Structural analysis by reductive cleavage with LiAlH<sub>4</sub> of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon <i>Methanopyrus kandleri</i>

Nishihara , Masateru; Morii , Hiroyuki; Matsuno , Koji; Ohga , Mami; Stetter , Karl  O.; Koga , Yosuke

doi:https://doi.org/10.1155/2002/682753

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Volume 1 | Article ID 682753 | https://doi.org/10.1155/2002/682753

Structural analysis by reductive cleavage with LiAlH₄ of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri

Masateru Nishihara ,¹Hiroyuki Morii ,¹Koji Matsuno ,²Mami Ohga ,¹Karl O. Stetter ,³and Yosuke Koga ¹

Received10 Jan 2002

Accepted23 Apr 2002

Abstract

A choline-containing phospholipid (PL-4) in Methanopyrus kandleri cells was identified as archaetidylcholine, which has been described by Sprott et al. (1997). The PL-4 consisted of a variety of molecular species differing in hydrocarbon composition. Most of the PL-4 was acid-labile because of its allyl ether bond. The identity of PL-4 was confirmed by thin-layer chromatography (TLC) followed by positive staining with Dragendorff-reagent and fast-atom bombardment–mass spectrometry. A new method of LiAlH₄ hydrogenolysis was developed to cleave allyl ether bonds and recover the corresponding hydrocarbons. We confirmed the validity of the LiAlH₄ method in a study of the model compound synthetic unsaturated archaetidic acid (2,3-di-O-geranylgeranyl-sn-glycerol-1-phosphate). Saturated ether bonds were not cleaved by the LiAlH₄ method. The hydrocarbons formed following LiAlH₄ hydrogenolysis of PL-4 were identified by gas–liquid chromatography and mass spectrometry. Four kinds of hydrocarbons with one to four double bonds were detected: 47% of the hydrocarbons had four double bonds; 11% had three double bonds; 14% had two double bonds; 7% had one double bond; and 6% were saturated species. The molecular species composition of PL-4 was also estimated based on acid lability: 77% of the molecular species had two acid-labile hydrocarbons; 11% had one acid-labile and one acid-stable hydrocarbon; and 11% had two acid-stable hydrocarbons. To our knowledge, this is the first report of a specific chemical degradation method for the structural analysis of allyl ether phospholipid in archaea.

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Copyright © 2002 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Structural analysis by reductive cleavage with LiAlH4 of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri

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Structural analysis by reductive cleavage with LiAlH₄ of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri