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The composition of membrane lipids varies in a number of ways as adjustment to growth conditions. Variations in head group composition and carbon skeleton and degree of unsaturation of glycerol-bound acyl or alkyl chains results in a high structural complexity of the lipidome of bacterial cells. We studied the lipidome of the mesophilic, sulfate-reducing bacterium, Desulfatibacillum alkenivorans strain PF2803T by ultra-high-pressure liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMSn). This anaerobic bacterium has been previously shown to produce high amounts of mono-and di-alkyl glycerol ethers as core membrane lipids. Our analyses revealed that these core lipids occur with phosphatidylethanomamine (PE) and phosphatidylglycerol (PG) head groups, representing each approximately one third of the phospholipids. The third class was a novel group of phospholipids, i.e., cardiolipins (CDLs) containing one (monoether/triester) to four (tetraether) ether-linked saturated straight-chain or methyl-branched alkyl chains. Tetraether CDLs have been shown to occur in archaea (with isoprenoid alkyl chains) but have not been previously reported in the bacterial Domain. Structurally related CDLs with one or two alkyl/acyl chains missing, so-called monolyso-and dilyso-CDLs, were also observed. The potential biosynthetic pathway of these novel CDLs was investigated by examining the genome of D. alkenivorans. Three CDL synthases were identified; one catalyzes the condensation of two PGs, the other two are probably involved in the condensation of a PE with a PG. A heterologous gene expression experiment showed the in vivo production of dialkylglycerols upon anaerobic expression of the glycerol ester reductase enzyme of D. alkenivorans in E. coli. Reduction of the ester bonds probably occurs first at the sn-1 and subsequently at the sn-2 position after the formation of PEs and PGs. [ABSTRACT FROM AUTHOR]

The composition of membrane lipids varies in a number of ways as adjustment to growth conditions. Variations in head group composition and carbon skeleton and degree of unsaturation of glycerol-bound acyl or alkyl chains results in a high structural complexity of the lipidome of bacterial cells. We studied the lipidome of the mesophilic, sulfate-reducing bacterium, Desulfatibacillum alkenivorans strain PF2803T by ultra-high-pressure liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMSn). This anaerobic bacterium has been previously shown to produce high amounts of mono-and di-alkyl glycerol ethers as core membrane lipids. Our analyses revealed that these core lipids occur with phosphatidylethanomamine (PE) and phosphatidylglycerol (PG) head groups, representing each approximately one third of the phospholipids. The third class was a novel group of phospholipids, i.e., cardiolipins (CDLs) containing one (monoether/triester) to four (tetraether) ether-linked saturated straight-chain or methyl-branched alkyl chains. Tetraether CDLs have been shown to occur in archaea (with isoprenoid alkyl chains) but have not been previously reported in the bacterial Domain. Structurally related CDLs with one or two alkyl/acyl chains missing, so-called monolyso-and dilyso-CDLs, were also observed. The potential biosynthetic pathway of these novel CDLs was investigated by examining the genome of D. alkenivorans. Three CDL synthases were identified; one catalyzes the condensation of two PGs, the other two are probably involved in the condensation of a PE with a PG. A heterologous gene expression experiment showed the in vivo production of dialkylglycerols upon anaerobic expression of the glycerol ester reductase enzyme of D. alkenivorans in E. coli. Reduction of the ester bonds probably occurs first at the sn-1 and subsequently at the sn-2 position after the formation of PEs and PGs.

The composition of membrane lipids varies in a number of ways as adjustment to growth conditions. Variations in head group composition and carbon skeleton and degree of unsaturation of glycerol-bound acyl or alkyl chains results in a high structural complexity of the lipidome of bacterial cells. We studied the lipidome of the mesophilic, sulfate-reducing bacterium, Desulfatibacillum alkenivorans strain PF2803 T by ultra-high-pressure liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMS n ). This anaerobic bacterium has been previously shown to produce high amounts of mono-and di-alkyl glycerol ethers as core membrane lipids. Our analyses revealed that these core lipids occur with phosphatidylethanomamine (PE) and phosphatidylglycerol (PG) head groups, representing each approximately one third of the phospholipids. The third class was a novel group of phospholipids, i.e., cardiolipins (CDLs) containing one (monoether/triester) to four (tetraether) ether-linked saturated straight-chain or methyl-branched alkyl chains. Tetraether CDLs have been shown to occur in archaea (with isoprenoid alkyl chains) but have not been previously reported in the bacterial Domain. Structurally related CDLs with one or two alkyl/acyl chains missing, so-called monolyso-and dilyso-CDLs, were also observed. The potential biosynthetic pathway of these novel CDLs was investigated by examining the genome of D. alkenivorans . Three CDL synthases were identified; one catalyzes the condensation of two PGs, the other two are probably involved in the condensation of a PE with a PG. A heterologous gene expression experiment showed the in vivo production of dialkylglycerols upon anaerobic expression of the glycerol ester reductase enzyme of D. alkenivorans in E. coli . Reduction of the ester bonds probably occurs first at the sn -1 and subsequently at the sn -2 position after the formation of PEs and PGs., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Hopmans, Grossi, Sahonero-Canavesi, Bale, Cravo-Laureau and Sinninghe Damsté.)

Over the last decade, glycerol dialkyl glycerol tetraethers (GDGTs) have become one of the most investigated lipid classes in marine and terrestrial organic geochemical research. GDGTs are microbial membrane core lipids biosynthesized as multiple homolog series of isoprenoid or methyl-branched isomers [isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) and Branched GDGTs (brGDGTs), respectively], whose relative abundance depend on a range of environmental parameters, including temperature. This has led to the development of GDGT-based temperature proxies. A key aspect in the analysis of GDGTs and the further development of their use as environmental proxies is good chromatographic separation of the full range of structural and stereo-isomers, with potential for discovery of novel GDGT variants. Several HPLC methods have been developed to this extent, but partial co-elution of GDGTs remains an issue despite long run times. In this study, we investigate the effects of different types of reverse phase (RP) chromatography on the separation of GDGT isomers. We found that the use of a Kinetex C18-XB column gives good separation of isoGDGT isomers in comparison to the recently developed double column HILIC analysis operated in normal phase (NP) and has a shorter run time. In marine samples, the regularly reported isoprenoid GDGTs separated in a similar way as in NP, however an earlier eluting group was observed to elute with the crenarchaeol isomer used in the TEX86 proxy. In a Swedish peat bog sample, a large range of isoGDGT isomers were observed. We observed a range of brGDGT isomers in several samples often with near baseline separation. Exact identification of all these isomers remained elusive, due to the different mechanism of separation in RP, and the complexity of the brGDGT family. The C18-XB method is rapid and versatile and can be set up on either low-pressure HPLC systems (max 400 bar) with a sample run time of 25 min for brGDGTs and 45 min to include isoGDGTs. On UHPLC-MS systems (>600 bar) the sample run time is reduced to 15 min. Most importantly, the C18-XB method presented here gives unusual separation of both isoprenoid and brGDGTs and could be a useful tool for the further elucidation of the biological sources and environmental factors that play a role in the production of different GDGT isomers.

Glycerol monoalkyl glycerol tetraethers (GMGTs) are a group of membrane spanning lipids produced by some species of archaea and bacteria. They differ from the more commonly studied glycerol dialkyl glycerol tetraethers (GDGTs) in having an additional covalent carbon-carbon bond connecting the two alkyl chain. The relative abundance and distribution of bacterial branched GMGTs (brGMGTs) in surface sediments from a set of East African lakes were studied. The abundance of brGMGTs relative to the brGDGTs is positively correlated to measured mean annual air temperature (MAAT), although with a significant amount of scatter. BrGMGT abundance was not correlated to lake water pH. Seven major brGMGTs that vary in degree of methylation were identified, with m / z 1020, 1034 and 1048. Further, the mass chromatograms of the m / z 1020 and 1034 brGMGTs show an interesting distribution of peaks, which likely relates to the occurrence of distinct brGMGT isomers. This structural complexity is higher than previously observed in peats and marine sediments. Principal component analysis of the fractional abundance of bacterial tetraether lipids revealed the brGMGTs behave similarly to one another but differently from both the 5- or 6-methyl brGDGTs. This suggests the brGMGTs are produced by a common source organism and are methylated at a different position. The distribution of the seven brGMGTs showed considerable correlation with MAAT. This variability was captured in a new proxy index (the brGMGTI), which showed a strong positive linear relationship with MAAT. Lacustrine brGMGTs show potential to be applied to ancient settings to provide information about paleoclimate. [ABSTRACT FROM AUTHOR]

Organic molecular proxies provide a record of the hydrogen isotopic composition of ambient precipitation and paleoenvironmental temperature. In terrestrial settings, two classes of organic biomarkers are commonly utilized to reconstruct these past environmental conditions: straight-chained normal alkanes ( n- alkanes) and branched glycerol dialkyl glycerol tetraethers (brGDGTs). We measured the δD n -alkane and the ratio of cyclisation and methylation indexes of branched tetraethers (CBT/MBT) from surface soils along a ∼1000 km transect along the southeast margin of the Tibetan Plateau to assess how these proxies record changes in climate parameters that are related to elevation, despite variations in ecosystem. Abundance-weighted δD n C27-31 data record the δD of precipitation across the orogen and indicate minimal change in apparent fractionation (ε n -alkane/water = −133‰) with elevation. n -Alkane δD mirrors the pattern of Rayleigh distillation of an air mass undergoing rainout as moisture moves from the Bay of Bengal into the SE margin of the Tibetan plateau. Soil tetraether temperatures provide a reliable measure of modern temperature with an MBT/CBT calculated temperature lapse rate (5.8 °C/km) close to the moist adiabat. These data reflect “ground-level” conditions that are independent of the shape of the orogen or the source of moisture. In combination with a Rayleigh distillation model that incorporates temperature and precipitation isotope data, paired tetraether temperature and leaf wax isotope data produce a reliable record of changes in environmental conditions associated with modern elevation change across the largest orogen. However, some tetraether calibrations may impart systematic temperature bias, most notably in cold or dry climates. These calibration uncertainties can result in underestimates of paleoelevations by up to 1.5–2 km. Paired isotopic and temperature paleoelevation reconstructions can minimize errors associated with an individual proxy method, however we recommend that application of tetraether temperature paleoelevation reconstruction take potential calibration biases into account in paleoelevation estimates. [ABSTRACT FROM AUTHOR]

The impact of hydrothermal activity on wider ocean geochemistry and microbial ecology remains a topic of much interest. To explore whether hydrothermal microbial signatures are exported to surrounding marine sediments or if such organisms serve as an important source of sedimentary organic matter, we determined the distributions of glycerol dialkyl glycerol tetraether (GDGT) membrane lipids in surficial normal marine sediments, metalliferous sediments and low-temperature hydrothermal deposits at newly discovered hydrothermal fields and adjacent areas at the Southwest Indian Ridge (SWIR). The GDGTs in those samples varied significantly, evidently representing a variable influence of the hydrothermal activity. GDGT compositions of surficial background sediments in SWIR were similar to those commonly observed in marine sediments, dominated by GDGTs associated with marine planktonic archaea and especially GDGT−0 and crenarchaeol. In contrast, the GDGTs of metalliferous sediments strongly impacted by hydrothermal activity and low-temperature hydrothermal deposits were markedly different, characterized by high relative abundances of isoprenoid GDGTs ( i GDGTs) bearing multiple rings (yielding a higher ring index), low relative abundances of crenarchaeol, and the presence of glycerol monoalkyl glycerol tetraether lipids (GMGTs; so called ‘H-tetraethers’) that were absent in the normal marine sediments. Sources for these hydrothermal-specific tetraether lipids likely include methanogens and anaerobic methanotrophic archaea (GDGT−0 and GDGT−1–3, respectively), Thermoprotei and Thermoplasmatales (elevated GDGT−3 and 4), and other thermophilic archaea including Methanobacteriales (GMGTs). Deposits influenced by low-temperature hydrothermal activity also contained higher abundances of branched GDGTs ( br GDGTs) typically attributed to soil bacteria. The more distal metalliferous sediments influenced by the neutrally buoyant plume did not contain putative hydrothermal GDGTs, having the same GDGT distribution as the background sediments. This suggests that the neutrally buoyant plume has a limited potential to directly influence the organic matter inputs to surrounding sediments, due to a rapidly waning chemosynthetic microbial contribution relative to normal marine contributions as the plume dispersed and was diluted. [ABSTRACT FROM AUTHOR]

Abstract: We estimated sea surface temperatures (SSTs) in the western Okhotsk Sea during the last glacial maximum (LGM) and the last glacial termination from measurements of the alkenone unsaturation index (UK′ 37), the Tetra Ether indeX of tetraethers consisting of 86 carbon atoms (TEX86), and TEX86 L in piston core sediments, which reveal the climate response of this region to different types of forcings. TEX86 L is a modification of TEX86 proposed for high-latitude ocean regions. The TEX86 L-derived temperatures were not different from the alkenone-derived temperatures from the same and nearby sediment samples. During the LGM, alkenone-derived temperatures in the Okhotsk Sea were relatively warm. These and similarly warm alkenone-derived temperatures found at many other sites in the western North Pacific may reflect a shift in the season of biomarker production from early summer and autumn to mid-summer during the LGM as a result of the expansion of the season of sea-ice cover. Empirical orthogonal function (EOF) analysis of alkenone-derived temperatures at 14 sites from the North Pacific suggested substantial cooling between 20 and 14calkyrBP during the deglaciation at 11 of the sites (including 4 sites in the Okhotsk Sea). This dominant EOF mode suggests either an overall seasonal bias in alkenone-derived temperatures or potential shifts in the Haptophyseae production season. The second EOF mode of variability indicated a deglacial warming trend punctuated by millennial-scale cold events, associated with reorganizations of the Atlantic Meridional Overturning Circulation. The SST pattern corresponding to this EOF mode is indicative of millennial-scale meridional shifts of the axis of the westerly jet, which may have affected heat transport across the Kuroshio. Reconstructed temperature changes, in particular in the Okhotsk Sea, provide insight into the conditions that modulated the ventilation history of intermediate waters in the North Pacific. [Copyright &y& Elsevier]

Abstract: Hydrocarbons and glycerol dialkyl glycerol tetraethers (GDGTs) were analyzed in Late Pleistocene sediments of Core HLY0503-08JPC collected at the Mendeleev Ridge during the Healy-Oden Trans Arctic Expedition 2005 (HOTRAX''05) to investigate environmental changes in the western Arctic Ocean during the last full glacial cycle, ca. 130 kyr. Variations in long-chain n-alkane and GDGT concentrations correspond to alternated color banding, brown (interglacial/interstadial) and grayish (glacial/stadial) layers. Grayish layers are characterized by abundant higher-plant n-alkanes and branched GDGTs, implying larger contribution of terrestrial plant and soil organic matter (OM) in glacial environments, possibly due to the deposition of fine-grained products of glacial erosion in the Amerasian basin. Lithic n-alkanes derived from mature OM show pronounced peaks, which can be classified into six types presumably indicative of various sediment sources. Some peaks are correlated to events of iceberg discharge and freshwater outbursts from proglacial lakes of the Eurasian and, possibly, Laurentide ice sheets, suggesting that other peaks may correspond to similar events. [Copyright &y& Elsevier]

Over the past several years, various archaeal symmetrical/unsymmetrical and acyclic/macrocyclic bipolar lipid analogues have been synthesized to study, from well-defined molecules, the membrane organizing and packing properties of this new class of amphiphiles. This review focuses on the structure and the synthesis of selected bolaamphiphiles and describes their supramolecular self-assembling properties in aqueous media. [Copyright &y& Elsevier]

Elucidating the lipidome of Archaea is essential to understand their tolerance to extreme environmental conditions. Previous characterizations of the lipid composition of Pyrococcus species, a model genus of hyperthermophilic archaea belonging to the Thermococcales order, led to conflicting results, which hindered the comprehension of their membrane structure and the putative adaptive role of their lipids. In an effort to clarify the lipid composition data of the Pyrococcus genus, we thoroughly investigated the distribution of both the core lipids (CL) and intact polar lipids (IPL) of the model Pyrococcus furiosus and, for the first time, of Pyrococcus yayanosii, the sole obligate piezophilic hyperthermophilic archaeon known to date. We showed a low diversity of IPL in the lipid extract of P. furiosus, which nonetheless allowed the first report of phosphatidyl inositol-based glycerol mono- and trialkyl glycerol tetraethers. With up to 13 different CL structures identified, the acid methanolysis of Pyrococcus furiosus revealed an unprecedented CL diversity and showed strong discrepancies with the IPL compositions reported here and in previous studies. By contrast, P. yayanosii displayed fewer CL structures but a much wider variety of polar heads. Our results showed severe inconsistencies between IPL and CL relative abundances. Such differences highlight the diversity and complexity of the Pyrococcus plasma membrane composition and demonstrate that a large part of its lipids remains uncharacterized. Reassessing the lipid composition of model archaea should lead to a better understanding of the structural diversity of their lipidome and of their physiological and adaptive functions. [ABSTRACT FROM AUTHOR]