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Arsenolipids in oil from blue whiting Micromesistius poutassou--evidence for arsenic-containing esters.

Taleshi MS, Raber G, Edmonds JS, Jensen KB, Francesconi KA - Sci Rep (2014)

Bottom Line: The polar lipid fraction constituting 24% of the total arsenolipid content (which totalled 2.16 μg As/g) contained four known dimethylarsinoyl fatty acids and three known dimethylarsinoyl hydrocarbons.The less polar fraction (ca 30% of the total arsenolipids) contained four new dimethylarsinoyl hydrocarbons with chain lengths 22-30 carbons, in addition to more complex arsenicals that hydrolysed to known dimethylarsinoyl fatty acids suggesting they were conjugated carboxylic acids, presumably esters.The rest of the lipid-soluble arsenic (ca 45% of the total) remained in the non-polar fraction together with the bulk of the fish oil lipids, a complex mixture of compounds that precluded identification of the small amounts of arsenolipids.

View Article: PubMed Central - PubMed

Affiliation: 1] Institute of Chemistry-Analytical Chemistry, University of Graz, Universitaetsplatz 1, 8010 Graz, Austria [2] Department of Marine Chemistry, Faculty of Marine Science, University of Mazandaran, Babolsar, Iran.

ABSTRACT
Arsenic-containing lipids in the oil from the blue whiting fish (Micromesistius poutassou) were separated into three broad polarity groups and investigated by HPLC and mass spectrometry. A total of 11 arsenolipids including 4 new compounds were identified. The polar lipid fraction constituting 24% of the total arsenolipid content (which totalled 2.16 μg As/g) contained four known dimethylarsinoyl fatty acids and three known dimethylarsinoyl hydrocarbons. The less polar fraction (ca 30% of the total arsenolipids) contained four new dimethylarsinoyl hydrocarbons with chain lengths 22-30 carbons, in addition to more complex arsenicals that hydrolysed to known dimethylarsinoyl fatty acids suggesting they were conjugated carboxylic acids, presumably esters. The rest of the lipid-soluble arsenic (ca 45% of the total) remained in the non-polar fraction together with the bulk of the fish oil lipids, a complex mixture of compounds that precluded identification of the small amounts of arsenolipids.

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Four new arsenolipids found in blue whiting oil.These structures were supported by high-resolution accurate mass spectrometry, and, for arsenolipid 444, confirmed by chemical synthesis. As-HC442 and As-HC440 were proposed, by analogy, to possess the same carbon skeletons as As-HC444, but with one or two double bonds in their structures, respectively. The position and geometry of the double bonds in arsenolipids As-HC440, As-HC442 and As-HC542 were not determined; they have been assigned by analogy to commonly occurring non-arsenic lipids in organisms14.
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f2: Four new arsenolipids found in blue whiting oil.These structures were supported by high-resolution accurate mass spectrometry, and, for arsenolipid 444, confirmed by chemical synthesis. As-HC442 and As-HC440 were proposed, by analogy, to possess the same carbon skeletons as As-HC444, but with one or two double bonds in their structures, respectively. The position and geometry of the double bonds in arsenolipids As-HC440, As-HC442 and As-HC542 were not determined; they have been assigned by analogy to commonly occurring non-arsenic lipids in organisms14.

Mentions: Considering these data, and comparison with normal hydrocarbons found in fish, molecular formulas for the compounds were postulated as C25H50AsO (molecular mass 440, two double bonds), C25H52AsO (molecular mass 442, one double bond), C25H54AsO (molecular mass 444, saturated) and C33H56AsO (molecular mass 542, seven double bonds). These molecular formulas were confirmed by accurate mass spectrometry (Table 1; Supplementary material Figs. S4–S7). In addition, the structure of one of the compounds (with molecular mass 444) was confirmed by chemical synthesis and comparison of the mass spectral and chromatographic properties of the natural and synthesised samples (Supplementary material, Figs. S8 & S9). Thus, the four new arsenolipids were assigned structures 8–11 (Fig. 2).


Arsenolipids in oil from blue whiting Micromesistius poutassou--evidence for arsenic-containing esters.

Taleshi MS, Raber G, Edmonds JS, Jensen KB, Francesconi KA - Sci Rep (2014)

Four new arsenolipids found in blue whiting oil.These structures were supported by high-resolution accurate mass spectrometry, and, for arsenolipid 444, confirmed by chemical synthesis. As-HC442 and As-HC440 were proposed, by analogy, to possess the same carbon skeletons as As-HC444, but with one or two double bonds in their structures, respectively. The position and geometry of the double bonds in arsenolipids As-HC440, As-HC442 and As-HC542 were not determined; they have been assigned by analogy to commonly occurring non-arsenic lipids in organisms14.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4265782&req=5

f2: Four new arsenolipids found in blue whiting oil.These structures were supported by high-resolution accurate mass spectrometry, and, for arsenolipid 444, confirmed by chemical synthesis. As-HC442 and As-HC440 were proposed, by analogy, to possess the same carbon skeletons as As-HC444, but with one or two double bonds in their structures, respectively. The position and geometry of the double bonds in arsenolipids As-HC440, As-HC442 and As-HC542 were not determined; they have been assigned by analogy to commonly occurring non-arsenic lipids in organisms14.
Mentions: Considering these data, and comparison with normal hydrocarbons found in fish, molecular formulas for the compounds were postulated as C25H50AsO (molecular mass 440, two double bonds), C25H52AsO (molecular mass 442, one double bond), C25H54AsO (molecular mass 444, saturated) and C33H56AsO (molecular mass 542, seven double bonds). These molecular formulas were confirmed by accurate mass spectrometry (Table 1; Supplementary material Figs. S4–S7). In addition, the structure of one of the compounds (with molecular mass 444) was confirmed by chemical synthesis and comparison of the mass spectral and chromatographic properties of the natural and synthesised samples (Supplementary material, Figs. S8 & S9). Thus, the four new arsenolipids were assigned structures 8–11 (Fig. 2).

Bottom Line: The polar lipid fraction constituting 24% of the total arsenolipid content (which totalled 2.16 μg As/g) contained four known dimethylarsinoyl fatty acids and three known dimethylarsinoyl hydrocarbons.The less polar fraction (ca 30% of the total arsenolipids) contained four new dimethylarsinoyl hydrocarbons with chain lengths 22-30 carbons, in addition to more complex arsenicals that hydrolysed to known dimethylarsinoyl fatty acids suggesting they were conjugated carboxylic acids, presumably esters.The rest of the lipid-soluble arsenic (ca 45% of the total) remained in the non-polar fraction together with the bulk of the fish oil lipids, a complex mixture of compounds that precluded identification of the small amounts of arsenolipids.

View Article: PubMed Central - PubMed

Affiliation: 1] Institute of Chemistry-Analytical Chemistry, University of Graz, Universitaetsplatz 1, 8010 Graz, Austria [2] Department of Marine Chemistry, Faculty of Marine Science, University of Mazandaran, Babolsar, Iran.

ABSTRACT
Arsenic-containing lipids in the oil from the blue whiting fish (Micromesistius poutassou) were separated into three broad polarity groups and investigated by HPLC and mass spectrometry. A total of 11 arsenolipids including 4 new compounds were identified. The polar lipid fraction constituting 24% of the total arsenolipid content (which totalled 2.16 μg As/g) contained four known dimethylarsinoyl fatty acids and three known dimethylarsinoyl hydrocarbons. The less polar fraction (ca 30% of the total arsenolipids) contained four new dimethylarsinoyl hydrocarbons with chain lengths 22-30 carbons, in addition to more complex arsenicals that hydrolysed to known dimethylarsinoyl fatty acids suggesting they were conjugated carboxylic acids, presumably esters. The rest of the lipid-soluble arsenic (ca 45% of the total) remained in the non-polar fraction together with the bulk of the fish oil lipids, a complex mixture of compounds that precluded identification of the small amounts of arsenolipids.

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