Vulpinic acid

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Vulpinic acid
Chemical structure of vulpinic acid Vulpinic acid Structural Formula V1.svg
Chemical structure of vulpinic acid
Vulpinic acid - 3D - Ball-and-stick Model.png
Names
Preferred IUPAC name
Methyl (E)-(5-hydroxy-3-oxo-4-phenylfuran-2(3H)-ylidene)phenylacetate
Identifiers
3D model (JSmol)
ChEMBL
ECHA InfoCard 100.007.560 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • COC(=O)/C(=C/1\C(=O)C(=C(O1)O)C2=CC=CC=C2)/C3=CC=CC=C3
Properties
C19H14O5
Molar mass 322.316 g·mol−1
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
toxic
GHS labelling:
GHS-pictogram-skull.svg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Vulpinic acid is a natural product first found in and important in the symbiosis underlying the biology of lichens. [1] It is a simple methyl ester derivative of its parent compound, pulvinic acid, and a close relative of pulvinone, both of which derive from aromatic amino acids such as phenylalanine via secondary metabolism. The roles of vulpinic acid are not fully established, but may include properties that make it an antifeedant for herbivores. The compound is relatively toxic to mammals.

Contents

Chemical description

Vulpinic acid was first isolated from lichens in 1925. [2] [ non-primary source needed ] As an isolated, purified substance, it is bright yellow in color. [3]

Vulpinic acid is derived biosynthetically by esterification from pulvinic acid; [4] pulvinate itself derives from the aromatic amino acids phenylalanine and tyrosine, via dimerization and oxidative ring-cleavage of arylpyruvic acids, a process that also produces the related pulvinones. [5] [ page range too broad ]

There have been several chemical syntheses reported for vulpinic acid. In one, butenolides were efficiently functionalized by Suzuki cross-coupling reactions via the corresponding enol triflates [ further explanation needed ]. [6]

Occurrence in lichens

The lichen Letharia vulpina, whose bright color is due in part to vulpinic acid. Letharia vulpina JHollinger.jpg
The lichen Letharia vulpina , whose bright color is due in part to vulpinic acid.

Pulvinic acid is found in several lichen species, as well as some non-lichenized fungi. [2] [ better source needed ] It is a secondary metabolite of the fungal partner in the lichen symbiosis.[ citation needed ] It was found in the bolete fungus Pulveroboletus ravenelii . [7] [5] In 2016, a new group of basidiomycetes distinct from the well known lichen fungal partner was implicated in producing vulpinic acid. [1]

Bioactivities

Vulpinic acid is relatively toxic to meat-eating mammals as well as insects and molluscs. However, it is not toxic to rabbits and mice. One biological function of vulpinic acid may be as a repellent that lichens have evolved to deter grazing by herbivores. [8] Lichens may also exploit the ultraviolet-blocking properties of the molecule, protecting the underlying photobionts. [9] For example, vulpinic acid is thought to function as a blue light screen in Letharia vulpina . [10] It had been shown previously to protect human skin cells in tissue culture against ultraviolet B-induced damage. [11]

Humans have exploited its mammalian toxicity, using lichens containing high amounts of the chemical (e.g., Letharia vulpina) to poison wolves in Scandinavia, sometimes adding it to baits containing reindeer blood and glass. [3]

Vulpinic acid has some antibacterial activity against gram-positive bacteria, and has been shown to disrupt cell division in MRSA. [12] [13]

See also

Related Research Articles

<span class="mw-page-title-main">Lichen</span> Symbiosis of fungi with algae or cyanobacteria

A lichen is a composite organism that arises from algae or cyanobacteria living among filaments of multiple fungi species in a mutualistic relationship. Lichens are important actors in nutrient cycling and act as producers which many higher trophic feeders feed on, such as reindeer, gastropods, nematodes, mites, and springtails. Lichens have properties different from those of their component organisms. They come in many colors, sizes, and forms and are sometimes plant-like, but are not plants. They may have tiny, leafless branches (fruticose); flat leaf-like structures (foliose); grow crust-like, adhering tightly to a surface (substrate) like a thick coat of paint (crustose); have a powder-like appearance (leprose); or other growth forms.

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

The phenylpropanoids are a diverse family of organic compounds that are synthesized by plants from the amino acids phenylalanine and tyrosine. Their name is derived from the six-carbon, aromatic phenyl group and the three-carbon propene tail of coumaric acid, which is the central intermediate in phenylpropanoid biosynthesis. From 4-coumaroyl-CoA emanates the biosynthesis of myriad natural products including lignols, flavonoids, isoflavonoids, coumarins, aurones, stilbenes, catechin, and phenylpropanoids. The coumaroyl component is produced from cinnamic acid.

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

Ethnolichenology is the study of the relationship between lichens and people. Lichens have and are being used for many different purposes by human cultures across the world. The most common human use of lichens is for dye, but they have also been used for medicine, food and other purposes.

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

Queuine (Q) is a hypermodified nucleobase found in the first position of the anticodon of tRNAs specific for Asn, Asp, His, and Tyr, in most eukaryotes and prokaryotes. Because it is utilized by all eukaryotes but produced exclusively by bacteria, it is a putative vitamin.

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

Pulvinone, an organic compound belonging to the esters, lactones, alcohols and butenolides classes, is a yellow crystalline solid. Although the pulvinone is not a natural product, several naturally occurring hydroxylated derivatives are known. These hydroxylated pulvinones are produced by fungal species, such as the in Europe common Larch Bolete, or by moulds such as Aspergillus terreus.

<i>Lobaria pulmonaria</i> Species of lichen

Lobaria pulmonaria is a large epiphytic lichen consisting of an ascomycete fungus and a green algal partner living together in a symbiotic relationship with a cyanobacterium—a symbiosis involving members of three kingdoms of organisms. Commonly known by various names like tree lungwort, lung lichen, lung moss, lungwort lichen, oak lungs or oak lungwort, it is sensitive to air pollution and is also harmed by habitat loss and changes in forestry practices. Its population has declined across Europe and L. pulmonaria is considered endangered in many lowland areas. The species has a history of use in herbal medicines, and recent research has corroborated some medicinal properties of lichen extracts.

<i>Vulpicida</i> Genus of lichen

Vulpicida is a genus of lichenized fungi in the family Parmeliaceae. Circumscribed in 1993 to contain species formerly placed in Cetraria, the genus is widespread in Arctic to northern temperate regions, and contains six species. The genus is characterized by the presence of the secondary metabolites pulvinic acid and vulpinic acid, compounds that when combined with usnic acid, give the species their characteristic yellow and green colors.

<i>Pseudocyphellaria</i> Genus of lichens

Pseudocyphellaria is a genus of large, leafy lichens that are sometimes referred to as "specklebelly" lichens. The genus has a widespread distribution, especially in south temperate regions, and contains about 170 species. They resemble Lobaria, except that most species of Pseudocyphellaria have conspicuous pseudocyphellae on their lower surface, a characteristic that was once considered unique to this genus. Some species contain pulvinic acid-related pigments; in these species the soredia and pseudocyphellae can be bright yellow.

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

Atromentin is a natural chemical compound found in Agaricomycetes fungi in the orders Agaricales and Thelephorales. It can also be prepared by laboratory synthesis. Chemically, it is a polyphenol and a benzoquinone.

<i>Pulveroboletus ravenelii</i> Species of fungus

Pulveroboletus ravenelii, commonly known as Ravenel's bolete or the powdery sulfur bolete, is a species of bolete fungus in the family Boletaceae. Described as new to science in 1853, the widely distributed species is known from Asia, Australia, North America, Central America, and South America. Mycorrhizal with oak, the fungus fruits on the ground singly, scattered, or in groups in woods. Fruit bodies (mushrooms) have convex to flat, yellowish to brownish-red caps up to 10 cm (4 in) in diameter. On the cap underside, the pore surface is bright yellow before turning dingy yellow to grayish brown with age; it stains greenish blue then grayish brown after injury. A cottony and powdery partial veil remains as a ring on the stipe. The mushrooms are edible, and have been used in traditional Chinese medicine and for mushroom dyeing.

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

Variegatic acid is an orange pigment found in some mushrooms. It is responsible for the bluing reaction seen in many bolete mushrooms when they are injured. When mushroom tissue containing variegatic acid is exposed to air, the chemical is enzymatically oxidized to blue quinone methide anions, specifically chinonmethid anions. It is derived from xerocomic acid, which is preceded by atromentic acid and atromentin, and its genetic basis is unknown. In its oxidized form is variegatorubin, similar to xerocomorubin.

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

Pulvinic acids are natural chemical pigments found in some lichens, derived biosynthetically from the aromatic amino acids phenylalanine and tyrosine, via dimerization and oxidative ring-cleavage of arylpyruvic acids, a process that also produces the related pulvinones.

Lichens of the Sierra Nevada have been little studied. A lichen is a composite organism consisting of a fungus and a photosynthetic partner growing together in a symbiotic relationship.

<span class="mw-page-title-main">Symbiosis in lichens</span>

Symbiosis in lichens is the mutually beneficial symbiotic relationship of green algae and/or blue-green algae (cyanobacteria) living among filaments of a fungus, forming lichen.

A spot test in lichenology is a spot analysis used to help identify lichens. It is performed by placing a drop of a chemical on different parts of the lichen and noting the colour change associated with application of the chemical. The tests are routinely encountered in dichotomous keys for lichen species, and they take advantage of the wide array of lichen products produced by lichens and their uniqueness among taxa. As such, spot tests reveal the presence or absence of chemicals in various parts of a lichen. They were first proposed by the botanist William Nylander in 1866.

<i>Candelariella vitellina</i> Species of fungus

Candelariella vitellina is a common and widespread green-yellow to orange-yellow crustose areolate lichen that grows on rock, wood, and bark, all over the world. It grows on non-calcareous rock, wood, and bark. It often has tiny lobate areoles in the shape of lion claws. The areoles may be flat or convex. Its sexual reproduction structures (apothecia) are a 0.35–1.0 mm-wide disc, darker yellow than the thallus, rimmed with thallus-like tissue lecanorine, flat but becoming convex with age. Lichen spot tests are K+ reddish, KC−, and C−. It produces calycin, pulvinic acid, pulvinic dilactone and vulpinic acid as secondary metabolites.

<span class="mw-page-title-main">Lichexanthone</span> Chemical compound found in some lichens

Lichexanthone is an organic compound in the structural class of chemicals known as xanthones. Lichexanthone was first isolated and identified by Japanese chemists from a species of leafy lichen in the 1940s. The compound is known to occur in many lichens, and it is important in the taxonomy of species in several genera, such as Pertusaria and Pyxine. More than a dozen lichen species have a variation of the word lichexanthone incorporated as part of their binomial name. The presence of lichexanthone in lichens causes them to fluoresce a greenish-yellow colour under long-wavelength UV light; this feature is used to help identify some species. Lichexanthone is also found in several plants, and some species of fungi that do not form lichens.

<i>Letharia columbiana</i> Species of lichen

Letharia columbiana (common name brown-eye wolf lichen, synonyms Letharia californica, Borrera columbiana) is a common lichen in subalpine forests, particularly in the Pacific Northwest of the United States, and parts of Canada. It is in the family Parmeliaceae, and the genus Letharia. Its characteristics include a bright citron color, “brown-eyes”, and rounded, irregular branches. Though previously believed to lump together several lineages such as Letharia gracilis and others, there now exists more specific characteristics to identify the species. This lichen grows on the bark of conifers a couple inches tall. L. Columbiana’s cousin, Letharia vulpina (common name wolf lichen), has similar geographical distribution and morphological features, with the major difference being the “brown-eyes” of L. columbiana.

<span class="mw-page-title-main">Outline of lichens</span> Overview of and topical guide to lichens

The following outline provides an overview of and topical guide to lichens.

<i>Umbilicaria muhlenbergii</i> Species of lichen

Umbilicaria muhlenbergii, commonly known as plated rock tripe, is a species of saxicolous (rock-dwelling, umbilicate lichen in the family Umbilicariaceae.

References

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  2. 1 2 Mazza, Franc Paolo (1925). "Constitution and physical properties of vulpinic acid". Rendiconto dell'Accademia delle Scienze Napoli. 31: 182–190.
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