Chlorobactane

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Chlorobactane
Chlorobactane with ChemDraw.png
Chlorobactane with JMol.png
Names
IUPAC name
2-(3,7,12,16,20,24-Hexamethylpentacosyl)-1,3,4-trimethylbenzene
Identifiers
3D model (JSmol)
PubChem CID
  • InChI=1S/C40H74/c1-31(2)17-13-20-34(5)23-15-25-35(6)24-14-21-32(3)18-11-12-19-33(4)22-16-26-36(7)27-30-40-38(9)29-28-37(8)39(40)10/h28-29,31-36H,11-27,30H2,1-10H3
  • CC1=C(C(=C(C=C1)C)CCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)CCCC(C)C)C
Properties
C40H74
Molar mass 555.032 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Chlorobactane is the diagenetic product of an aromatic carotenoid produced uniquely by green-pigmented green sulfur bacteria (GSB) in the order Chlorobiales . [1] Observed in organic matter as far back as the Paleoproterozoic, its identity as a diagnostic biomarker has been used to interpret ancient environments. [2] [3]

Contents

Background

Chlorobactene Biosynthesis Chlorobactene Biosynthesis.png
Chlorobactene Biosynthesis

Chlorobactene is a monocyclic accessory pigment used by green sulfur bacteria to capture electrons from wavelengths in the visible light spectrum. Green sulfur bacteria (GSB) live in anaerobic and sulfidic (euxinic) zones in the presence of light, so they are found most often in meromictic lakes and ponds, sediments, and certain regions of the Black Sea. [4] The enzyme CrtU converts γ-carotene into chlorobactene by shifting the C17 methyl group from the C1 site to the C2 site. [5] [6]

Preservation

Following transport and burial, diagenetic processes saturate the hydrocarbon chain, turning it into the fully saturated structure of chlorobactane.

Isoreneiratene is an aromatic light-harvesting molecule interpreted as a biomarker for brown-pigmented GSB in the same order, Chlorobiales, and its fossil form (isoreneiratane) is often found co-occurring with chlorobactene in ancient organic material. [7] Purple sulfur bacteria (PSB) also live in euxinic regions. [4] They produce a different accessory pigment, okenone, that is preserved as okenane and often observed co-occurring with chlorobactane. [3]

Measurement techniques

Gas chromatography coupled to mass spectrometry (GC/MS)

Organic molecules are first extracted from rocks using solvents, capitalizing on chemical properties like the polarity of the molecules to dissolve the molecules. Usually, less than one percent of the organic material from a rock is successfully pulled out in this process, leaving behind undissolved material called kerogen. The organic-rich extract is subsequently purified using silica gel column packed chromatography – eluting the extract through the column with targeted solvents pulls out contaminants and remnant undissolved organic material, which will bind to the polar silica moieties. When the sample is then run through a gas chromatography (GC) column, the compounds separate based on their boiling points and interaction with a stationary phase within the column. The temperature ramping of a gas chromatography column can be programmed to obtain optimal separation of the compounds. After the GC, the molecules are ionized and fragmented into smaller, charged molecules. A mass spectrometer then separates the individual compounds based on their mass-to-charge (M/Z) ratio and measures their relative abundance, producing a characteristic mass spectrum. Peaks representing the relative abundance of the compounds are identified as molecules based on their relative retention times, matches to a library of mass spectra with known compound identities, and comparison to standards.

Case Study: Ocean Euxinia

Because green-pigmented green sulfur bacteria require higher light intensities than their brown-pigmented counterparts, [8] the presence of chlorobactane in the rock record has been used as key evidence in interpretations for a very shallow euxinic layer in the ocean. [9] The euxinic zone may have changed depth in the ocean at various points in Earth's history, such as with the advent of an oxygenated atmosphere around 2.45 billion years ago and the shallowing of the oxic zone within the last six kyr. [10] [11]

See also

Related Research Articles

The purple sulfur bacteria (PSB) are part of a group of Proteobacteria capable of photosynthesis, collectively referred to as purple bacteria. They are anaerobic or microaerophilic, and are often found in stratified water environments including hot springs, stagnant water bodies, as well as microbial mats in intertidal zones. Unlike plants, algae, and cyanobacteria, purple sulfur bacteria do not use water as their reducing agent, and therefore do not produce oxygen. Instead, they can use sulfur in the form of sulfide, or thiosulfate (as well, some species can use H2, Fe2+, or NO2) as the electron donor in their photosynthetic pathways. The sulfur is oxidized to produce granules of elemental sulfur. This, in turn, may be oxidized to form sulfuric acid.

Chromatiaceae Family of purple sulfur bacteria

The Chromatiaceae are one of the two families of purple sulfur bacteria, together with the Ectothiorhodospiraceae. They belong to the order Chromatiales of the class Gammaproteobacteria, which is composed by unicellular Gram-negative organisms. Most of the species are photolithoautotrophs and conduct an anoxygenic photosynthesis, but there are also representatives capable of growing under dark and/or microaerobic conditions as either chemolithoautotrophs or chemoorganoheterotrophs.

Photoheterotrophs are heterotrophic phototrophs – that is, they are organisms that use light for energy, but cannot use carbon dioxide as their sole carbon source. Consequently, they use organic compounds from the environment to satisfy their carbon requirements; these compounds include carbohydrates, fatty acids, and alcohols. Examples of photoheterotrophic organisms include purple non-sulfur bacteria, green non-sulfur bacteria, and heliobacteria. Recent research has indicated that the oriental hornet and some aphids may be able to use light to supplement their energy supply.

TEX<sub>86</sub>

TEX86 is an organic paleothermometer based upon the membrane lipids of mesophilic marine Thaumarchaeota (formerly Marine Group 1 Crenarchaeota).

A light-harvesting complex consists of a number of chromophores which are complex subunit proteins that may be part of a larger super complex of a photosystem, the functional unit in photosynthesis. It is used by plants and photosynthetic bacteria to collect more of the incoming light than would be captured by the photosynthetic reaction center alone. The light which is captured by the chromophores is capable of exciting molecules from their ground state to a higher energy state, known as the excited state. This excited state does not last very long and is known to be short-lived. Light-harvesting complexes are found in a wide variety among the different photosynthetic species. The complexes consist of proteins and photosynthetic pigments and surround a photosynthetic reaction center to focus energy, attained from photons absorbed by the pigment, toward the reaction center using Förster resonance energy transfer.

A chlorosome is a photosynthetic antenna complex found in green sulfur bacteria (GSB) and some green filamentous anoxygenic phototrophs (FAP). They differ from other antenna complexes by their large size and lack of protein matrix supporting the photosynthetic pigments. Green sulfur bacteria are a group of organisms that generally live in extremely low-light environments, such as at depths of 100 metres in the Black Sea. The ability to capture light energy and rapidly deliver it to where it needs to go is essential to these bacteria, some of which see only a few photons of light per chlorophyll per day. To achieve this, the bacteria contain chlorosome structures, which contain up to 250,000 chlorophyll molecules. Chlorosomes are ellipsoidal bodies, in GSB their length varies from 100 to 200 nm, width of 50-100 nm and height of 15 - 30 nm, in FAP the chlorosomes are somewhat smaller.

Cholestane Chemical compound

Cholestane is a saturated tetracyclic triterpene. This 27-carbon biomarker is produced by diagenesis of cholesterol and is one of the most abundant biomarkers in the rock record. Presence of cholestane, its derivatives and related chemical compounds in environmental samples is commonly interpreted as an indicator of animal life and/or traces of O2, as animals are known for exclusively producing cholesterol, and thus has been used to draw evolutionary relationships between ancient organisms of unknown phylogenetic origin and modern metazoan taxa. Cholesterol is made in low abundance by other organisms (e.g., rhodophytes, land plants), but because these other organisms produce a variety of sterols it cannot be used as a conclusive indicator of any one taxon. It is often found in analysis of organic compounds in petroleum.

Biological pigment Substances produced by living organisms

Biological pigments, also known simply as pigments or biochromes, are substances produced by living organisms that have a color resulting from selective color absorption. Biological pigments include plant pigments and flower pigments. Many biological structures, such as skin, eyes, feathers, fur and hair contain pigments such as melanin in specialized cells called chromatophores. In some species, pigments accrue over very long periods during an individual's lifespan.

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.

Isorenieratene Chemical compound

Isorenieratene is a carotenoid light harvesting pigment with the chemical formula C40H48. Isorenieratene and its derivatives are useful to marine chemists studying the carbon cycle as biomarkers that indicate photic zone anoxia.

Abietane Chemical compound

Abietane is a diterpene that forms the structural basis for a variety of natural chemical compounds such as abietic acid, carnosic acid, and ferruginol which are collectively known as abietanes or abietane diterpenes.

Kliti Grice, is a Chemist, an Organic and Isotope Geochemist and Earth Scientist known for her work in identifying geological and environmental causes for mass extinction events. Her multidisciplinary research integrates geological information with data on molecular fossils and their stable carbon, hydrogen and sulfur isotopic compositions to reconstruct details of microbial, fungal and floral inhabitants of modern and ancient aquatic environments and biodiversity hot spots. This information expands our understanding of both the Earth's history and its current physical state, with implications ranging from energy and mineral resource exploration strategies to environmental sustainability encompassing climate dynamics and expected rates, durations and scale of our future planet's health. As one of the youngest women professors in Earth Sciences, she is the founding director of the Western Australian Organic and Isotope Geochemistry Centre (WA-OIGC) and is a Professor of Organic and Isotope Geochemistry at Curtin University in Perth, Western Australia.

Crocetane, or 2,6,11,15-tetramethylhexadecane, is an isoprenoid hydrocarbon compound. Unlike its isomer phytane, crocetane has a tail-to-tail linked isoprenoid skeleton. Crocetane has been detected in modern sediments and geological records as a biomarker, often associated with anaerobic methane oxidation.

Okenane

Okenane, the diagenetic end product of okenone, is a biomarker for Chromatiaceae, the purple sulfur bacteria. These anoxygenic phototrophs use light for energy and sulfide as their electron donor and sulfur source. Discovery of okenane in marine sediments implies a past euxinic environment, where water columns were anoxic and sulfidic. This is potentially tremendously important for reconstructing past oceanic conditions, but so far okenane has only been identified in one Paleoproterozoic rock sample from Northern Australia.

Euxinia or euxinic conditions occur when water is both anoxic and sulfidic. This means that there is no oxygen (O2) and a raised level of free hydrogen sulfide (H2S). Euxinic bodies of water are frequently strongly stratified, have an oxic, highly productive, thin surface layer, and have anoxic, sulfidic bottom water. The word euxinia is derived from the Greek name for the Black Sea (Εὔξεινος Πόντος (Euxeinos Pontos)) which translates to "hospitable sea". Euxinic deep water is a key component of the Canfield ocean, a model of oceans during the Proterozoic period (known as the Boring Billion) proposed by Donald Canfield, an American geologist, in 1998. There is still debate within the scientific community on both the duration and frequency of euxinic conditions in the ancient oceans. Euxinia is relatively rare in modern bodies of water, but does still happen in places like the Black Sea and certain fjords.

24-Norcholestane Chemical compound

24-Norcholestane, a steroid derivative, is used as a biomarker to constrain the source age of sediments and petroleum through the ratio between 24-norcholestane and 27-norcholestane, especially when used with other age diagnostic biomarkers, like oleanane. While the origins of this compound are still unknown, it is thought that they are derived from diatoms due to their identification in diatom rich sediments and environments. In addition, it was found that 24-norcholestane levels increased in correlation with diatom evolution. Another possible source of 24-norcholestane is from dinoflagellates, albeit to a much lower extent.

Crenarchaeol is a glycerol biphytanes glycerol tetraether (GDGT) biological membrane lipid. It has a distinctive cyclohexane moiety and has been proposed as a specific biomarker for pelagic ammonia-oxidizing archaea (AOA). Structurally, the molecule consists of two long hydrocarbon chains that extend through the cell membrane and are bound on each to glycerol through ether linkage. Crenarchaeol can be preserved for hundreds of millions of years in the environment and is part of the TEX86 paleothermometer, a temperature proxy for sea surface temperatures that has been used to reconstruct paleoclimate through to the middle Jurassic (~160 Ma).

Tetrahymanol Chemical compound

Tetrahymanol is a gammacerane-type membrane lipid first found in the marine ciliate Tetrahymena pyriformis. It was later found in other ciliates, fungi, ferns, and bacteria. After being deposited in sediments that compress into sedimentary rocks over millions of years, tetrahymanol is dehydroxylated into gammacerane. Gammacerane has been interpreted as a proxy for ancient water column stratification.

Lycopane Chemical compound

Lycopane (C40H82; 2,6,10,14,19,23,27,31-octamethyldotriacontane), a 40 carbon alkane isoprenoid, is a widely present biomarker that is often found in anoxic settings. It has been identified in anoxically deposited lacustrine sediments (such as the Messel formation and the Condor oil shale deposit). It has been found in sulfidic and anoxic hypersaline environments (such as the Sdom Formation). It has been widely identified in modern marine sediments, including the Peru upwelling zone, the Black Sea, and the Cariaco Trench. It has been found only rarely in crude oils.

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 abundances in natural materials can be useful as proxies for temperature, terrestrial organic matter input, and soil pH for past periods in Earth history. Some structural forms of GDGT form the basis for the TEX86 paleothermometer. Isoprenoid GDGTs, now known to be synthesized by many archaeal classes, were first discovered in extremophilic archaea cultures. Branched GDGTs, likely synthesized by acidobacteria, were first discovered in a natural Dutch peat sample in 2000.

References

  1. Summons, R.E.; Powell, T.G. (1987). “Identification of aryl isoprenoids in source rocks and crude oils: Biological markers for the green sulphur bacteria”. Geochimica et Cosmochimica Acta. 51: 557 – 566.
  2. Brocks, J. J.; Love, G. D.; Summons, R. E.; Knoll, A. H.; Logan, G. A.; Bowden, S. A. (2005). "Biomarker evidence for green and purple sulphur bacteria in a stratified Palaeoproterozoic sea". Nature. 437 (7060): 866–70. Bibcode:2005Natur.437..866B. doi:10.1038/nature04068. PMID   16208367. S2CID   4427285.
  3. 1 2 French, K. L.; Rocher, D.; Zumberge, J. E.; Summons, R. E. (2015). "Assessing the distribution of sedimentary C40carotenoids through time". Geobiology. 13 (2): 139–151. doi:10.1111/gbi.12126. PMID   25631735.
  4. 1 2 Imhoff, Johannes F. (1995). “Taxonomy and Physiology of Phototrophic Purple Bacteria and Green Sulfur Bacteria”. Anoxygenic Photosynthetic Bacteria, pp 1 – 15. Kluwer Academic Publishers.
  5. Canniffe, Daniel P.; Thweatt, Jennifer L.; Gomez Maqueo Chew, Aline; Hunter, C. Neil; Bryant, Donald A. (2018). "A paralog of a bacteriochlorophyll biosynthesis enzyme catalyzes the formation of 1,2-dihydrocarotenoids in green sulfur bacteria". Journal of Biological Chemistry. 293 (39): 15233–15242. doi: 10.1074/jbc.RA118.004672 . PMC   6166724 . PMID   30126840.
  6. Maresca, J. A.; Romberger, S. P.; Bryant, D. A. (2008). "Isorenieratene Biosynthesis in Green Sulfur Bacteria Requires the Cooperative Actions of Two Carotenoid Cyclases". Journal of Bacteriology. 190 (19): 6384–6391. doi:10.1128/JB.00758-08. PMC   2565998 . PMID   18676669.
  7. Sinninghe Damste, Jaap S.; Schouten, S.; Van Duin, Adri C. T. (2001). “Isorenieratene derivatives in sediments: Possible controls on their distribution”. Geochimica et Cosmochimica Acta, 65(10): 1557 – 1571.
  8. Vila, X.; Abella, C. A. (1994). "Effects of light quality on the physiology and the ecology of planktonic green sulfur bacteria in lakes". Photosynthesis Research. 41 (1): 53–65. doi:10.1007/BF02184145. PMID   24310013. S2CID   25001156.
  9. Kuypers, M.; Pancost, R.; Nijenhuis, I.; Sinninghe Damste, J.S. (2002). “Enhanced productivity led to increased organic carbon burial in the euxinic North Atlantic basin during the late Cenomian oceanic anoxic event. Paleoceanography. 17: 1051.
  10. Meyer, Katja M.; Kump, Lee R. (2008). “Ocean Euxinia in Earth History: Causes and Consequences”. Annual Reviews in Earth and Planetary Sciences. 36: 251 – 288.
  11. Sinninghe Damste et al., 1993c [ full citation needed ]