Glucobrassicin

Last updated
Glucobrassicin
Glucobrassicin structure.svg
Names
IUPAC name
1-S-[(1Z)-2-(1H-Indol-3-yl)-N-(sulfooxy)ethanimidoyl]-1-thio-β-D-glucopyranose
Other names
Indol-3-ylmethylglucosinolate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.231.968 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C16H20N2O9S2/c19-7-11-13(20)14(21)15(22)16(26-11)28-12(18-27-29(23,24)25)5-8-6-17-10-4-2-1-3-9(8)10/h1-4,6,11,13-17,19-22H,5,7H2,(H,23,24,25)/b18-12-/t11-,13-,14+,15-,16+/m1/s1 X mark.svgN
    Key: DNDNWOWHUWNBCK-PIAXYHQTSA-N X mark.svgN
  • c1ccc2c(c1)c(c[nH]2)C/C(=N/OS(=O)(=O)O)/S[C@H]3[C@@H]([C@H]([C@@H]([C@H](O3)CO)O)O)O
Properties
C16H20N2O9S2
Molar mass 448.46 g·mol−1
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 ?)

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 (plus glucose, sulfate, and hydrogen 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 [1] or in intact plants. [2] [3]

Contents

Glucobrassicin is also known to be a highly active egg-laying stimulant of cabbage white butterflies such as the small white ( Pieris rapae ) and the large white ( Pieris brassicae ).

Several derivatives of glucobrassicin are known. The compound itself was first isolated from Brassica plants, hence the ending of the name. When a second, similar natural product was discovered, it was named neoglucobrassicin. When further derivatives were discovered, a more systematic nomenclature was used. Currently, the following six derivatives are known from plants:

The three first mentioned derivatives are as frequent in crucifers as glucobrassicin itself. The additional three derivatives appear to be rare in nature. 4-methoxyglucobrassicin was recently reported to be a signal molecule involved in plant defence against bacteria and fungi. [2] [3]

Biosynthesis from tryptophan

The biosynthesis of glucobrassicin begins with tryptophan produced through several steps from the shikimic acid pathway compound, chorismic acid. [4] Tryptophan is converted to indole-3-acetaldoxime (IAOx) by cytochrome p450 enzymes (the redundant CYP92B3 and CYP79B3 in Arabidopsis thaliana) using NADPH and molecular Oxygen. [5] A separate p450 enzyme (CYP83B1 in Arabidopsis) catalyzes a second subsequent monooxygenase reaction to create a proposed the intermediate 1-aci-nitro-2-indolyl-ethane. [5] A cysteine is utilized by glutathione S-transferase (GST) in a conjugation process to produce an S-alkylthiohydroximate derivative, which is then cleaved off by a carbon–sulfur lyase (like the SUR1 enzyme found in Arabidopsis) to create a free thiol. [6] A single glucosylation occurs attaching a glucose molecule to the indole hydroximate through a thioether linkage. Finally, the hydroximate itself is sulfated creating glucobrassicin. [5]

Biosynthesis of glucobrassicin Biosynthesis of Glucobrassicin.png
Biosynthesis of glucobrassicin

See also

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">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">Tryptophan synthase</span>

Tryptophan synthase or tryptophan synthetase is an enzyme that catalyses the final two steps in the biosynthesis of tryptophan. It is commonly found in Eubacteria, Archaebacteria, Protista, Fungi, and Plantae. However, it is absent from Animalia. It is typically found as an α2β2 tetramer. The α subunits catalyze the reversible formation of indole and glyceraldehyde-3-phosphate (G3P) from indole-3-glycerol phosphate (IGP). The β subunits catalyze the irreversible condensation of indole and serine to form tryptophan in a pyridoxal phosphate (PLP) dependent reaction. Each α active site is connected to a β active site by a 25 angstrom long hydrophobic channel contained within the enzyme. This facilitates the diffusion of indole formed at α active sites directly to β active sites in a process known as substrate channeling. The active sites of tryptophan synthase are allosterically coupled.

<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">Indole-3-acetic acid</span> Chemical compound

Indole-3-acetic acid is the most common naturally occurring plant hormone of the auxin class. It is the best known of the auxins, and has been the subject of extensive studies by plant physiologists. IAA is a derivative of indole, containing a carboxymethyl substituent. It is a colorless solid that is soluble in polar 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">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.

<i>Erysimum cheiranthoides</i> Species of flowering plant

Erysimum cheiranthoides, the treacle-mustard,wormseed wallflower, or wormseed mustard is a species of Erysimum native to most of central and northern Europe and northern and central Asia. Like other Erysimum species, E. cheiranthoides accumulates two major classes of defensive chemicals: glucosinolates and cardiac glycosides.

<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.

<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.

<span class="mw-page-title-main">Indole-3-glycerol-phosphate synthase</span> Class of enzymes

The enzyme indole-3-glycerol-phosphate synthase (IGPS) (EC 4.1.1.48) catalyzes the chemical reaction

<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.

Tryptophan N-monooxygenase (EC 1.14.13.125, tryptophan N-hydroxylase, CYP79B1, CYP79B2, CYP79B3) is an enzyme with systematic name L-tryptophan,NADPH:oxygen oxidoreductase (N-hydroxylating). This enzyme catalyses the following chemical reaction

L-tryptophan—pyruvate aminotransferase is an enzyme with systematic name L-tryptophan:pyruvate aminotransferase. This enzyme catalyses the following chemical reaction

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

Camalexin (3-thiazol-2-yl-indole) is a simple indole alkaloid found in the plant Arabidopsis thaliana and other crucifers. The secondary metabolite functions as a phytoalexin to deter bacterial and fungal pathogens.

<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">Georg Jander</span> American plant biologist

Georg Jander is an American plant biologist at the Boyce Thompson Institute in Ithaca, New York. He has an adjunct appointment in the Plant Biology Section of the School of Integrative Plant Sciences at Cornell University. Jander is known for his molecular research identifying genes for biochemical compounds of ecological and agricultural importance, particularly those plant traits involved in resistance to insect pests.

References

  1. Agerbirk, Niels; Vos, Martin; Kim, Jae Hak; Jander, Georg (2008). "Indole glucosinolate breakdown and its biological effects". Phytochemistry Reviews. 8: 101. doi:10.1007/s11101-008-9098-0.
  2. 1 2 Clay, N. K.; Adio, A. M.; Denoux, C.; Jander, G.; Ausubel, F. M. (2009). "Glucosinolate Metabolites Required for an Arabidopsis Innate Immune Response". Science. 323 (5910): 95–101. Bibcode:2009Sci...323...95C. doi:10.1126/science.1164627. PMC   2630859 . PMID   19095898.
  3. 1 2 Bednarek, P.; Pislewska-Bednarek, M.; Svatos, A.; Schneider, B.; Doubsky, J.; Mansurova, M.; Humphry, M.; Consonni, C.; Panstruga, R.; Sanchez-Vallet, A.; Molina, A.; Schulze-Lefert, P. (2009). "A Glucosinolate Metabolism Pathway in Living Plant Cells Mediates Broad-Spectrum Antifungal Defense". Science. 323 (5910): 101–106. Bibcode:2009Sci...323..101B. doi: 10.1126/science.1163732 . PMID   19095900.
  4. Herrman, Klaus M.; Weaver, Lisa M. (1999). "The Shikimate Pathway". Annu. Rev. Plant Physiol. Plant Mol. Biol. 50: 473–503. doi:10.1146/annurev.arplant.50.1.473. PMID   15012217.
  5. 1 2 3 Bender, Judith; Celenza, John L. (2008). "Indolic Glucosinolates at the Crossroads of Tryptophan Metabolism". Phytochem. Rev. 8: 25–37. doi:10.1007/s11101-008-9111-7.
  6. Mikkelsen, Michael; Naur, Peter; Halkier, Barbara (March 2004). "Arabidopsis Mutants in the C–S Lyase of Glucosinolate Biosynthesis Establish a Critical Role for Indole-3-acetaldoxime in Auxin Homeostasis". The Plant Journal. 37 (5): 770–777. doi: 10.1111/j.1365-313x.2004.02002.x . PMID   14871316.

Further reading