The Source of Oxygen in the Ether Bond of Glycerolipids

Snyder, Fred; Rainey, W.T.; Blank, Merle L.; Christie, W. H.

doi:10.1016/s0021-9258(18)62731-0

Cited by 71 publications

(7 citation statements)

References 20 publications

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“…Thus, there appears to be a specific incorporation of the methylene-interrupted dienoic and trienoic acids into the ether-linked core of cutin, suggesting that the ds-1,4pentadiene structure may be involved in the formation of ether bonds in cutin. One possible route of synthesis could involve displacement of an acyl function from in-chain esterified -ketol, produced by the action of lipoxygenase and hydroperoxide isomerase on linoleic acid (Veldink et al, 1970(Veldink et al, , 1972Zimmerman, 1966) in a manner similar to that observed in glyceryl ether biosynthesis (Hajra, 1970;Snyder et al, 1970;Friedberg and Heifetz, 1973), although a more nonspecific radical mechanism cannot be ruled out.…”

Section: 0mentioning

confidence: 99%

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ¹²-unsaturated analogs

Kolattukudy¹,

Walton²,

Kushwaha³

1973

Biochemistry

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Section: 0mentioning

confidence: 99%

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ¹²-unsaturated analogs

Kolattukudy¹,

Walton²,

Kushwaha³

1973

Biochemistry

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“…Concurrently, the pro-R hydrogen at the carbon of DHAP esterified to the fatty acid (DHAP C-l) is exchanged with the medium (Friedberg et al, 1971(Friedberg et al, , 1972. Another feature of the reaction is the donation of the oxygen in the ether linkage by the fatty alcohol (Snyder et al, 1970); both oxygens in the fatty acyl ester of acyl-DHAP are lost during the formation…”

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confidence: 99%

Alkyldihydroxyacetone phosphate synthase mechanism: oxygen-18 studies of fatty acid release from acyldihydroxyacetone phosphate

et al. 1985

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Alkyldihydroxyacetonephosphate synthase (alkyl-DHAP synthase) catalyzes the exchange of the ester-linked fatty acid of 1-O-acyldihydroxyacetone phosphate (1-O-acyl-DHAP) for a fatty alcohol that is attached in an ether linkage to form 1-O-alkyldihydroxyacetone phosphate (1-O-alkyl-DHAP). In our continuing investigation of the mechanism of this enzyme, we have examined the fatty acid released during the reaction. In contrast to the reports of others using whole microsomes, we found that the cleavage of fatty acid by purified preparations of alkyl-DHAP synthase was dependent on the presence of the cosubstrate, fatty alcohol. Furthermore, the amount of fatty acid produced was equivalent to the alkyl-DHAP formed. Our previously proposed detailed mechanism for alkyl-DHAP synthase predicted that the fatty acid should retain both of the carboxyl ester oxygens upon cleavage. Reactions carried out with palmitoyl-[18O]DHAP as substrate yielded [18O]palmitic acid as the product in agreement with this scheme.

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“…In another series of experiments we have shown that tritiated dihydroxyacetone phosphate yields tritiated acyldihydroxyacetone (via acyldihydroxyacetone phosphate) T A he known steps m O-alkyl-DHAP1 synthesis include the initial formation of acyl-DHAP from fatty acid and DHAP in the presence of ATP, magnesium, and coenzyme A. Acyl-DHAP, hexadecanol, ATP, and magnesium then interact to form O-alkyl-DHAP (Hajra, 1970;Wykle et al, 1972). In this process it is known that the oxygen of hexadecanol is retained in the product (Snyder et al, 1970).When [1,3-3H]dihydroxyacetone phosphate is incorporated enzymatically into O-alkyl lipids, there is a loss of half of the tritium atoms from C-32 (Friedberg et al, 1971). Since there is no net loss of hydrogen in the product, the findings point to an exchange reaction.…”

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Hydrogen exchange in the synthesis of glyceryl ether and in the formation of dihydroxyacetone in Tetrahymena pyriformis

Friedberg¹,

Heifetz²

1973

Biochemistry

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We have previously shown that [l,3-3H]dihydroxyacetone phosphate is incorporated enzymatically into O-alkyl lipids with the loss of one tritium from C-3. Further evidence for a tritium exchange has been presented in this investigation by showing, in a microsomal system from Tetrahymena pyriformis, that tritiated O-alkyl lipids are formed in the presence of tritiated water from dihydroxyacetone phosphate and hexadecanol. In another series of experiments we have shown that tritiated dihydroxyacetone phosphate yields tritiated acyldihydroxyacetone (via acyldihydroxyacetone phosphate) T A he known steps m O-alkyl-DHAP1 synthesis include the initial formation of acyl-DHAP from fatty acid and DHAP in the presence of ATP, magnesium, and coenzyme A. Acyl-DHAP, hexadecanol, ATP, and magnesium then interact to form O-alkyl-DHAP (Hajra, 1970;Wykle et al., 1972). In this process it is known that the oxygen of hexadecanol is retained in the product (Snyder et al., 1970).When [1,3-3H]dihydroxyacetone phosphate is incorporated enzymatically into O-alkyl lipids, there is a loss of half of the tritium atoms from C-32 (Friedberg et al., 1971). Since there is no net loss of hydrogen in the product, the findings point to an exchange reaction. It is also known that this reaction is specific for the same hydrogen lost in the triosephosphate isomerase reaction, but not the one lost in the fructose-1,6diphosphate aldolase reaction (Friedberg et al., 1972).The present investigation was undertaken to obtain more information on the nature of the hydrogen loss which occurs in the formation of O-alkyl lipids. Evidence will be presented to show that the tritium lost from [1,3-3H]dihydroxyacetone phosphate is exchanged with a hydrogen from the aqueous environment and that this exchange occurs on C-3 of the dihydroxyacetone phosphate moiety. It will also be shown that the hydrogen loss depends on the presence of coenzyme A, that acyldihydroxyacetones are formed without loss of hydrogen, and that the number of hydrogen atoms exchanged greatly exceeds the number of moles of O-alkyl lipid formed. The difference is in part or entirely accounted for by the formation of dihydroxyacetone. The formation of this compound also involves a hydrogen exchange. This finding will be discussed.

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The Source of Oxygen in the Ether Bond of Glycerolipids

Cited by 71 publications

References 20 publications

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ¹²-unsaturated analogs

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ¹²-unsaturated analogs

Alkyldihydroxyacetone phosphate synthase mechanism: oxygen-18 studies of fatty acid release from acyldihydroxyacetone phosphate

Hydrogen exchange in the synthesis of glyceryl ether and in the formation of dihydroxyacetone in Tetrahymena pyriformis

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The Source of Oxygen in the Ether Bond of Glycerolipids

Cited by 71 publications

References 20 publications

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ12-unsaturated analogs

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ12-unsaturated analogs

Alkyldihydroxyacetone phosphate synthase mechanism: oxygen-18 studies of fatty acid release from acyldihydroxyacetone phosphate

Hydrogen exchange in the synthesis of glyceryl ether and in the formation of dihydroxyacetone in Tetrahymena pyriformis

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Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ¹²-unsaturated analogs

Biosynthesis of the C18 family of cutin acids. ι-Hydroxyoleic acid, ι-hydroxy-9,10-epoxystearic acid, 9,10,18-trihydroxystearic acid, and their Δ¹²-unsaturated analogs