Chamaecydin

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Chamaecydin
Chamaecydin.svg
Skeletal diagram
Names
IUPAC name
(1'R,4S,5'S,6aS,10aS)-1-hydroxy-7,7,10a-trimethyl-1',3-di(propan-2-yl)spiro[6a,8,9,10-tetrahydro-6H-acephenanthrylene-4,4'-bicyclo[3.1.0]hexane]-2,5-dione
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C30H40O3/c1-15(2)20-22-21-17(26(33)30(22)12-11-29(16(3)4)14-19(29)30)13-18-27(5,6)9-8-10-28(18,7)23(21)25(32)24(20)31/h15-16,18-19,32H,8-14H2,1-7H3/t18-,19-,28-,29+,30-/m0/s1
    Key: CTGGVCKBMLNHNX-WLHXYQFRSA-N
  • CC(C)C1=C2C3=C(C[C@@H]4[C@@](C3=C(C1=O)O)(CCCC4(C)C)C)C(=O)[C@]25CC[C@]6([C@@H]5C6)C(C)C
Properties
C30H40O3
Molar mass 448.647 g·mol−1
Melting point 197–198 °C (387–388 °F; 470–471 K)
Structure
Orthorhombic
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Chamaecydin is a chemical compound with the molecular formula C30H40O3. It is made up of three six-membered rings and two five-membered rings and has one polar hydroxyl functional group. It is well preserved in the rock record and is only found in a specific family of conifers, the swamp cypress subfamily. The presence and abundance of chamaecydin in the rock record can reveal environmental changes in ancient biomes.

Contents

Background

Notable properties

Chamaecydin is a hexacarboxylic triterpene with a highly conjugated core. [1] Its melting point is 197–198 °C. Its crystal structure is orthorhombic. [2] Chamaecydin shows significant antifeedant activity against the larvae of Spodoptera litura and has an antifeedant index (AFI) of +0.44 [3] [4]

Preservation

Chamaecydin is a biomarker for certain species of Conifer trees. Once living organism die, the organic molecules they biosynthesized often undergo various chemical transformations in the soil and thus usually retain only basic structures of the molecules that were synthesized. These modified molecules are biomarkers but can often only be used as chemical tracers for a wide group of organisms. Chamaecydin is rare because it is a polar molecule that is found perfectly preserved millions of years later, and can therefore be used to trace specific species. [5] Despite being a polar compound, chamaecydin is likely preserved because it is found trapped in resinous plant material, where it is prevented from bonding to kerogen. In the paleorecord, it is found in clayey sediments, which prevents further oxidation. [5] Chamaecydin is found in concentrations ranging 3–8.7 mg/g of organic carbon. [6]

Biological sources

It was first isolated from the seed of Chamaecyparis obtusa (Cupressaceae) and then from the leaves of Cryptomeria japonica D. Don. [1] Chamaecydin has since been found to be unique to the swamp cypress subfamily (Taxodioideae), specifically, it has been most studied in these species: Cryptomeria japonica , Glyptostrobus pensilis , Taxodium distichum , and Taxodium mucronatum . The molecule is found in the leaflets, seed cones, and wood of the cypress trees and can be traced back to the Cretaceous period (c.  145.5  million years ago). The other key biomarkers for this sub-family are ferruginol and 7α-p-cymenylferruginol. [7] The synthesis methods of chamaecydin have not yet been studied.

Occurrence

Conifers, deduced by the presence of chamaecydin in the paleorecord, managed to flourish across a wide range of latitudes over Earth's history. Below are some well studied occurrences of conifers.

  1. The paleoflora of the Maritza-East basin was a marine environment that developed limnic conditions due to a marine regression. The area then experienced alternating dry and wet periods from intense precipitation during the Oligocene to Pliocene epochs (33.9-2.58 Ma). We can infer that the forested flood plains were dominated by Taxodioideae because of the presence of chamaecydin. The biomarker is captured in 3 thick lignite beds that formed in the dry periods, with one bed reaching 30 m in thickness. [6]
  2. Chamaecydin also confirms that large deciduous conifer forests were present north of the Arctic Circle (78 N) during the mid Eocene (45 Ma) at Axel Heiberg island. This is a unique habitat, which required them to be dormant during 3 months of winter darkness. The Arctic Circle at this time was very different from today: it was ice free and warm (12-17 degrees warmer than today) with lots of precipitation. These deposits occur in fluvial and lacustrine settings. [8]
  3. The mid Eocene (45 Ma) resinites from brown coal pits in northern Germany contain chamaecydin and reveal a cypress semitropical swamp environment. [9]

Related Research Articles

<i>Taxodium</i> Genus of conifers

Taxodium is a genus of one to three species of extremely flood-tolerant conifers in the cypress family, Cupressaceae. The generic name is derived from the Latin word taxus, meaning "yew", and the Greek word εἶδος (eidos), meaning "similar to." Within the family, Taxodium is most closely related to Chinese swamp cypress and sugi.

Cypress is a common name for various coniferous trees or shrubs of northern temperate regions that belong to the family Cupressaceae. The word cypress is derived from Old French cipres, which was imported from Latin cypressus, the latinisation of the Greek κυπάρισσος (kyparissos). Cypress trees are a large classification of conifers, encompassing the trees and shrubs from the cypress family (Cupressaceae) and many others with the word cypress in their common name. Many cypress trees have needle-like, evergreen foliage and acorn-like seed cones.

<span class="mw-page-title-main">Cupressaceae</span> Cypress family of conifers

Cupressaceae is a conifer family, the cypress, with worldwide distribution. The family includes 27–30 genera, which include the junipers and redwoods, with about 130–140 species in total. They are monoecious, subdioecious or (rarely) dioecious trees and shrubs up to 116 m (381 ft) tall. The bark of mature trees is commonly orange- to red-brown and of stringy texture, often flaking or peeling in vertical strips, but smooth, scaly or hard and square-cracked in some species.

<i>Chamaecyparis</i> Genus of conifers

Chamaecyparis, common names cypress or false cypress, is a genus of conifers in the cypress family Cupressaceae, native to eastern Asia and to the western and eastern margins of the United States. The name is derived from the Greek khamai (χαμαί), meaning "on the earth", and kuparissos (κυπάρισσος) for "cypress".

<i>Cryptomeria</i> Species of conifer in the family Cupressaceae

Cryptomeria is a monotypic genus of conifer in the cypress family Cupressaceae, formerly belonging to the family Taxodiaceae. It includes only one species, Cryptomeria japonica. It used to be considered by some to be endemic to Japan, where it is known as Sugi. The tree is called Japanese cedar or Japanese redwood in English. It has been extensively introduced and cultivated for wood production on the Azores.

<i>Chamaecyparis thyoides</i> Species of plant

Chamaecyparis thyoides, a species of Cupressaceae, is native to the Atlantic coast of North America and is found from southern Maine to Georgia and along the Gulf of Mexico coast from Florida to Mississippi. It is one of two species of Chamaecyparis found in North America. C. thyoides resides on the East Coast and C. lawsoniana can be found on the West Coast. There are two geographically isolated subspecies, treated by some botanists as distinct species, by others at just varietal rank: Chamaecyparis thyoides thyoides and Chamaecyparis thyoides henryae (H.L.Li) E.Murray The species grows in forested wetlands where they tend to dominate the canopy. The trees are associated with a wide variety of other wetland species because of their wide north-south range. The remaining populations are now found mostly in remote locations that would be difficult to harvest, so its popularity as a source of lumber has decreased.

<i>Chamaecyparis obtusa</i> Tree, a species of cypress

Chamaecyparis obtusa is a species of cypress native to central Japan in East Asia, and widely cultivated in the temperate northern hemisphere for its high-quality timber and ornamental qualities, with many cultivars commercially available.

<i>Chamaecyparis pisifera</i> Species of conifer

Chamaecyparis pisifera is a species of false cypress, native to central and southern Japan, on the islands of Honshū and Kyūshū.

<i>Glyptostrobus</i> Genus of conifers

Glyptostrobus is a small genus of conifers in the family Cupressaceae. The sole living species, Glyptostrobus pensilis, is native to subtropical southeastern China, from Fujian west to southeast Yunnan, and also very locally in northern Vietnam and Borikhamxai Province of eastern Laos near the Vietnam border.

<span class="mw-page-title-main">Ferruginol</span> Chemical compound

Ferruginol is a natural phenol with a terpenoid substructure. Specifically, it is a diterpene of the abietane chemical class, meaning it is characterized by three fused six-membered rings and alkyl functional groups. Ferruginol was first identified in 1939 by Brandt and Neubauer as the main component in the resin of the Miro tree and has since been isolated from other conifer species in the families Cupressaceae and Podocarpaceae. As a biomarker, the presence of ferruginol in fossils, mainly resin, is used to describe the density of these conifers in that particular biosphere throughout time.

<span class="mw-page-title-main">Pine–cypress forest</span>

Pine–cypress forest is a type of mixed conifer woodland in which at least one species of pine and one species of cypress are present. Such forests are noted in several parts of the world, but are particularly well studied in Japan, and the United States.

<span class="mw-page-title-main">Thujaplicin</span> Chemical compound

Thujaplicins are a series of tropolone-related chemical substances that have been isolated from the softwoods of the trees of Cupressaceae family. These compounds are known for their antibacterial, antifungal, and antioxidant properties. They were the first natural tropolones to be made synthetically.

<span class="mw-page-title-main">Hinokitiol</span> Chemical compound

Hinokitiol (β-thujaplicin) is a natural monoterpenoid found in the wood of trees in the family Cupressaceae. It is a tropolone derivative and one of the thujaplicins. Hinokitiol is used in oral and skin care products, and is a food additive used in Japan.

<span class="mw-page-title-main">Taxodone</span> Chemical compound

Taxodone is a naturally occurring diterpenoid found in Taxodium distichum, Rosmarinus officinalis (rosemary), several salvia species and other plants, along with its oxidized rearrangement product, taxodione. Taxodone and taxodione exhibit anticancer, antibacterial, antioxidant, antifungal, insecticide, and antifeedant activities.

<span class="mw-page-title-main">Abietane</span> 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.

<i>Amylostereum laevigatum</i> Species of fungus

Amylostereum laevigatum is a species of crust fungus in the family Amylostereaceae. Originally named Thelephora laevigata by Elias Fries in 1828, it was given its current name when transferred to the genus Amylostereum by French mycologist Jacques Boidin in 1958.

Urocerus japonicus, commonly known as the Japanese horntail, is a species of sawfly, native to southeastern Asia. Studies show that the dispersal distance of the female is higher than the male. The fungal species Amylostereum laevigatum had its first appearance in Japan via this sawfly.

<i>Taxodium dubium</i> Extinct species of conifer

Taxodium dubium is an extinct species of cypress in the genus Taxodium in the family Cupressaceae which lived from the Late Paleocene to the Pliocene in North America and Europe. The species was first described in 1823 by Kaspar Maria von Sternberg.

<span class="mw-page-title-main">Sugiol</span> Chemical compound

Sugiol is a phenolic abietane derivative of ferruginol and can be used as a biomarker for specific families of conifers. The presence of sugiol can be used to identify the Cupressaceae s.1., podocarpaceae, and Araucaraiaceae families of conifers. The polar terpenoids are among the most resistant molecules to degradation besides n-alkanes and fatty acids, affording them high viability as biomarkers due to their longevity in the sedimentary record. Significant amounts of sugiol has been detected in fossil wood dated to the Eocene and Miocene periods, as well as a sample of Protopodocarpoxylon dated to the middle Jurassic.

Highly branched isoprenoids (HBIs) are long-chain alkenes produced by a small number of marine diatoms. There are a variety of highly branched isoprenoid structures, but C25 Highly branched isoprenoids containing 1 to 3 double bonds are the most common in the sedimentary record. Highly branched isoprenoids have been used as environmental proxies for sea ice conditions in the Arctic and Antarctic throughout the Holocene, and more recently, are being used to reconstruct more ancient ice records.

References

  1. 1 2 Su, Wen-Chiung; Fang, Jim-Min; Cheng, Yu-Shia (1993-10-01). "Hexacarbocyclic triterpenes from leaves of Cryptomeria japonica". Phytochemistry. 34 (3): 779–782. Bibcode:1993PChem..34..779S. doi:10.1016/0031-9422(93)85358-X. ISSN   0031-9422.
  2. Hirose, Yoshiyuki; Hasegawa, Shinichi; Ozaki, Naotake; Iitaka, Yoichi (1983-01-01). "Three new terpenoid quinone methides from the seed of Chamaecyparis obtusa". Tetrahedron Letters. 24 (14): 1535–1538. doi:10.1016/S0040-4039(00)81702-5. ISSN   0040-4039.
  3. AFI ranges from –1 to +1, with +1 being the most powerful antifeedant
  4. Fukushima, Jun-ichi; Yatagai, Mitsuyoshi; Ohira, Tatsuro (August 2002). "Abietane-type and labdane-type diterpenoids from the cones of Chamaecyparis obtusa". Journal of Wood Science. 48 (4): 326–330. doi: 10.1007/bf00831355 . ISSN   1435-0211. S2CID   93215171.
  5. 1 2 Otto, A. (2002-08-30). "Natural Product Terpenoids in Eocene and Miocene Conifer Fossils". Science. 297 (5586): 1543–1545. Bibcode:2002Sci...297.1543O. doi:10.1126/science.1074225. ISSN   0036-8075. PMID   12202827. S2CID   41346998.
  6. 1 2 Stefanova, Maya; Simoneit, Bernd R.T.; Marinov, Stefan P.; Zdravkov, Alexander; Kortenski, Jordan (June 2016). "Novel polar biomarkers of the Miocene Maritza-East lignite, Bulgaria". Organic Geochemistry. 96: 1–10. Bibcode:2016OrGeo..96....1S. doi:10.1016/j.orggeochem.2016.03.002. ISSN   0146-6380.
  7. Simoneit; Otto; Oros; Kusumoto (2019-08-21). "Terpenoids of the Swamp Cypress Subfamily (Taxodioideae), Cupressaceae, an Overview by GC-MS". Molecules. 24 (17): 3036. doi: 10.3390/molecules24173036 . ISSN   1420-3049. PMC   6751496 . PMID   31438610.
  8. Simoneit, Bernd R.T.; Otto, Angelika; Kusumoto, Norihisa; Basinger, James F. (December 2016). "Biomarker compositions of Glyptostrobus and Metasequoia (Cupressaceae) fossils from the Eocene Buchanan Lake Formation, Axel Heiberg Island, Nunavut, Canada reflect diagenesis from terpenoids of their related extant species". Review of Palaeobotany and Palynology. 235: 81–93. Bibcode:2016RPaPa.235...81S. doi:10.1016/j.revpalbo.2016.07.012. ISSN   0034-6667.
  9. Simoneit, Bernd R.T.; Otto, Angelika; Menor-Sálvan, Cesar; Oros, Daniel R.; Wilde, Volker; Riegel, Walter (February 2021). "Composition of resinites from the Eocene Geiseltal brown coal basin, Saxony-Anhalt, Germany and comparison to their possible botanical analogues". Organic Geochemistry. 152: 104138. Bibcode:2021OrGeo.15204138S. doi:10.1016/j.orggeochem.2020.104138. ISSN   0146-6380. S2CID   228967077.