Structural complexity in isoprenoid glycerol dialkyl glycerol tetraether lipid cores of Sulfolobus and other archaea revealed by liquid chromatography–tandem mass spectrometry

Knappy, Chris S.; Barillà, Daniela; Blaquiere, J.P.A. de; Morgan, Hugh W.; Nunn, Charlotte E.M.; Suleman, Muhammad; Tan, C.H.W.; Keely, Brendan J.

doi:10.1016/j.chemphyslip.2012.06.009

Cited by 8 publications

(43 citation statements)

References 51 publications

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“…Several recent studies have explored ether lipid diversity in archaeal cultures, soils and sediments, revealing novel and overlooked lipids that have the potential to serve as more informative archaeal biomarkers . Most studies relied on the use of liquid chromatography‐tandem mass spectrometry (LC‐MS/MS), which allows structural features of the lipids to be inferred, even for minor and co‐eluting components that are not readily amenable to nuclear magnetic resonance (NMR) . Among the compounds revealed were higher homologues of the C 86 tetraethers, including variants containing homo‐ or dihomoglycerol groups (e.g.…”

Section: Introductionmentioning

confidence: 99%

Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance

et al. 2015

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Higher homologues of widely reported C(86) isoprenoid diglycerol tetraether lipid cores, containing 0-6 cyclopentyl rings, have been identified in (hyper)thermophilic archaea, representing up to 21% of total tetraether lipids in the cells. Liquid chromatography-tandem mass spectrometry confirms that the additional carbon atoms in the C(87-88) homologues are located in the etherified chains. Structures identified include dialkyl and monoalkyl ('H-shaped') tetraethers containing C(40-42) or C(81-82) hydrocarbons, respectively, many representing novel compounds. Gas chromatography-mass spectrometric analysis of hydrocarbons released from the lipid cores by ether cleavage suggests that the C(40) chains are biphytanes and the C(41) chains 13-methylbiphytanes. Multiple isomers, having different chain combinations, were recognised among the dialkyl lipids. Methylated tetraethers are produced by Methanothermobacter thermautotrophicus in varying proportions depending on growth conditions, suggesting that methylation may be an adaptive mechanism to regulate cellular function. The detection of methylated lipids in Pyrobaculum sp. AQ1.S2 and Sulfolobus acidocaldarius represents the first reported occurrences in Crenarchaeota. Soils and aquatic sediments from geographically distinct mesotemperate environments that were screened for homologues contained monomethylated tetraethers, with di- and trimethylated structures being detected occasionally. The structural diversity and range of occurrences of the C(87-89) tetraethers highlight their potential as complementary biomarkers for archaea in natural environments.

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Section: Introductionmentioning

confidence: 99%

Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance

et al. 2015

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“…Structural analysis of archaeal lipids has mainly been focused on characterizing either the molecular details of core structures at high structural resolution or the intact lipids but with a lower level of structural resolution. High‐resolution structural characterization of core structures has typically been performed using workflows requiring large amounts of sample, several purification steps and chemical derivatization to remove head groups for subsequent analysis by nuclear magnetic resonance spectroscopy, thin‐layer chromatography and liquid chromatography‐mass spectrometry . These cumbersome approaches have been used to elucidate the stereochemistry of glycerol moieties in core structures as well as to determine the position of methyl groups and cyclopentane moieties in isoprenoid chains .…”

Section: Introductionmentioning

confidence: 99%

“…High‐resolution structural characterization of core structures has typically been performed using workflows requiring large amounts of sample, several purification steps and chemical derivatization to remove head groups for subsequent analysis by nuclear magnetic resonance spectroscopy, thin‐layer chromatography and liquid chromatography‐mass spectrometry . These cumbersome approaches have been used to elucidate the stereochemistry of glycerol moieties in core structures as well as to determine the position of methyl groups and cyclopentane moieties in isoprenoid chains . The structural characterization of intact archaeal lipids has been performed using both shotgun lipidomics and chromatography‐mass spectrometry‐based approaches .…”

Section: Introductionmentioning

confidence: 99%

“…These approaches typically require a relatively small amount of sample and a short time of analysis but provide data with limited structural information, which, to varying extends, only allows inferring putative head group structures, the total number of carbon atoms and cyclopentane moieties or double bonds in the core structure and occasionally the position of structural features provided that high‐quality synthetic standards are available as a reference. Employing such lipidomics approaches have successfully been used for mapping microbial communities in environmental samples and the lipid composition of Archaea in culture . However, so far no high‐resolution lipidomics approach has been deployed for detailed lipid profiling of Archaea.…”

Section: Introductionmentioning

confidence: 99%

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Structural characterization of ether lipids from the archaeonSulfolobus islandicusby high-resolution shotgun lipidomics

et al. 2015

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The molecular structures, biosynthetic pathways and physiological functions of membrane lipids produced by organisms in the domain Archaea are poorly characterized as compared with that of counterparts in Bacteria and Eukaryota. Here we report on the use of high-resolution shotgun lipidomics to characterize, for the first time, the lipid complement of the archaeon Sulfolobus islandicus. To support the identification of lipids in S. islandicus, we first compiled a database of ether lipid species previously ascribed to Archaea. Next, we analyzed the lipid complement of S. islandicus by high-resolution Fourier transform mass spectrometry using an ion trap-orbitrap mass spectrometer. This analysis identified five clusters of molecular ions that matched ether lipids in the database with sub-ppm mass accuracy. To structurally characterize and validate the identities of the potential lipid species, we performed structural analysis using multistage activation on the ion trap-orbitrap instrument as well as tandem mass analysis using a quadrupole time-of-flight machine. Our analysis identified four ether lipid species previously reported in Archaea, and one ether lipid species that had not been described before. This uncharacterized lipid species features two head group structures composed of a trisaccharide residue carrying an uncommon sulfono group (-SO3) and an inositol phosphate group. Both head groups are linked to a glycerol dialkyl glycerol tetraether core structure having isoprenoid chains with a total of 80 carbon atoms and 4 cyclopentane moieties. The shotgun lipidomics approach deployed here defines a novel workflow for exploratory lipid profiling of Archaea.

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“…Structural studies on archaeal lipids using ESI with tandem quadrupole and with ion-trap instruments coupled with HPLC have been reported [9,16–20]. Among them, Yoshinaga et al conducted a systematic study on a variety of archaeal lipids ionized as the [M + H] + and [M + NH 4 ] + ions by ESI, unveiling the fragmentation patterns useful for characterization of novel lipid structures [17].…”

Section: Introductionmentioning

confidence: 99%

Structural studies on archaeal phytanyl-ether lipids isolated from membranes of extreme halophiles by linear ion-trap multiple-stage tandem mass spectrometry with electrospray ionization

Hsu

Lobasso

Turk

et al. 2013

Analytica Chimica Acta

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The structures of archaeal glycerophospholipids and glycolipids are unique in that they consist of phytanyl substituents ether linked to the glycerol backbone, imparting stability to the molecules. In this contribution, we described multiple-stage linear ion-trap combined with high resolution mass spectrometry toward structural characterization of this lipid family desorbed as lithiated adduct ions or as the [M –H]− and [M – 2H]2− ions by ESI. MSn on various forms of the lithiated adduct ions yielded rich structurally informative ions leading to complete structure identification of this lipid family, including the location of the methyl branches of the phytanyl chain. By contrast, structural information deriving from MSn on the [M –H]− and [M – 2H]2− ions is not complete. The fragmentation pathways in an ion-trap, including unusual internal loss of glycerol moiety and internal loss of hexose found for this lipid family were proposed. This mass spectrometric approach provides a simple tool to facilitate confident characterization of this unique lipid family.

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Structural complexity in isoprenoid glycerol dialkyl glycerol tetraether lipid cores of Sulfolobus and other archaea revealed by liquid chromatography–tandem mass spectrometry

Cited by 8 publications

References 51 publications

Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance

Mono‐, di‐ and trimethylated homologues of isoprenoid tetraether lipid cores in archaea and environmental samples: mass spectrometric identification and significance

Structural characterization of ether lipids from the archaeonSulfolobus islandicusby high-resolution shotgun lipidomics

Structural studies on archaeal phytanyl-ether lipids isolated from membranes of extreme halophiles by linear ion-trap multiple-stage tandem mass spectrometry with electrospray ionization

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