Archaeol is composed of two phytanyl chains linked to the sn-2 and sn-3 positions of

glycerol Glycerol (), also called glycerine in British English and glycerin in American English, is a simple triol compound. It is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. The glycerol backbone is found in lipids known ...

. As its phosphate ester, it is a common component of the membranes of

archaea Archaea ( ; singular archaeon ) is a domain of single-celled organisms. These microorganisms lack cell nuclei and are therefore prokaryotes. Archaea were initially classified as bacteria, receiving the name archaebacteria (in the Archaebac ...

Structure and contrast with other lipids

Archaeol is a diether. The 2,3-sn-glycerol structure and ether bond linkage are two key differences between lipids found in archaea vs those of

bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria were among ...

and

eukarya Eukaryotes () are organisms whose cells have a nucleus. All animals, plants, fungi, and many unicellular organisms, are Eukaryotes. They belong to the group of organisms Eukaryota or Eukarya, which is one of the three domains of life. Bacte ...

. The latter use 1,2-sn-glycerol, and mostly, ester bonds. Natural archaeol has 3R, 7R, 11R configurations for the three

chiral centers In stereochemistry, a stereocenter of a molecule is an atom (center), axis or plane that is the focus of stereoisomerism; that is, when having at least three different groups bound to the stereocenter, interchanging any two different groups cr ...

in the isoprenoid chains. There are four structural variations, contributing to the complexity of the

membrane lipid Membrane lipids are a group of compounds (structurally similar to fats and oils) which form the double-layered surface of all cells (lipid bilayer). The three major classes of membrane lipids are phospholipids, glycolipids, and cholesterol. Lipid ...

s in function and properties. The two phytanyl chains can form a 36-member ring to yield macrocyclic archaeol. Hydroxylated archaeol has phytanyl chains hydroxylated at the first

tertiary carbon Tertiary ( ) is a widely used but obsolete term for the geologic period from 66 million to 2.6 million years ago. The period began with the demise of the non-avian dinosaurs in the Cretaceous–Paleogene extinction event, at the star ...

atom, while sesterterpanyl archaeol have the phytanyl side chains with C25 sesterterpanyl chains, substituting at C2 of glycerol or at both carbons. Unsaturated archaeol, with the same carbon skeleton as standard archaeol but one or multiple double bonds in the phytanyl side chains is also discovered.

Biological role and synthesis

Two archaeol molecules can undergo head-to-head linkage to form

caldarchaeol Caldarchaeol is a membrane-spanning lipid found in hyperthermophilic archaea. Membranes made up of caldarchaeol are more stable since the hydrophobic chains are linked together, allowing the microorganisms to withstand high temperatures. It is a ...

(one typical

glycerol dialkyl glycerol tetraether Glycerol dialkyl glycerol tetraether lipids (GDGTs) are a class of membrane lipids synthesized by archaea and some bacteria, making them useful biomarkers for these organisms in the geological record. Their presence, structure, and relative abundan ...

, GDGT), one of the most common tetraether lipid in archaea. Alternate MVA pathway

Biological role

Archaeol has been found in all archaea so far, at least in trace amounts. It represents 100% of the diether core lipids in most

neutrophil Neutrophils (also known as neutrocytes or heterophils) are the most abundant type of granulocytes and make up 40% to 70% of all white blood cells in humans. They form an essential part of the innate immune system, with their functions varying ...

halophile The halophiles, named after the Greek word for "salt-loving", are extremophiles that thrive in high salt concentrations. While most halophiles are classified into the domain Archaea, there are also bacterial halophiles and some eukaryotic species, ...

s and sulfur-dependent

thermophile A thermophile is an organism—a type of extremophile—that thrives at relatively high temperatures, between . Many thermophiles are archaea, though they can be bacteria or fungi. Thermophilic eubacteria are suggested to have been among the earl ...

s (though their most core lipids are tetraether lipids). Methanogens contain

hydroxyarchaeol Hydroxyarchaeol is a core lipid unique to archaea, similar to archaeol, with a hydroxide functional group at the carbon-3 position of one of its ether side chains. It is found exclusively in certain taxa of methanogenic archaea, and is a common ...

and macrocyclic other than the standard archaeol, and sesterterpanyl-chain-containing archaeol is characteristic of alkaliphilic extreme halophiles. It is noteworthy that tetraether lipids are also widely present in archaea.

Liposome A liposome is a small artificial vesicle, spherical in shape, having at least one lipid bilayer. Due to their hydrophobicity and/or hydrophilicity, biocompatibility, particle size and many other properties, liposomes can be used as drug deliver ...

s (a spherical vesicle having at least at least one lipid bilayer) of lipids from archaea typically demonstrate extremely low permeability for molecules and ions, even including protons. The ion permeability induced by

ionophore In chemistry, an ionophore () is a chemical species that reversibly binds ions. Many ionophores are lipid-soluble entities that transport ions across the cell membrane. Ionophores catalyze ion transport across hydrophobic membranes, such as liq ...

s (ion transporters across the membranes) are also quite low, and only comparable to that of egg

phosphatidylcholine Phosphatidylcholines (PC) are a class of phospholipids that incorporate choline as a headgroup. They are a major component of biological membranes and can be easily obtained from a variety of readily available sources, such as egg yolk or soyb ...

(a very common biological membrane component) at 37˚C when the temperature rises up to c.a. 70˚C. Compared to

and

, the isoprenoid side chains of archaeol are highly branched. This structural difference is believed lower the permeability of archaea over the whole growth temperature range which enables archaea to adapt to extreme environments.

Biosynthesis

Archaeol's biosynthesis proceeds by a multistep process mediated by several enzymes. In simplified terms,

glycerol 1-phosphate ''sn''-Glycerol 1-phosphate is the conjugate base of a phosphoric ester of glycerol. It is a component of ether lipids, which are common for archaea. Biosynthesis and metabolism Glycerol 1-phosphate is synthesized by reducing dihydroxyaceton ...

is etherified to two geranylgeranyl substituents contributed by

geranylgeranyl pyrophosphate Geranylgeranyl pyrophosphate is an intermediate in the biosynthesis of diterpenes and di terpenoids. It is also the precursor to carotenoids, gibberellins, tocopherols, and chlorophylls. It is also a precursor to geranylgeranylated proteins, wh ...

. The double bonds are reduced by nicotinamide and flavins. The phosphate group is subject to modification. Archaea utilize biosynthetic pathways of isoprenoids that is distinct compared to bacteria and eukarya. The C5 precursors to the geranylgeranyl chains are

isopentenyl pyrophosphate Isopentenyl pyrophosphate (IPP, isopentenyl diphosphate, or IDP) is an isoprenoid precursor. IPP is an intermediate in the classical, HMG-CoA reductase pathway (commonly called the mevalonate pathway) and in the ''non-mevalonate'' MEP pathway of i ...

(IPP) and

dimethylallyl pyrophosphate Dimethylallyl pyrophosphate (DMAPP; or alternatively, dimethylallyl diphosphate (DMADP); also isoprenyl pyrophosphate) is an isoprenoid precursor. It is a product of both the mevalonate pathway and the MEP pathway of isoprenoid precursor biosynt ...

(DMAPP), which are produced by modified

mevalonic acid pathway The mevalonate pathway, also known as the isoprenoid pathway or HMG-CoA reductase pathway is an essential metabolic pathway present in eukaryotes, archaea, and some bacteria. The pathway produces two five-carbon building blocks called isopentenyl ...

Ether lipids in bacteria

Though archaeol, featuring the ether linkage between isoprenoid chain to glycerol, has been considered as a biomarker for archaea, ether membrane lipids have also been discovered in some

aerobic Aerobic means "requiring air," in which "air" usually means oxygen. Aerobic may also refer to * Aerobic exercise, prolonged exercise of moderate intensity * Aerobics, a form of aerobic exercise * Aerobic respiration, the aerobic process of cel ...

and

anaerobic Anaerobic means "living, active, occurring, or existing in the absence of free oxygen", as opposed to aerobic which means "living, active, or occurring only in the presence of oxygen." Anaerobic may also refer to: * Anaerobic adhesive, a bonding a ...

bacteria, including lipids with one ester bond and one ether bond to alkyl chains. Many strictly anoxic bacteria and a few aerobic species contain plasmalogens (Pla), which has an alkyl chain bound to sn-1 position of the glycerol via a vinyl-ether bond. Similar to archaea, these lipids are thought to increase the resistivity of bacteria to adverse environments. More stunning is the discovery of nonisoprenoid dialkyl glycerol diether lipids(DGD) and branched dialkyl glycerol tetraether lipids (brGDGT), which are formed, in the similar way to archaeol, by binding alkyls chains (but not isoprenoid chains) to glycerol molecules via ether linkage. It's highly notable that these lipids are only different from archaea ether lipids in the side chains and binding positions on the glycerol. DGD is reported in thermophilic bacteria, a few

mesophilic A mesophile is an organism that grows best in moderate temperature, neither too hot nor too cold, with an optimum growth range from . The optimum growth temperature for these organisms is 37°C. The term is mainly applied to microorganisms. Organi ...

bacteria and aggregating

myxobacteria The myxobacteria ("slime bacteria") are a group of bacteria that predominantly live in the soil and feed on insoluble organic substances. The myxobacteria have very large genomes relative to other bacteria, e.g. 9–10 million nucleotides except ...

Used as a lipid biomarker

Archaeol in the sediments typically originates from the hydrolysis of archaea membrane phospholipids during diagenesis. Due to its high preservation potential, it is often detected and used by organic geochemists as a biomarker for archaea activity, especially for methanogen biomass and activity. As a methanogen proxy, it is used by Michinari Sunamura et al. to directly measure the methanogens in the sediments of

Tokyo Bay is a bay located in the southern Kantō region of Japan, and spans the coasts of Tokyo, Kanagawa Prefecture, and Chiba Prefecture. Tokyo Bay is connected to the Pacific Ocean by the Uraga Channel. The Tokyo Bay region is both the most populous a ...

, and also used by Katie L. H. Lim et al. as an indicator of

methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group ...

in water-saturated soils. C. A. McCartney et al. used it as a proxy for methane production in cattle. In the meantime, it's also used to help understand ancient biogeochemistry. It was used as a biomarker by Richard D. Pancost et al. in order to reconstruct the

Holocene The Holocene ( ) is the current geological epoch. It began approximately 11,650 cal years Before Present (), after the Last Glacial Period, which concluded with the Holocene glacial retreat. The Holocene and the preceding Pleistocene togethe ...

biogeochemistry in

ombrotrophic Ombrotrophic ("cloud-fed"), from Ancient Greek ὄμβρος (''ómvros'') meaning "rain" and τροφή (''trofí'') meaning "food"), refers to soils or vegetation which receive all of their water and nutrients from precipitation, rather than ...

peatlands. A pilot study led by Ian D. Bull et al. also used archaeol as a biomarker to reveal the differences between fermenting digestive systems in foregut and hindgut of ancient

herbivorous A herbivore is an animal anatomically and physiologically adapted to eating plant material, for example foliage or marine algae, for the main component of its diet. As a result of their plant diet, herbivorous animals typically have mouthpart ...

mammals. Additionally, because of different degradation kinetics of intact archaeol and

, the ratio of archaeol to caldarchaeol was proposed as a

salinity Salinity () is the saltiness or amount of salt dissolved in a body of water, called saline water (see also soil salinity). It is usually measured in g/L or g/kg (grams of salt per liter/kilogram of water; the latter is dimensionless and equal ...

proxy in highland lakes, providing a tool for paleosalinity studies. Archaeol can also get hydrolyzed in some cases, with its side chains preserved as

phytane Phytane is the isoprenoid alkane formed when phytol, a constituent of chlorophyll, loses its hydroxyl group. When phytol loses one carbon atom, it yields pristane. Other sources of phytane and pristane have also been proposed than phytol. Pris ...

pristane Pristane is a natural saturated terpenoid alkane obtained primarily from shark liver oil, from which its name is derived (Latin ''pristis'', "shark"). It is also found in the stomach oil of birds in the order Procellariiformes and in mineral oil ...

, depending on the redox conditions.

Measurement

To analyze archaeol, lipids are commonly extracted via the traditional Bligh-Dyer procedure, usually followed by fractionation (by thin layer or column chromatography) and

derivatization Derivatization is a technique used in chemistry which converts a chemical compound into a product (the reaction's derivate) of similar chemical structure, called a derivative. Generally, a specific functional group of the compound participates ...

. Kazuhiro Demizu et al. and Sadami Ohtsubo et al. proposed similar processes involving acid Bligh and Dyer extraction, acid treatment and derivatization, with the core lipids finally being subjected to

chromatography In chemical analysis, chromatography is a laboratory technique for the separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it through a system (a ...

. To determine the concentration of archaeol present in a sample, chromatography technologies are commonly employed, including

high-performance liquid chromatography High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify each component in a mixture. It relies on pumps to pa ...

(HPLC), gas chromatography (GC), and

supercritical fluid chromatography Supercritical fluid chromatography (SFC) is a form of normal phase chromatography that uses a supercritical fluid such as carbon dioxide as the mobile phase. It is used for the analysis and purification of low to moderate molecular weight, thermal ...

(SFC), with

mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...

(MS) often applied to aid the identification.

References

{{reflist Lipids Ethers