Identification, quantification and comparison of major non‐polar lipids in normal and dry eye tear lipidomes by electrospray tandem mass spectrometry

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Abstract
Millions of individuals suffer from a health condition known as keratoconjunctivitis sicca (KCS, also known as ‘dry eye’). Studies have indicated that the lipids in the tear film layer, which covers the outer portion of the eye, may be directly correlated with the existence of dry eye syndrome. By identifying and comparing the major, non‐polar lipids in normal eye tears with a dry eye model, it may be possible to identify a symptom of, or a contributing factor to, dry eye. Electrospray tandem mass spectrometry (ES‐MS/MS) was used to identify and compare the non‐polar lipids, detected as lithium adducts, from normal and dry eye tear samples obtained from rabbits. A limited number of normal human tear samples were also examined for lipid content, and a close resemblance to rabbit was observed. Three distinct regions were delineated in the ES mass spectra of the non polar lipids, m/z 20–500, 500–800 and 800–1100. A common feature noted among identified lipid components was a glycerol backbone with fatty acyl substituents attached. Product ion spectra were obtained for lithiated monoacyl‐, 1,2‐ and 1,3‐diacyl‐ and triacylglyceride standards. Newly proposed structures and fragmentation pathways for the major product ions are presented for the 1,2‐ and 1,3‐diglycerides, and also for the monoglyceride. New approaches to distinguishing asymmetric 1,2‐diglycerides and 1,2‐ from 1,3‐diglycerides are proposed. For the rabbit tear samples, the m/z 20–500 range contains monoester diols with empirical formulas CnH2nO4, the m/z 500–800 range includes diesters with empirical formulas CnH2n−2O5 and the m/z 800–1100 range contains triesters with empirical formulas CnH2n−4O6. Also found in the extracts were three isoprene acetals (terpenoids). Copyright © 2004 John Wiley & Sons, Ltd.