lipophilic aldehydes and related carbonyl compounds to factors that stimulate lipid peroxidation in vivo. Lipids 35:855–862
Hunt DF, Stafford GC, Crow FW, Russell JW (1976) Pulsed positive negative ion chemical ionization mass spectrometry. Anal Chem 48:2098–2104
Kawai Y, Takeda S, Terao J (2007) Lipidomic analysis for lipid peroxidation-derived aldehydes using gas chromatography-mass spectrometry. Chem Res Toxicol 20:99–107
Hsu FF, Hazen SL, Giblin D, Turk J, Heinecke JW, Gross ML (1999) Mass spectrometric analysis of pentafluorobenzyl oxime derivative of reactive biological aldehydes. Int J Mass Spectr 187:795–812
Morand OH, Zoeller RA, Raetz CR (1988) Disappearance of plasmalogens from membranes of animal cells subjected to photosensitized oxidation. J Biol Chem 263:11597–11606
Nagan N, Zoeller RA (2001) Plasmalogens: biosynthesis and functions. Prog Lipid Res 40:199–229
Hayashi H, Hara M (1997) 1-Alkenyl group of ethanolamine plasmalogen derives mainly from de novo-synthesized fatty alcohol within peroxisomes, but not extraperoxisomal fatty alcohol or fatty acid. J Biochem (Tokyo) 121:978–983
Dess DB, Martin JC (1983) Readily accessible 12-I-5 oxidant for the conversion of primary and secondary alcohols to aldehydes and ketones. J Org Chem 48:4155–4156
Han XL, Zupan LA, Hazen SL, Gross RW (1992) Semisynthesis and purification of homogeneous plasmenylcholine molecular species. Anal Biochem 200:119–124
Bligh EG, Dyer WJ (1959) A rapid method of total lipid extraction and purification. Can J Biochem Physiol 37:911–917
Zoeller RA, Lake AC, Nagan N, Gaposchkin DP, Legner MA, Lieberthal W (1999) Plasmalogens as endogenous antioxidants: somatic cell mutants reveal the importance of the vinyl ether. Biochem J 338(Pt 3):769–776
Margoliash E, Novogrodsky A, Schejter A (1960) Irreversible reaction of 3-amino-1:2:4-triazole and related inhibitors with the protein of catalase. Biochem J 74:339–348
Nauseef WM, Metcalf JA, Root RK (1983) Role of myeloperoxidase in the respiratory burst of human neutrophils. Blood 61:483–492
Seppanen CM, Csallany AS (2001) Simultaneous determination of lipophilic aldehydes by high-performance liquid chromatography in vegetable oil. J Am Oil Chem Soc 78:1253–1260
Tyagi SR, Burnham DN, Lambeth JD (1989) On the biological occurrence and regulation of 1-acyl and 1-O-alkyl-diradylglycerols in human neutrophils. Selective destruction of diacyl species using Rhizopus lipase. J Biol Chem 264:12977–12982
Kates M (1986) in Laboratory techniques in biochemistry and molecular biology. In: Burdon RH, Knippenberg PHV (eds) vol. 3, part 2, 2nd revised edn. Elsevier, New York
Acknowledgments
This research was supported by National Institutes of Health grants HL 74214 (DAF) and RR19232 (DAF) as well as Grant-in-Aid 0650044Z (DAF) and Pre-doctoral fellowship grant 0710121Z (VVB) from the American Heart Association.
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Brahmbhatt, V.V., Nold, C., Albert, C.J. et al. Quantification of Pentafluorobenzyl Oxime Derivatives of Long Chain Aldehydes by GC–MS Analysis. Lipids 43, 275–280 (2008). https://doi.org/10.1007/s11745-008-3153-x
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DOI: https://doi.org/10.1007/s11745-008-3153-x