Degradation of sphingosine, dihydrosphingosine, and phytosphingosine in rats

Barenholz, Yechezkel; Gátt, Shimon

doi:10.1021/bi00847a023

Cited by 18 publications

(3 citation statements)

References 27 publications

(28 reference statements)

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“…Starting from the alcohol 7, a straightforward synthesis 20 of (6R,7R)- [4,5,6, H 2 ]palmitic acid 14, an alternative metabolic probe for the analysis of the stereochemical course of sphinganine desaturation (cf. Scheme 1), was also realised.…”

Section: Methodsmentioning

confidence: 99%

“…The additional deuterium atoms in a metabolic inert position are of particular value in those cases where both hydrogen atoms are simultaneously removed from C-6 and C-7 of the metabolic probe, for example in syn-eliminations leading to (Z)-olefins. 20a As the biosynthesis of many lepidopteran pheromones starts from palmitic acid, 23 the labelled (6R,7R)- [4,5,6, H 2 ]palmitoate (14) not only represents a valuable tool to unravel the stereochemical course of the phytosphingenine biosynthesis, but also to gain information on the stereochemical course of hitherto unexplored D 6 -desaturases from insects 24 and plants. 25 All reactions were carried out under argon using standard gastight syringes, cannulas and septa.…”

Section: Methodsmentioning

confidence: 99%

“…3 Far less is known about the physiological role of the 1,3,4-trihydroxy-2-amino alcohols, the phytosphingolipids, occurring widely in animals (e.g. kidney 4 and liver 5 of human beings), plants and yeasts. 6 Phytosphingosines and sphingosines originate from sphinganine (2) via dihydroceramide (N-acylsphinganine) as a common precursor by either action of a desaturase introducing a (4E)-double bond to yield sphingosines 7 or by action of a hydroxylase placing the characteristic third hydroxy group of phytosphingosines 3a and 3b onto C-4 of dihydroceramide 8 as depicted in Scheme 1.…”

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(6R,7R)-[4,5,6,7-2H4]-Palmitoate and (8S,9R)-[8,9-2H2]-l-erythro-Sphinganine: Probes for the Analysis of the Stereochemical Course of Δ6-Desaturases from Plants and Insects

Thum

Hertweck

Simon³

et al. 1999

Synthesis

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The stereospecifically labelled (6R,7R)- [4,5,6,7-2 H 4 ]-palmitic acid (14) and (8S,9R)- [8, H 2 ]-L-erythro-sphinganine (10) have been prepared in good yield from (E)-[2,3-2 H 2 ]-dodec-2-enoate 5 via biocatalytic reduction with broken cells of Clostridium tyrobutyricum, DSM 1460, and hydrogen gas as the ultimate electron donor. The sphingoid base was assembled from (2R,3R)-dodecyl iodide (8) by cuprate mediated S N 2' type nucleophilic substitution of the serinal-derived oxazolidine vinyl oxirane 4.The sphingoid bases constitute a large group of structurally diverse, biologically important long chain amino alcohols [e.g. (E)-1,3-dihydroxy-2-aminooctadec-4-ene] serving as substructures of membrane components in eukaryotic cells and in a few bacteria. 1 More recently, the importance of sphingolipid metabolites has been recognized. Sphingosine-1-phosphate and ceramide play critical roles as second messengers in regulatory processes and cell signalling such as apoptosis, 2 cell proliferation and survival. 3 Far less is known about the physiological role of the 1,3,4-trihydroxy-2-amino alcohols, the phytosphingolipids, occurring widely in animals (e.g. kidney 4 and liver 5 of human beings), plants and yeasts. 6 Phytosphingosines and sphingosines originate from sphinganine (2) via dihydroceramide (N-acylsphinganine) as a common precursor by either action of a desaturase introducing a (4E)-double bond to yield sphingosines 7 or by action of a hydroxylase placing the characteristic third hydroxy group of phytosphingosines 3a and 3b onto C-4 of dihydroceramide 8 as depicted in Scheme 1.In contrast to animal and yeast cells, plant phytosphingolipids contain an additional E/Z-double bond at C-8 of the aminotriol backbone which is assumed to be relevant for chilling resistance, 9 but nothing is known about the stereochemical course and the molecular mechanism responsible for their formation. Recently, the corresponding enzyme has been cloned and identified as a non-stereoselective D 6 -desaturase introducing the E/Z-double bond into the alkyl chain six carbon atoms remote from the hydroxyl group next to the alkyl chain. 10 As the sequence of hydroxylation and desaturation is not strictly defined (Scheme 1), two compounds, N-acyl-D 8 -phytosphingeBiosynthesis of N-acylphytosphingenines 3a/b from palmitic acid. The sequence of hydroxylation and desaturation of sphinganine 2 may be reversed leading to a mixture of 3a/b. Black dots (•) denote the position of carbon atoms carrying an isotope label (e.g. 2 H or 13 C) introduced by the early precursor palmitic acid Scheme 1Downloaded by: University of Pittsburgh. Copyrighted material.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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(6R,7R)-[4,5,6,7-2H4]-Palmitoate and (8S,9R)-[8,9-2H2]-l-erythro-Sphinganine: Probes for the Analysis of the Stereochemical Course of Δ6-Desaturases from Plants and Insects

Thum

Hertweck

Simon³

et al. 1999

Synthesis

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Mass spectrometric identification of 2-hydroxy-sebacic acid in the urines of patients with neonatal adrenoleukodystrophy and zellweger syndrome

Rocchiccioli

Cartier

Aubourg

et al. 1986

Biol. Mass Spectrom.

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The urines of children with neonatal adrenoleukodystrophy and Zellweger syndrome contained an excess of unusual even- and odd-numbered dicarboxylic acids with a chain length of from 5 to 15 carbon atoms, as well as 2-hydroxy-compounds, including 2-hydroxy-isocaproate, 2-hydroxy-glutarate and 2-hydroxy-sebacate. The latter product, not previously found in metabolic diseases, appears as an additional useful marker of these peroxisomal disorders.

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