Squid oil is a good source for ethyl esters enriched in DHA. As usually with marine oils, ethyl esters undergo winterization. The stearin obtained from cold filtration is a mixture of relatively high melting point mostly saturated compounds. Stearin from squid ethyl esters released a solid material upon treatment with methanol. This was characterized as a mixture of 1‐O‐alkylglycerols. Replacing methanol precipitation with chromatographic separation of stearin gave the same results, ruling out preferential precipitation. Alkyl chains of 1‐O‐alkylglycerols are C16:0 preponderantly, C14:0, C18:0, and traces of C15:0 and C17:0. No unsaturated alkyl chains were detected by GC‐MS and 13C‐NMR. However, 1‐O‐alkylglycerols were not detected in crude squid oil. They were contained in the crude oil mainly in the form of 1‐O‐alkyl‐2,3‐diacylglycerols and lesser amounts of plasmanyl‐phospholipids. The alkyl chain distribution recalls the result found in the case of acyl chains of cholesteryl esters in crude squid oil. These findings suggest that the biochemical build‐up of 1‐O‐alkylglycerols and cholesteryl esters in squid follows a common compartmented pathway, different than the metabolism of glycerides, rich in mono‐ and polyunsaturated fatty acid. A hypothesis is put forward based on the fatty alcohol cycle.Practical applications: Ethyl esters from squid crude oil are enriched by short path distillation to give ethyl esters containing high amounts of DHA. As a part of usual processes leading to omega‐3 concentrated marine oils, enriched ethyl esters undergo winterization. During this step, ethyl esters with relatively high melting point are crystallized at low temperature and removed by filtration. The usual effect of winterization is to contribute to a slight further enrichment in polyunsaturated compounds. The present work shows that winterization also contributes in removing 1‐O‐alkylglycerols, produced from 1‐O‐alkyl‐2,3‐diacylglycerols during ethanolysis of squid oil. A smaller part of 1‐O‐alkylglycerols is contained in the starting squid oil in the form of plasmanyl‐phospholipids, which are likely removed during initial degumming.A gas chromatogram of fatty acid methyl esters from squid cholesteryl esters (top) compared to a gas chromatogram of isopropylidene derivatives from squid 1‐O‐alkylglycerols (down).
Read full abstract