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Reaction of ionised steryl esters with ozone in the gas phase

Hancock, Sarah E., Maccarone, Alan T., Poad, Berwyck L.J., Trevitt, Adam J., Mitchell, Todd W., Blanksby, Stephen J.
Chemistry and physics of lipids 2019 v.221 pp. 198-206
bioactive compounds, carbon, cations, chemical bonding, cholesterol, cholesteryl esters, gases, ionization, liquid-air interface, lithium, oleic acid, ozone, ozonolysis, sebum, sodium, stearic acid, steroid hormones
Cholesterol is an ubiquitous membrane lipid, that also serves as a precursor to many steroid hormones. The 5,6 carbon-carbon double bond on the tetracyclic carbon backbone of cholesterol is an attractive target for ozone with the reaction giving rise to a wide range of possibly bioactive molecules. Despite this, little is known about the ozonolysis of cholesterol esters, which often possess an additional double bond(s) on the fatty acyl chain. Understanding the intrinsic gas phase reaction of ozone with the two disparate double bond positions on cholesteryl esters can inform our understanding of these processes in vivo, particularly reactions occurring at the air-water interface (e.g., tear film lipid layer) and on the surfaces of the body where these cholesterol and cholesteryl esters may be present (e.g., sebum). In the present work we describe the gas phase ozonolysis of lithium and sodium cations formed from three steryl esters: two isomeric for double bond position (cholestanyl oleate and cholesteryl stearate), and a third with carbon-carbon double bonds present in both the sterol ring system and fatty acyl chain (cholesteryl oleate). We confirm the enhanced reactivity of the endocyclic carbon-carbon double bond with ozone over double bonds present in the acyl chain, and elucidate competitive interactions between the two double bond positions during ozonolysis. Elucidation of the mechanisms underlying this interaction is important for both understanding these processes in vivo and for deploying ozonolysis chemistry in analytical strategies for lipidomics.