Gluconasturtiin

Last updated
Gluconasturtiin
Gluconasturtiin structure.svg
Names
IUPAC name
1-S-[(1Z)-3-Phenyl-N-(sulfooxy)propanimidoyl]-1-thio-β-D-glucopyranose
Other names
Phenethyl glucosinolate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.231.959 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C15H21NO9S2/c17-8-10-12(18)13(19)14(20)15(24-10)26-11(16-25-27(21,22)23)7-6-9-4-2-1-3-5-9/h1-5,10,12-15,17-20H,6-8H2,(H,21,22,23)/b16-11-/t10-,12-,13+,14-,15+/m1/s1 Yes check.svgY
    Key: CKIJIGYDFNXSET-OOMJLXHVSA-N Yes check.svgY
  • c1ccc(cc1)CC/C(=N/OS(=O)(=O)O)/S[C@H]2[C@@H]([C@H]([C@@H]([C@H](O2)CO)O)O)O
Properties
C15H21NO9S2
Molar mass 423.45 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Gluconasturtiin or phenethyl glucosinolate is one of the most widely distributed glucosinolates in the cruciferous vegetables, mainly in the roots, and is probably one of the plant compounds responsible for the natural pest-inhibiting properties of growing crucifers, such as cabbage, mustard or rape, in rotation with other crops. This effect of gluconasturtiin is due to its degradation by the plant enzyme myrosinase into phenethyl isothiocyanate, which is toxic to many organisms. [1]

Contents

Gluconasturtiin is named from its occurrence in watercress (Nasturtium officinale). Among the vegetables, it is also found in horseradish (Armoracia rusticana) along with sinigrin. Both compounds elicit a pungent taste. [2]

Occurrence

The compound was first reported in 1899, after its isolation from watercress, Nasturtium officinale , and the cress Barbarea verna . [1] :Section 2 Gluconasturtiin is now known to occur widely in other brassica families including Brassicaceae and Resedaceae. [3]

In one investigation of horseradish roots, sinigrin represented 83% and gluconasturtiin 11% of the extracted glucosinolates. [4]

Synthesis

Biosynthesis

Gluconasturtiin is biosynthesised from the amino acid phenylalanine in a multi-step pathway. [1]

Laboratory synthesis

The first laboratory synthesis served to confirm the compound's structure. [5] Later work allowed many glucosinolates including this phenethyl derivative to be made. These processes are more efficient than isolating pure materials from the plants in which they are naturally found. [1] :Section 3

Function

The natural role of glucosinolates are as plant defense compounds. The enzyme myrosinase removes the glucose group in gluconasturiin to give an intermediate which spontaneously rearranges to phenethyl isothiocyanate. This is a reactive material which is toxic to many insect predators and its production is triggered when the plant is damaged. [6] This effect has been called the mustard oil bomb. [7] At concentrations typically found in foods, the glucosinolates are not toxic to humans and can be useful flavor components. [8]

Related Research Articles

<span class="mw-page-title-main">Brassicaceae</span> Family of flowering plants

Brassicaceae or Cruciferae is a medium-sized and economically important family of flowering plants commonly known as the mustards, the crucifers, or the cabbage family. Most are herbaceous plants, while some are shrubs. The leaves are simple, lack stipules, and appear alternately on stems or in rosettes. The inflorescences are terminal and lack bracts. The flowers have four free sepals, four free alternating petals, two shorter free stamens and four longer free stamens. The fruit has seeds in rows, divided by a thin wall.

<span class="mw-page-title-main">Wasabi</span> Species of edible plant

Wasabi or Japanese horseradish is a plant of the family Brassicaceae, which also includes horseradish and mustard in other genera. The plant is native to Japan and the Russian Far East including Sakhalin, as well as the Korean Peninsula. It grows naturally along stream beds in mountain river valleys in Japan.

<span class="mw-page-title-main">Horseradish</span> Species of flowering plants in the cabbage family Brassicaceae

Horseradish is a perennial plant of the family Brassicaceae. It is a root vegetable, cultivated and used worldwide as a spice and as a condiment. The species is probably native to Southeastern Europe and Western Asia.

<span class="mw-page-title-main">Isothiocyanate</span> Chemical group (–N=C=S)

In organic chemistry, isothiocyanate is the functional group −N=C=S, formed by substituting the oxygen in the isocyanate group with a sulfur. Many natural isothiocyanates from plants are produced by enzymatic conversion of metabolites called glucosinolates. These natural isothiocyanates, such as allyl isothiocyanate, are also known as mustard oils. An artificial isothiocyanate, phenyl isothiocyanate, is used for amino acid sequencing in the Edman degradation.

<span class="mw-page-title-main">Watercress</span> Species of flowering plant in the cabbage family

Watercress or yellowcress is a species of aquatic flowering plant in the cabbage family Brassicaceae.

<span class="mw-page-title-main">Mustard oil</span> Oil derived from mustard plants

Mustard oil can mean either the pressed oil used for cooking, or a pungent essential oil also known as volatile oil of mustard. The essential oil results from grinding mustard seed, mixing the grounds with water, and isolating the resulting volatile oil by distillation. It can also be produced by dry distillation of the seed. Pressed mustard oil is used as cooking oil in some cultures, but sale is restricted in some countries due to high levels of erucic acid. Varieties of mustard seed also exist that are low in erucic acid.

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

Allyl isothiocyanate (AITC) is a naturally occurring unsaturated isothiocyanate. The colorless oil is responsible for the pungent taste of Cruciferous vegetables such as mustard, radish, horseradish, and wasabi. This pungency and the lachrymatory effect of AITC are mediated through the TRPA1 and TRPV1 ion channels. It is slightly soluble in water, but more soluble in most organic solvents.

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

Sulforaphane is a compound within the isothiocyanate group of organosulfur compounds. It is produced when the enzyme myrosinase transforms glucoraphanin, a glucosinolate, into sulforaphane upon damage to the plant, which allows the two compounds to mix and react.

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

Glucoraphanin is a glucosinolate found in broccoli, mustard and other cruciferous vegetables.

<span class="mw-page-title-main">Glucosinolate</span> Class of chemical compounds

Glucosinolates are natural components of many pungent plants such as mustard, cabbage, and horseradish. The pungency of those plants is due to mustard oils produced from glucosinolates when the plant material is chewed, cut, or otherwise damaged. These natural chemicals most likely contribute to plant defence against pests and diseases, and impart a characteristic bitter flavor property to cruciferous vegetables.

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

Sinigrin or allyl glucosinolate is a glucosinolate that belongs to the family of glucosides found in some plants of the family Brassicaceae such as Brussels sprouts, broccoli, and the seeds of black mustard. Whenever sinigrin-containing plant tissue is crushed or otherwise damaged, the enzyme myrosinase degrades sinigrin to a mustard oil, which is responsible for the pungent taste of mustard and horseradish. Seeds of white mustard, Sinapis alba, give a less pungent mustard because this species contains a different glucosinolate, sinalbin.

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

Glucobrassicin is a type of glucosinolate that can be found in almost all cruciferous plants, such as cabbages, broccoli, mustards, and woad. As for other glucosinolates, degradation by the enzyme myrosinase is expected to produce an isothiocyanate, indol-3-ylmethylisothiocyanate. However, this specific isothiocyanate is expected to be highly unstable, and has indeed never been detected. The observed hydrolysis products when isolated glucobrassicin is degraded by myrosinase are indole-3-carbinol and thiocyanate ion, which are envisioned to result from a rapid reaction of the unstable isothiocyanate with water. However, a large number of other reaction products are known, and indole-3-carbinol is not the dominant degradation product when glucosinolate degradation takes place in crushed plant tissue or in intact plants.

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

Myrosinase is a family of enzymes involved in plant defense against herbivores, specifically the mustard oil bomb. The three-dimensional structure has been elucidated and is available in the PDB.

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

Sinalbin is a glucosinolate found in the seeds of white mustard, Sinapis alba, and in many wild plant species. In contrast to mustard from black mustard seeds which contain sinigrin, mustard from white mustard seeds has only a weakly pungent taste.

<i>Brevicoryne brassicae</i> Species of true bug

Brevicoryne brassicae, commonly known as the cabbage aphid or cabbage aphis, is a destructive aphid native to Europe that is now found in many other areas of the world. The aphids feed on many varieties of produce, including cabbage, broccoli (especially), Brussels sprouts, cauliflower and many other members of the genus Brassica, but do not feed on plants outside of the family Brassicaceae. The insects entirely avoid plants other than those of Brassicaceae; even though thousands may be eating broccoli near strawberries, the strawberries will be left untouched.

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

Phenethyl isothiocyanate (PEITC) is a naturally occurring isothiocyanate whose precursor, gluconasturtiin is found in some cruciferous vegetables, especially watercress.

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

Antifeedants are organic compounds produced by plants to repel herbivores through distaste or toxicity. These chemical compounds are typically classified as secondary metabolites in that they are not essential for the metabolism of the plant, but instead confer longevity. Antifeedants exhibit a wide range of activities and chemical structures as biopesticides. Examples include rosin, which inhibits attack on trees, and many alkaloids, which are highly toxic to specific insect species, such as quassinoids against the diamondback moth. Samadera indica also has quassinoids used for insect antifeedant uses.

Phenylalanine N-monooxygenase (EC 1.14.14.40, phenylalanine N-hydroxylase, CYP79A2) is an enzyme with systematic name L-phenylalanine,NADPH:oxygen oxidoreductase (N-hydroxylating). This enzyme catalyses the following chemical reaction

The mustard oil bomb, formerly known as the glucosinolate–myrosinase complex, is a chemical herbivory defense system found in members of the Brassicaceae. The mustard oil bomb requires the activation of a common plant secondary metabolite, glucosinolate, by an enzyme, myrosinase. The defense complex is typical among plant defenses to herbivory in that the two molecules are stored in different compartments in the leaves of plants until the leaf is torn by an herbivore. The glucosinolate has a β-glucose and a sulfated oxime. The myrosinase removes the β-glucose to form mustard oils that are toxic to herbivores. The defense system was named a "bomb" by Matile, because it like a real bomb is waiting to detonate upon disturbance of the plant tissue.

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

Glucotropaeolin or benzyl glucosinolate is a glucosinolate found in cruciferous vegetables, particularly garden cress. Upon enzymatic activity, it is transformed into benzyl isothiocyanate, which contributes to the characteristic flavor of these brassicas.

References

  1. 1 2 3 4 Blažević, Ivica; Montaut, Sabine; Burčul, Franko; Olsen, Carl Erik; Burow, Meike; Rollin, Patrick; Agerbirk, Niels (2020). "Glucosinolate structural diversity, identification, chemical synthesis and metabolism in plants". Phytochemistry. 169: 112100. doi: 10.1016/j.phytochem.2019.112100 . PMID   31771793. S2CID   208318505.
  2. (in French) RICHARD H. Arômes alimentaires PDF Document Archived February 14, 2007, at the Wayback Machine
  3. Fahey, Jed W.; Zalcmann, Amy T.; Talalay, Paul (2001). "The chemical diversity and distribution of glucosinolates and isothiocyanates among plants". Phytochemistry. 56 (1): 5–51. doi:10.1016/S0031-9422(00)00316-2. PMID   11198818.
  4. Li, Xian; Kushad, Mosbah M. (2004). "Correlation of Glucosinolate Content to Myrosinase Activity in Horseradish (Armoracia rusticana)". Journal of Agricultural and Food Chemistry. 52 (23): 6950–6955. doi:10.1021/jf0401827. PMID   15537302.
  5. Benn, M. H. (1964). "The Synthesis of Gluconasturiin". Journal of the Chemical Society (Resumed): 4072–3. doi:10.1039/JR9640004053.
  6. Morant, Anne Vinther; Jørgensen, Kirsten; Jørgensen, Charlotte; Paquette, Suzanne Michelle; Sánchez-Pérez, Raquel; Møller, Birger Lindberg; Bak, Søren (2008). "β-Glucosidases as detonators of plant chemical defense". Phytochemistry. 69 (9): 1795–1813. doi:10.1016/j.phytochem.2008.03.006. PMID   18472115.
  7. Matile, Ph. (1980). ""Die Senfolbombe": Zur Kompartimentierung des Myrosinasesystems". Biochemie und Physiologie der Pflanzen (in German). 175 (8–9): 722–731. doi:10.1016/S0015-3796(80)80059-X.
  8. Fenwick, G. Roger; Heaney, Robert K.; Mullin, W. John; Vanetten, Cecil H. (1983). "Glucosinolates and their breakdown products in food and food plants". C R C Critical Reviews in Food Science and Nutrition. 18 (2): 123–201. doi:10.1080/10408398209527361. PMID   6337782.

See also