Positive and negative tandem mass spectrometric fingerprints of lipids from the halophilic Archaea Haloarcula marismortui.
Lipids from the extremely halophilic Archaea, Haloarcula marismortui, contain abundant phytanyl diether phospholipids, namely archaetidic acid (AA), archaetidylglycerol (AG), archaetidylglycerosulfate (AGS), with mainly archaetidylglycerophosphate methyl ester (AGP-Me). These were accompanied by a triglycosyl archaeol (TGA), lacking characteristic sulfate groups. Tandem-mass spectrometry was employed to provide fingerprints for identifying these known lipids, as well as small amounts of unsaturated phospholipids. These contained 3 and 6 double bonds in their archaeol moiety, suggested by negative tandem-MS of intact phospholipids, as indicated by differences between their pseudo-molecular ion and specific fragment ions designated as pi(2). The core ether lipids were confirmed by electrospray ionization mass spectrometry (ESI-MS) as 2,3-di-O-phytanyl-sn-glycerol (C20, C20), which gave rise to a precursor-ion at m/z 660 [M+Li](+), and its fragment ion at m/z 379 [M+Li](+), consistent with mono-O-phytanyl-glycerol. Furthermore, lithiated ions at m/z 654 (MS(1)), 379 (MS(2)) and m/z 648 (MS(1)), 373 (MS(2)), combined with (1)H/(13)C NMR chemical shifts at delta 5.31-121.6 (C2/2'-H2/2'), 5.08-124.9 (C6/6'-H6/6') and 5.10-126.0 (10/10'-H10/10') confirmed the presence of unsaturated homologs of archaeol. We carried out a comprehensive study on the lipids present in cells of H. marismortui. We used positive and negative ESI-MS with tandem-MS, which served as a fingerprint analysis for identifying the majority of component lipids.
de Souza
Lauro M
LM
Departamento de Bioquímica e Biologia Molecular, Universidade Federal do Paraná, Curitiba-PR, Brazil.
Müller-Santos
Marcelo
M
Iacomini
Marcello
M
Gorin
Philip A J
PA
Sassaki
Guilherme L
GL
D004987:Ethers / Q000737:chemistry; D005995:Glyceryl Ethers / Q000032:analysis*; D019614:Haloarcula marismortui / Q000737:chemistry*; D008055:Lipids / Q000032:analysis*; D015394:Molecular Structure; D010743:Phospholipids / Q000032:analysis*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D053719:Tandem Mass Spectrometry / Q000379:methods*
D004987:Ethers; D005995:Glyceryl Ethers; D008055:Lipids; D010743:Phospholipids; C094417:archaeol lipid