Glucoraphanin

Last updated
Glucoraphanin
Glucoraphanin.png
Potassium salt of glucoraphanin
Names
IUPAC name
1-S-[(1E)-5-(methylsulfinyl)-N-(sulfonatooxy)pentanimidoyl]-1-thio-β-D-glucopyranose
Other names
Glucorafanin; 4-Methylsulfinylbutyl glucosinolate, Sulforaphane glucosinolate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
UNII
  • InChI=1S/C12H23NO10S3/c1-25(18)5-3-2-4-8(13-23-26(19,20)21)24-12-11(17)10(16)9(15)7(6-14)22-12/h7,9-12,14-17H,2-6H2,1H3,(H,19,20,21)/p-1/t7-,9-,10+,11-,12+,25?/m1/s1
    Key: GMMLNKINDDUDCF-SISVVIKZSA-M
  • InChI=1/C12H23NO10S3/c1-25(18)5-3-2-4-8(13-23-26(19,20)21)24-12-11(17)10(16)9(15)7(6-14)22-12/h7,9-12,14-17H,2-6H2,1H3,(H,19,20,21)/p-1/t7-,9-,10+,11-,12+,25?/m1/s1
    Key: GMMLNKINDDUDCF-XQSZSTCOBC
  • [O-]S(=O)(=O)ON=C(S[C@@H]1O[C@@H]([C@@H](O)[C@H](O)[C@H]1O)CO)CCCCS(=O)C
Properties
C12H23NO10S3
Molar mass 437.49 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Glucoraphanin is a glucosinolate found in broccoli, [1] [2] mustard and other cruciferous vegetables. [3] [4]

Contents

Glucoraphanin is converted to sulforaphane by the enzyme myrosinase. [5] In plants, sulforaphane deters insect predators and acts as a selective antibiotic. [6]

Synthesis

Glucoraphanin is derived from dihomomethionine, which is methionine chain-elongated twice. [7] The sulfinyl group is chiral, and has R absolute configuration. The stereochemistry is set when an oxygen atom added to 4-methylthiobutylglucosinolate by a flavin monooxygenase. [8]

Research

Sulforaphane and other isothiocyanates have been studied for their potential biological effects. [3] The isothiocyanates formed from glucosinolates are under laboratory research to assess the expression and activation of enzymes that metabolize xenobiotics, such as carcinogens. [3] Observational studies have been conducted to determine if consumption of cruciferous vegetables affects cancer risk in humans, but there is insufficient clinical evidence to indicate that consuming glucoraphanin and other isothiocyanates in cruciferous vegetables is beneficial, according to a 2017 review. [3]

Plant breeding

Cultivars of broccoli have been bred to contain two to three times more glucoraphanin than standard broccoli. [9] Romanesco broccoli may contain up to ten times more glucoraphanin than typical broccoli varieties. [10] Frostara, Black Tuscany, and red cabbage also contain higher levels of glucoraphanin than broccoli. [10]

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">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">Broccoli</span> Edible green plant in the cabbage family

Broccoli is an edible green plant in the cabbage family whose large flowering head, stalk and small associated leaves are eaten as a vegetable. Broccoli is classified in the Italica cultivar group of the species Brassica oleracea. Broccoli has large flower heads, or florets, usually dark green, arranged in a tree-like structure branching out from a thick stalk, which is usually light green. The mass of flower heads is surrounded by leaves. Broccoli resembles cauliflower, which is a different but closely related cultivar group of the same Brassica species.

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

In organic chemistry, isothiocyanate is a functional group as found in compounds with the formula R−N=C=S. Isothiocyanates are the more common isomers of thiocyanates, which have the formula R−S−C≡N.

<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">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">Cruciferous vegetables</span> Vegetables of the family Brassicaceae

Cruciferous vegetables are vegetables of the family Brassicaceae with many genera, species, and cultivars being raised for food production such as cauliflower, cabbage, kale, garden cress, bok choy, broccoli, Brussels sprouts, mustard plant and similar green leaf vegetables. The family takes its alternative name from the shape of their flowers, whose four petals resemble a cross.

<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> Class of enzymes

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">Gluconasturtiin</span> Chemical compound

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.

<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">Broccoli sprouts</span> Edible young broccoli plants

Broccoli sprouts are three- to four-day-old broccoli plants that look like alfalfa sprouts, but taste like radishes.

<span class="mw-page-title-main">Mustard (condiment)</span> Condiment made from mustard seeds

Mustard is a condiment made from the seeds of a mustard plant.

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

Allyl cyanide is an organic compound with the formula CH2CHCH2CN. Like other small alkyl nitriles, allyl cyanide is colorless and soluble in organic solvents. Allyl cyanide occurs naturally as an antifeedant and is used as a cross-linking agent in some polymers.

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">Paul Talalay</span> American cancer researcher and pharmacologist

Paul Talalay was the John Jacob Abel Distinguished Service Professor of Pharmacology and director of the Laboratory for Molecular Sciences at the Johns Hopkins School of Medicine in Baltimore. He was the founder of the Brassica Chemoprotection Laboratory for the study of edible plants that induce protective enzyme activity in the body and may help prevent the development of cancer.

<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.

<span class="mw-page-title-main">4-Hydroxybenzyl isothiocyanate</span> Chemical compound

4-Hydroxybenzyl isothiocyanate is a naturally occurring isothiocyanate. It is formed as a degradation product of sinalbin from white mustard and contributes to the pungent taste of mustard seeds.

References

  1. James, D.; Devaraj, S.; Bellur, P.; Lakkanna, S.; Vicini, J.; Boddupalli, S. (2012). "Novel concepts of broccoli sulforaphanes and disease: Induction of phase II antioxidant and detoxification enzymes by enhanced-glucoraphanin broccoli". Nutrition Reviews. 70 (11): 654–65. doi: 10.1111/j.1753-4887.2012.00532.x . PMID   23110644.
  2. Jeffery, E. H.; Brown, A. F.; Kurilich, A. C.; Keck, A. S.; Matusheski, N.; Klein, B. P.; Juvik, J. A. (2003). "Variation in content of bioactive components in broccoli". Journal of Food Composition and Analysis. 16 (3): 323–330. doi:10.1016/S0889-1575(03)00045-0.
  3. 1 2 3 4 "Isothiocyanates". Micronutrient Information Center, Linus Pauling Institute, Oregon State University. 1 April 2017. Retrieved 26 June 2022.
  4. Oh, K.; SangOk, K.; Rak, C. (2015). "Sinigrin content of different parts of Dolsan leaf mustard". Korean Journal of Food Preservation. 22 (4): 553–558. doi: 10.11002/kjfp.2015.22.4.553 .
  5. Cuomo, Valentina; Luciano, Fernando B.; Meca, Giuseppe; Ritieni, Alberto; Mañes, Jordi (26 November 2014). "Bioaccessibility of glucoraphanin from broccoli using an gastrointestinal digestion model". CyTA - Journal of Food. 13 (3): 361–365. doi:10.1080/19476337.2014.984337. S2CID   96578211.
  6. Fahey, Jed W.; Holtzclaw, W. David; Wehage, Scott L.; Wade, Kristina L.; Stephenson, Katherine K.; Talalay, Paul; Mukhopadhyay, Partha (2 November 2015). "Sulforaphane Bioavailability from Glucoraphanin-Rich Broccoli: Control by Active Endogenous Myrosinase". PLOS ONE. 10 (11): e0140963. Bibcode:2015PLoSO..1040963F. doi: 10.1371/journal.pone.0140963 . PMC   4629881 . PMID   26524341.
  7. Agerbirk N, Olsen CE (May 2012). "Glucosinolate structures in evolution". Phytochemistry . 77: 16–45. Bibcode:2012PChem..77...16A. doi:10.1016/j.phytochem.2012.02.005. PMID   22405332.
  8. Fredd Vergara; et al. (Nov 2008). "Determination of the absolute configuration of the glucosinolate methyl sulfoxide group reveals a stereospecific biosynthesis of the side chain". Phytochemistry. 69 (15): 2737–2742. Bibcode:2008PChem..69.2737V. doi:10.1016/j.phytochem.2008.09.008. PMID   18945459.
  9. Cheng, Maria (October 26, 2011). "UK scientists grow super broccoli". Boston.com. Associated Press. Archived from the original on 3 June 2012. Retrieved 10 November 2011.{{cite news}}: CS1 maint: bot: original URL status unknown (link)
  10. 1 2 Hahn, Christoph; Müller, Anja; Kuhnert, Nikolai; Albach, Dirk (2016-04-27). "Diversity of Kale (Brassica oleracea var. sabellica): Glucosinolate Content and Phylogenetic Relationships". Journal of Agricultural and Food Chemistry. 64 (16): 3215–3225. doi:10.1021/acs.jafc.6b01000. ISSN   0021-8561. PMID   27028789.