Identification of 0 - Alkyldihydroxyacetone Phosphate , O - Alkyldihydroxyacetone , and Diacyl Glyceryl
نویسنده
چکیده
0-Alkyldihydroxyacetone-P and 0-alkyldihydroxyacetone were identified as intermediates in the biosynthesis of Oalkyl-linked lipids. The substrates for the initial reaction are dihydroxyacetone-P and fatty alcohols, and the cofactor requirements are coenzyme A, ATP, and Mg++. The enzyme complex that carries out this reaction was found in microsomes of preputial gland tumors. The keto-intermediates were identified by thin layer and gas-liquid chromatography of derivatives and standards prepared by the following techniques: LiAlH4 reduction, periodate oxidation before and after LiAlH4 reduction, acid and alkaline hydrolysis, and removal of the phosphate moiety by bacterial alkaline phosphatase. We analyzed the fatty alcohols and 0-alkyl ethylene glycols resulting from these treatments as the acetates; the 0-alkylglycerols were identified as the isopropylidene derivatives. Both keto-intermediates can be enzymically reduced with NADPH. After reduction of the ketone group of the phosphorylated intermediate, acylation can result in the formation of diacyl glyceryl ethers.
منابع مشابه
Biosynthesis of an O-alkyl analogue of phosphatidic acid and O-alkylglycerols via O-alkyl ketone intermediates by microsomal enzymes of Ehrlich ascites tumor.
Microsomal enzymes from Ehrlich ascites tumors synthesized 0-alkyl glyceryl ethers from hexadecanol and dihydroxyacetone phosphate in the presence of ATP, CoA, and Mg++. Glyceryl ether synthesis occurred via the formation of 0-alkyldihydroxyacetone phosphate and O-alkyldihydroxyacetone. Although NADPH inhibited the initial reaction of dihydroxyacetone phosphate with fatty alcohol, it was requir...
متن کاملReductase, phosphatase, and kinase activities in the metabolism of alkyldihydroxyacetone phosphate and alkyldihydroxyacetone.
متن کامل
Enzymic synthesis of O-alkyl bonds in glycerolipids.
We have found that 0-alkyl bonds in glycerolipids are synthesized by microsomal enzymes of preputial gland tumors when diiydroxyacetone-P or glyceraldehyde-3-P and 1 J4C long chain fatty alcohols are used as substrates; ATP, coenzyme A, and Mg++ are essential cofactors. The 0-alkyl moieties formed from the 1-“Cand 9,10-3H-labeled long chain fatty alcohols show that the fatty alcohol chains are ...
متن کاملBiosynthesis of glycerolipids via acyldihydroxyacetone phosphate.
Acyldihydroxyacetone phosphate was first discovered as a lipid rapidly labelled by ’’Pi or by [p”P]ATP in guinea-pig liver mitochondria (Hajra & Agranoff, 1967,1968). This rapid labelling was due to the dephosphorylation and rephosphorylation of endogenous acyldihydroxyacetone phosphate in mitochondria (Hajra et al., 1968). Acyldihydroxyacetone phosphate was shown to be biosynthesized by the di...
متن کاملThe role of acyldihydroxyacetone phosphate, reduced nicotinamide adenine dinucleotide, and reduced nicotinamide adenine dinucleotide phosphate in the biosynthesis of O-alkyl glycerolipids by microsomal enzymes of Ehrlich ascites tumor.
Pahnitoyl dihydroxyacetone phosphate and [1-14C]hexadecanol were found to serve as precursors of 0-alkyl lipids in a microsomal system from Ehrlich ascites tumor. Both acyldihydroxyacetone phosphate and dihydroxyacetone phosphate were tested. The system required no CoA when acyldihydroxyacetone phosphate was used as the glycerol source, and significantly lower concentrations of acyldihydroxyace...
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تاریخ انتشار 2003