The enigmatic structure of the crenarchaeol isomer

Jaap S. Sinninghe Damsté; W. Irene C. Rijpstra; Ellen C. Hopmans; Mimi J. den Uijl; Johan W.H. Weijers; Stefan Schouten

doi:10.1016/j.orggeochem.2018.06.005

The enigmatic structure of the crenarchaeol isomer

Jaap S. Sinninghe Damsté^*, W. Irene C. Rijpstra, Ellen C. Hopmans, Mimi J. den Uijl, Johan W.H. Weijers, Stefan Schouten

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Isolation of crenarchaeol and its isomer from marine surface sediments, followed by ether cleavage and GC–MS characterization using supersonic molecular beam (SMB) ionization of the biphytanes formed, revealed that the crenarchaeol isomer comprises a tricyclic biphytane that is stereochemically different from the tricyclic biphytane of crenarchaeol. This isomeric tricyclic biphytane was also released from the crenarchaeol isomer in extant Thaumarchaeotal biomass. Reinterpretation of previously obtained ¹³C NMR data of the crenarchaeol isomer suggested that the cyclopentane moiety adjacent to the cyclohexyl moiety of the tricyclic biphytane of the crenarcheaol isomers possesses the unusual cis stereochemistry in comparison to the trans stereochemistry of all cyclopentane moieties in crenarchaeol. This stereochemical difference likely affects the packing of lipid membranes of Thaumarchaeota and therefore provides a biophysical explanation for the role of the crenarchaeol isomer in the TEX₈₆ palaeothermometer based on fossilized Thaumarcheotal lipids.

Original language	English
Pages (from-to)	22-28
Number of pages	7
Journal	Organic Geochemistry
Volume	124
DOIs	https://doi.org/10.1016/j.orggeochem.2018.06.005
Publication status	Published - 1 Oct 2018

Funding

We thank Elise Jonkheim and Lennart van Maldegem for their help in isolating crenarchaeol and its isomer, Wim Genuit for assistance in obtaining the SMB mass spectra, Marton Palatinszky and Michael Wagner for a kind gift of biomass of “ Ca. Nitrosotenuis uzonensis”, and two anonymous referees for helpful suggestions. JSSD, ECH, and SS receive funding from the Netherlands Earth System Science Center (NESSC) though a gravitation grant (024.002.001) from the Dutch ministry for Education, Culture and Science.

Keywords

Archaea
Crenarchaeol
GDGTs
Structural determination
TEX
Thaumarchaeota

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.orggeochem.2018.06.005

sinninghe damsteFinal published version, 570 KBLicence: CC BY

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abstract = "Isolation of crenarchaeol and its isomer from marine surface sediments, followed by ether cleavage and GC–MS characterization using supersonic molecular beam (SMB) ionization of the biphytanes formed, revealed that the crenarchaeol isomer comprises a tricyclic biphytane that is stereochemically different from the tricyclic biphytane of crenarchaeol. This isomeric tricyclic biphytane was also released from the crenarchaeol isomer in extant Thaumarchaeotal biomass. Reinterpretation of previously obtained 13C NMR data of the crenarchaeol isomer suggested that the cyclopentane moiety adjacent to the cyclohexyl moiety of the tricyclic biphytane of the crenarcheaol isomers possesses the unusual cis stereochemistry in comparison to the trans stereochemistry of all cyclopentane moieties in crenarchaeol. This stereochemical difference likely affects the packing of lipid membranes of Thaumarchaeota and therefore provides a biophysical explanation for the role of the crenarchaeol isomer in the TEX86 palaeothermometer based on fossilized Thaumarcheotal lipids.",

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AU - den Uijl, Mimi J.

AU - Weijers, Johan W.H.

AU - Schouten, Stefan

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AB - Isolation of crenarchaeol and its isomer from marine surface sediments, followed by ether cleavage and GC–MS characterization using supersonic molecular beam (SMB) ionization of the biphytanes formed, revealed that the crenarchaeol isomer comprises a tricyclic biphytane that is stereochemically different from the tricyclic biphytane of crenarchaeol. This isomeric tricyclic biphytane was also released from the crenarchaeol isomer in extant Thaumarchaeotal biomass. Reinterpretation of previously obtained 13C NMR data of the crenarchaeol isomer suggested that the cyclopentane moiety adjacent to the cyclohexyl moiety of the tricyclic biphytane of the crenarcheaol isomers possesses the unusual cis stereochemistry in comparison to the trans stereochemistry of all cyclopentane moieties in crenarchaeol. This stereochemical difference likely affects the packing of lipid membranes of Thaumarchaeota and therefore provides a biophysical explanation for the role of the crenarchaeol isomer in the TEX86 palaeothermometer based on fossilized Thaumarcheotal lipids.

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ER -

The enigmatic structure of the crenarchaeol isomer

Abstract

Funding

Keywords

UN SDGs

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