Abstract
Coordination ionspray mass spectrometry (CIS-MS) is a useful tool in the detection and identification of cholesterol ester and phospholipid hydroperoxides and diacyl peroxides. Extensive studies of a series of cholesterol esters using CIS-MS revealed the following: (1) Cholesterol esters with equal number of double bonds as the internal standard showed a linear relative response in the mass spectrometer while compounds with non-equal numbers of double bonds gave a nonlinear relative response. (2) Complex adducts containing cholesterol ester, silver ion, AgF, AgBF4, and 2-propanoxide form when silver is in molar excess of cholesterol esters, reducing the [M+Ag]+ signal. (3) In a mixture of cholesterol esters where silver is limiting, Ch22:6 and Ch20:4 bind to silver at the expense of Ch18:2 and have a higher signal in the mass spectrometer. (4) In a mixture of cholesterol esters where silver concentration is twofold greater than total cholesterol ester concentration, Ch22:6 and Ch20:4 form large complex adducts more frequently than Ch18:2 and have a lower signal in the mass spectrometer.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Marnett, L. J. Lipid Peroxidation-Dependent Mutagenesis: Chemistry and Biology. Free Radicals Chem. Biol. Med. 2000, 7–15.
Beal, M. F. Aging, Energy, and Oxidative Stress in Neurodegenerative Diseases. Ann. Neurol. 1995, 38, 357–366.
Steinberg, D. Nutrition and Biotechnology in Heart Disease and Cancer. Plenum Press: New York, 1995; 39–48.
Havrilla, C. M.; Hachey, D. L.; Porter, N. A. Coordination (Ag+) Ion Spray-Mass Spectrometry of Peroxidation Products of Cholesterol Linoleate and Cholesterol Arachidonate: High-Performance Liquid Chromatography-Mass Spectrometry Analysis of Peroxide Products from Polyunsaturated Lipid Autoxidation. J. Am. Chem. Soc. 2000, 122, 8042–8055.
Morrow, J. D.; Chen, Y.; Brame, C. J.; Yang, J.; Sanchez, S. C.; Zu, J.; Zackert, W. E.; Awad, J. A.; Roberts, L. J. The Isoprostanes: Unique Prostaglandin-Like Products of Free-Radical-Initiated Lipid Peroxidation. Drug Metab. Rev. 1999, 31, 117–139.
Funk, M. O.; Isaac, R.; Porter, N. A. Preparation and Purification of Lipid Hydroperoxides from Arachidonic and g-Linolenic Acids. Lipids 1976, 11, 113–117.
Porter, N. A.; Logan, J.; Kontoyiannidou, V. Preparation and Purification of Arachidonic Acid Hydroperoxides of Biological Importance. J. Org. Chem. 1979, 44, 3177–3181.
MacMillan, D. K.; Murphy, R. C. Analysis of Lipid Hydroperoxides and Long-Chain Conjugated Keto Acids by Negative Ion Electrospray Mass Spectrometry. J. Am. Soc. Mass. Spectrom. 1995, 6, 1190–1201.
Hall, L. M.; Murphy, R. C. Electrospray Mass Spectrometric Analysis of 5-Hydroperoxy and 5-Hydroxyeicosatetraenoic Acids Generated by Lipid Peroxidation of Red Blood Cell Ghost Phospholipids. J. Am. Soc. Mass. Spectrom. 1998, 9, 527–532.
Teesh, L. M.; Adams, J. Org. Mass. Spectrom. 1992, 27, 931–943.
Mallis, L. M.; Russell, D. H. Fast Atom Bombardment-Tandem Mass Spectrometry Studies of Organo-Alkali Metal Ions of Small Peptides. Anal. Chem. 1986, 58, 1076–1080.
Hu, P.; Gross, M. L. Strong Interactions of Anionic Peptides and Alkaline Earth Metal Ions: Metal-Ion-Bound Peptides in the Gas Phase. J. Am. Chem. Soc. 1992, 114, 9153–9160.
Yin, H.; Havrilla, C. M.; Morrow, J. D.; Porter, N. A. Formation of Isoprostane Bicyclic Endoperoxides from the Autoxidation of Cholesteryl Arachidonate. J. Am. Chem. Soc. 2002, 124, 7745–7754.
Milne, G. L.; Porter, N. A. Separation and Idenfication of Phospholipid Peroxidation Products. Lipids 2001, 36, 1265–1275.
Yin, H.; Hachey, D. L.; Porter, N. A. Analysis of Diacyl Peroxides by Ag+ Coordination Ionspray Tandem Mass Spectrometry: Free Radical Pathways of Complex Decomposition. J. Am. Soc. Mass. Spectrom. 2001, 12, 449–455.
Waugh, R. J.; Morrow, J. D.; Roberts, L. J. Identification and Relative Quantitation of F2-Isoprostane Regioisomers Formed in Vivo in the Rat. Free Rad. Biol. Med. 1997, 23, 943–954.
Kim, S.; Kim, Y. C.; Lee, J. I. A New Convenient Method for the Esterification of Carboxylic Acids. Tet. Lett. 1983, 24, 3365–3368.
Frimer, A. A. The Reaction of Singlet Oxygen with Olefins: The Question of Mechanism. Chem. Rev. 1979, 79, 359–387.
Bayer, E.; Gfrorer, P.; Rentel, C. Coordination-Ionspray-MS (CIS-MS), a Universal Detection and Characterization Method for Direct Coupling with Separation Techniques. Angew. Chem. Int. Ed. 1999, 38, 992–995.
Beck, W.; Sunkel, K. Metal Complexes of Weakly Coordinating Anions. Precursors of Strong Cationic Organometallic Lewis Acids. Chem. Rev. 1988, 88, 1405–1421.
Su, C.; Kuraoka, K.; Yazawa, T. Increasing the Stability of Silver(I) Ions in Inorganic-Organic Hybrid Membranes for C2H4/C2H6 Separation by using Weakly Self-Coordinating Anions of the Silver Salts. J. Mater. Sci. Lett. 2002, 21, 525–527.
Lancashire, R. J.; Silver, Comprehensive Coordination Chemistry: The Synthesis, Reactions, Properties, and Applications of Coordination Compounds; Wilkinson, G.; Gillard, R. D.; McCleverty, J. A., Eds.; Pergamon Press: New York, 1987; 818–821.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online June 18, 2003
Rights and permissions
About this article
Cite this article
Seal, J.R., Havrilla, C.M., Porter, N.A. et al. Analysis of unsaturated compounds by Ag+ coordination ionspray mass spectrometry: Studies of the formation of the Ag+/lipid complex. J Am Soc Mass Spectrom 14, 872–880 (2003). https://doi.org/10.1016/S1044-0305(03)00339-8
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(03)00339-8