Molecular analysis of intact preen waxes of Calidris canutus (Aves: Scolopacidae) by gas chromatography/mass spectrometry |
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Authors: | Marlèn H A Dekker Theunis Piersma Jaap S Sinninghe Damsté |
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Affiliation: | (1) Department of Marine Biogeochemistry and Toxicology, Netherlands Institute for Sea Research, 1790 AB Den Burg, P.O. Box 59, Texel, The Netherlands;(2) Department of Marine Ecology, Netherlands Institute for Sea Research, 1790 AB Den Burg, P.O. Box 59, Texel, The Netherlands;(3) Centre for Ecological and Evolutionary Studies, University of Groningen, Groningen, The Netherlands |
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Abstract: | The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the
molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing additional resolution
to the analysis of wax esters. The C21−C32 wax esters are composed of complex mixtures of hundreds of individual isomers. The odd carbon-numbered wax esters are predominantly
composed of even carbon-numbered n-alcohols (C14, C16, and C18) esterified predominantly with odd carbon-numbered 2-methyl fatty acids (C7, C9, C11, and C13), resulting in relatively simple distributions. The even carbon-numbered wax esters show a far more complex distribution
due to a number of factors: (i) Their n-alcohol moieties are not dominated by even carbon-numbered n-alcohol moieties are not dominated by even carbon-numbered n-alcohols esterified with odd carbon-numbered 2-methyl fatty acids, but odd and even carbon-numbered n-alcohols participate in approximately equal amounts; (ii) odd carbon-numbered methyl-branched alcohols participate abundantly
in these wax ester clusters; and (iii) with increasing molecular weight, various isomers of the 2,6-, 2,8-, and 2,10-dimethyl
branched fatty acids also participate in the even carbon-numbered wax esters. The data demonstrate that there is a clear biosynthetic
control on the wax ester composition although the reasons for the complex chemistry of the waxes are not yet understood. |
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