Mustard oil glycosides

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General structural formula of mustard oil glycosides (glucosinolates)

The mustard oil glycosides , also known as glucosinolates , belong to the group of glycosides . Since the aglycon is bound to the sugar part (glycon) via a sulfur atom, it is more precisely referred to as a thioglycoside.

Mustard oil glycosides are chemical compounds that contain sulfur and nitrogen and are formed from amino acids. These phytochemicals give members of the cruciferous family such as radish , horseradish , mustard , cress and cabbage the somewhat pungent and bitter taste and are contained in the mustard oils made from them . Even more plants from the order of Kreuzblütlerartigen like nasturtiums sometimes contain glucosinolates in significant quantities.

Substance group

There are around 120 different glucosinolates, which only differ in terms of the aglycon residue. Glucose always appears as sugar . The cleavage enzyme of the glucosinolates is myrosinase , which is spatially separated in the cells. If the cells are damaged (chewing or cutting), myrosinase and mustard oil glycosides come together, which are hydrolyzed to mustard oils . Mustard oils are either non-volatile and have a pungent taste, or they are volatile and have a pungent smell.

Since mustard oil glycosides act as constitutive defense substances ( phytoanticipins ) against animal damage, it can be assumed in the context of evolutionary theory that this group of substances resulted in a selection advantage. According to recent findings, these flavors prevent infections and support cancer prevention , such as sulforaphane or Iberine. Mustard oil glycosides from nasturtium and horseradish root are combined in medicine as a phytotherapeutic agent for the treatment and prophylaxis of respiratory and urinary tract infections.

Under certain conditions, mustard oil glycosides can also form thiocyanates . These can lead to goiter formation in humans and animals ( goiter- inherent substance ) in high concentrations or in high intake, especially after consumption of large amounts of cabbage (with the glucosinolate glucobrassicin ), as occurs in times of need . The ions of the pseudohalide thiocyanate displace iodide ions from the thyroid tissue, so that less iodine is available for the synthesis of the thyroid hormone thyroxine .

For glucosinolates and their hydrolysis products as well as metabolites chemoprotective effects against various carcinogens have been demonstrated. They block tumors from developing in a number of tissues and organs such as the liver , colon , mammary glands , pancreas, and others.

Use in medicine

Mustard oils (e.g. allyl mustard oil ) are used therapeutically as topical skin irritants (rubefacientia). Some of them have a strong antibacterial effect .

Preparations made from plants containing mustard oil are also used medicinally. Because of its benzyl mustard oil content, nasturtiums have a bacteriostatic effect (in gram-positive and gram-negative bacteria and in vitro against multi-resistant staphylococci ), virustatic ( in vitro also 90 percent reduction in H1N1 viruses), antifungal and hyperemic.

The antimicrobial effect of the mustard oils in horseradish (especially against Bacillus subtilis , Escherichia coli and Staphylococcus aureus ) and a hyperaemic effect have also been scientifically proven . The essential oil contains allyl mustard oil (approx. 90%) and 2-phenylethylene mustard oil . Depending on the dose, the horseradish has a bacteriostatic or bactericidal effect in vitro . The allyl mustard oil from the horseradish root shows a good effectiveness in the gram-negative spectrum, while the 2-phenylethyl mustard oil from the horseradish root has an extended spectrum of action in the gram-positive range.

Mustard oil glycosides from nasturtium and horseradish root are combined in practice as a phytotherapeutic agent for the treatment and prophylaxis of respiratory and urinary tract infections.

Numerous in-vitro studies show that even in small doses, the plant substances fight a large number of clinically relevant pathogens - including the most common pathogens causing urinary tract and bacterial respiratory infections - and also have anti-inflammatory effects. The S3 guideline for the treatment of uncomplicated urinary tract infections, updated in 2017, recommends the use of medicinal products with nasturtiums and horseradish as herbal treatment options for frequently recurring cystitis .

In 2010, studies at the Institute for Medical Virology at the University of Giessen showed that mustard oils made from nasturtiums and horseradish can inhibit the multiplication of H1N1 flu viruses. In the in vitro model with human lung cells, reproduction was inhibited by around 90 percent. As early as 1958, scientific studies on exembryonated hen's eggs under the influence of mustard oils from nasturtiums and horseradish demonstrated a strong inhibition of the multiplication of influenza viruses.

Occurrence and biochemical characteristics

Small nasturtium ( Tropaeolum minus )

Mustard oil glycosides are found in cruciferous vegetables in Central Europe without exception . Otherwise they are widespread in the caper family , but they occur sporadically in the nasturtium family , milkweed family and other plant families . Glycosinolates are split by myrosinase into glucose , hydrogen sulfate HSO 4 - and one of the following aglycones : isothiocyanate , thiocyanate , nitrile , or oxazolidine-2-thione. These can cause symptoms of poisoning in (mostly only) higher concentrations:

  • Isothiocyanates (chemical: R – N = C = S) irritate the mucous membrane , but are usually absorbed in such small amounts that no further damage is caused. When glycosinolates are absorbed and broken down into isothiocyanates in the intestine, they can have a negative impact on the production of thyroid hormones.
The mustard oil glycoside 1 is converted into the isothiocyanate 3 (a mustard oil). Glucose 2 is released at the same time, only the β-form of D -glucose is shown.
R = allyl , benzyl , 2-phenylethyl etc.
  • Oxazolidine-2-thiones are formed from isothiocyanates of glucosinolates with 2- hydroxy side groups , e.g. B. the glucosinolate Progoitrin via the intermediate stage of Goitrin. Oxazolidine-2-thiones disrupt growth and increase the likelihood of goiter formation. They block thyroid function by inhibiting iodine uptake in thyroxine precursors and by inhibiting thyroxine secretion from the thyroid gland.
  • Nitriles (R – C = N) disrupt growth, cause liver and kidney damage, and in severe cases lead to liver necrosis.
  • Thiocyanates (R − S − C = N) prevent iodine uptake in the thyroid gland, thereby reducing tyrosine iodination and reduced thyroxine synthesis.
The table shows glycosides, the organic-chemical side residue R and their biosynthetic origin, mustard oils and plants in which these occur (according to the lexicon of biology and other specialist literature).
Mustard oil glycoside R = chemical residue biosynthesized from Mustard oil and other breakdown products Occurrence
Sinigrin 2-propenyl, allyl (CH 2 = CH – CH 2 -) Methionine Allyl isothiocyanate Black mustard , horseradish , garlic mustard , wasabi , broccoli , Brussels sprouts , cabbage
Glucosinalbine 4-hydroxybenzyl, p -hydroxybenzyl Tyrosine , phenylalanine ? 4-hydroxybenzyl isothiocyanate, 4-hydroxybenzyl nitrile Brassica seeds
Sinalbin Sinapine salt of glucosine bin Tyrosine , phenylalanine ? 4-hydroxybenzyl isothiocyanate, 4-hydroxybenzyl nitrile White mustard
Glucotropaeolin (GTL) Benzyl Tyrosine , phenylalanine ? Benzyl isothiocyanate, tropaeolin Nasturtium , garden cress , garlic mustard , horseradish tree , maca
Gluconasturtiin (GNAST, GST) 2-phenethyl, 2-phenylethyl Tyrosine , phenylalanine ? Phenylethyl isothiocyanate (PEITC), nasturtiine (NAS) Horseradish , watercress , winter cress , broccoli ,
Gluconapine (GNA) 3-butenyl (CH = CH – CH 2 –CH 2 -) Methionine 3-butenyl isothiocyanate, napin Rapeseed , turnip rape , Chinese cabbage , cabbage , shepherd's purse , Lesquerella fendleri , Lobularia maritima
Glucoraphenin 4-methylsulfinyl-3-butenyl (CH 3 –SO – CH = CH – CH 2 –CH 2 -) Methionine Sulforaphene, sulforaphenenitrile Garden radish , radish , Matthiola longipetala
Glucoraphanin 4-methylsulfinylbutyl (CH 3 –SO– (CH 2 ) 4 -) Methionine Sulforaphane , sulforaphanenitrile Broccoli , radish , white cabbage , cauliflower , cabbage , Erysimum allionii , rocket
Glucobrassicin 3-indolylmethyl Tryptophan Indole-3-carbinol , 3-indolylmethyl-isothiocyanate, brassicin Cabbage , broccoli , woad , palm kale , (especially red) cauliflower
Glucocochlearin (1MP) 1-methylpropyl (CH 3 –CH 2 - (CH 3 ) CH–) Isoleucine sec -butyl isothiocyanate, cochlearin Real spoonwort , meadowfoam , wasabi , boechera holboellii
Glucobrassicanapine (GBN) 4-pentenyl (CH 2 = CH 2 –CH 2 –CH 2 –CH 2 -) Methionine Brassicanapine Chinese cabbage
Progoitrin (2 R ) -2-hydroxy-3-butenyl (CH 2 = CH – CHOH – CH 2 -) Methionine Goitrin Broccoli , cabbage , rapeseed , arugula
Epiprogoitrin (2 S ) -2-Hydroxy-3-butenyl (CH 2 = CH – CHOH – CH 2 - Methionine Goitrin Broccoli , cabbage , rapeseed , arugula
Gluconapoleiferin 2-hydroxy-4-pentenyl (CH 2 = CH 2 –CH 2 –CHOH – CH 2 -) Methionine Napoleiferin
Glucoiberin 3-methylsulfinylpropyl (CH 3 –SO – CH 2 –CH 2 –CH 2 -) Methionine Iberin (IBN) Candytufts , broccoli , cabbage , lesquerella fendleri
Glucoibeverine, glucoiberverine (GIV) 3-methylthiopropyl (CH 2 –S – CH 2 –CH 2 –CH 2 -) Methionine Ibe (r) verin Cabbage
Glucocheiroline 3-methylsulfonylpropyl (CH 3 –SO 2 –CH 2 –CH 2 –CH 2 -) Methionine Cheirolin Erysimum allionii , Erysimum cheiri
Neoglucobrassicin (NGBS) 1-methoxy-3-indolylmethyl Tryptophan Winter cress , cabbage
Glucocapparin Methyl (CH 3 -) Methionine Methyl isothiocyanate, caparin Capers , Boscia senegalensis
Glucolepidine Ethyl (CH 3 - CH 2 -) Methionine Lepidine Garden cress
Glucopurtanjivin, Glucoputranjivin? Isopropyl, 2-propyl (CH 3 - (CH 3 ) CH–) Methionine Purtanjivin, Putranjivin? Sisymbrium officinale , Tovaria
Glucojiaputin 2-methylbutyl (CH 3 –CH 2 - (CH 3 ) CH – CH 2 -) Methionine Jiaputin
Glucobarbarin (BAR) ( S ) -2-hydroxy-2-phenylethyl Tyrosine , phenylalanine ? Barbarian Winter cress
Glucoaubrietin p -methoxybenzyl Tyrosine , phenylalanine ? Aubrietin Aubrietia spec.
Glucolimnanthin m -methoxybenzyl Tyrosine , phenylalanine ? Limnanthin, 2- (3-methoxyphenyl) acetamide, 2- (3-methoxymethyl) ethanthioamide, 3-methoxyphenylacetonitrile) Limnanthes alba ( Limnanthaceae )
Glucoerucine (GER) 4-methylthiobutyl, 4-methylsulfanylbutyl (CH 3 –S – CH 2 –CH 2 –CH 2 –CH 2 -) Methionine Erucine, erucine nitrile Rocket ( Eruca sativa ), Erysimum allionii , Rutabaga, cabbage
Glucoraphasatin (glucodehydroerucin) 4-methylthiobut-3-enyl; 4-methylsulfanyl-3-butenyl; vinyl sulfide (CH 3 –S – CH = CH – CH 2 –CH 2 -) Methionine Raphasatin radish
Glucoberteroin 5-methylthiopentyl (CH 3 –S– (CH 2 ) 5 -) Methionine Berteroin
Glucolesquerellin 6-methylthiohexyl (CH 3 –S– (CH 2 ) 6 -) Methionine Lesquerellin Lesquerella spec. , Lobularia maritima
Glucojirsutin, glucoarabishirsuin 8-methylthiooctyl (CH 3 –S– (CH 2 ) 8 -) Methionine Jirsutin Arabis spec.
Glucoarabine 9-methylthiononyl (CH 3 –S– (CH 2 ) 9 -) Methionine Arabin Arabis spec.
Glucoerysoline 4- (methylsulfonyl) butyl (CH 3 –SO 2 - (CH 2 ) 4 -) Methionine Erysoline Erysimum allionii
N-acetyl-3-indolylmethyl-GLS N-acetyl-3-indolylmethyl Tryptophan Tovaria
Glucoalyssin Methylsulfinylpentyl (CH 3 –SO– (CH 2 ) 5 -) Methionine Alyssin Rapeseed , pak choi , rocket
4-hydroxy glucobrassicin 4-OH-3-indolylmethyl Tryptophan 4-hydroxy brassicin Cabbage
4-methoxy-glucobrassicin 4-methoxy-3-indolylmethyl Tryptophan 4-methoxy brassicin Cabbage
3- (hydroxymethyl) pentyl (CH 3 –CH 2 - (CHOH) CH – CH 2 –CH 2 -) Methionine Meadowfoam
Glucosativin ( dimer ) 4-mercaptobutyl Methionine Sativin arugula
Glucohesperin 6-methylsulfinylhexyl Methionine 6-methylsulfinylhexyl isothiocyanate (6-MSITC) Wasabi
Glucoputranjivin 1-methylethyl (CH 3 - (CH 3 ) CH–) Valine Boechera holboellii
(2MP) 2-methylpropyl (CH 3 - (CH 3 ) CH 2 –CH 2 -) Leucine Boechera holboellii
Glucoarabidopsithalianain 4-hydroxybutyl Methionine Arabidopsithalianain Arabidopsis thaliana , rapeseed
Glucoarabishirsutain 7-methylthioheptyl Methionine Arabishirsutain horseradish
Glucocleomine 2-hydroxy-2-methylbutyl Methionine Cleomin Spider flower
Glucoconringiin 2-hydroxy-2-methylpropyl Methionine Conringiin Conringia orientalis
Glucoerysimumhieracifolium 3-hydroxypropyl Methionine Erysimumhieracifolium Rod Schöterich
Glucohirsutin 8-methylsulfinyloctyl Methionine Hirsutin Arabidopsis thaliana
Glucomalcomiin 3-benzoyloxypropyl Methionine Malcomiin Carrichtera annua
Glucosymbrin 2-hydroxy-1-methylethyl Methionine Sisymbrin Sisymbrium austriacum

Individual evidence

  1. ↑ The genetic basis of a plant-insect coevolutionarykey innovation Christopher W. Wheat et al. PNAS December 18, 2007, Vol. 104 (51) pages 20427-20431; https://doi.org/10.1073/pnas.0706229104 accessed on May 22, 2019.
  2. ↑ a b Srinibas Das, Amrish Kumar Tyagi, Harjit Kaur: Cancer modulation by glucosinolates: A review. ( Memento of the original from March 4, 2016 in the Internet Archive ) Info: The @1@ 2Template: Webachiv / IABot / tejas.serc.iisc.ernet.in archive link was inserted automatically and has not yet been checked. Please check the original and archive link according to the instructions and then remove this notice. (PDF; 68 kB) Current Science , Vol. 79, No. 12, December 25, 2000, 1665-1671.
  3. ↑ Entry on glucosinolates. In: Römpp Online . Georg Thieme Verlag, accessed on June 18, 2013.
  4. ↑ a b Heinz Schilcher (Ed.): Guideline Phytotherapy , Verlag Urban & Fischer, Munich 2016, pp. 178–180; 220-221.
  5. ↑ A. Winter: Antibiotic therapy with medicinal plants . In: Planta Medica . tape 3 , no. 01 , January 15, 1955, p. 1-16 , doi : 10.1055 / s-0028-1101750 .
  6. ↑ a b Andreas Conrad, Teena Kolberg, Inge Engels, Uwe Frank: In-vitro studies on the antibacterial effectiveness of a combination of nasturtium herb (Tropaeoli majoris herba) and horseradish root (Armoraciae rusticanae radix) . In: drug research . tape 56 , no. 12 , p. 842-849 .
  7. ↑ a b A Conrad, H Richter, D Bauer, T Nobis, I Engels, U Frank: Broad antibacterial effect of a mixture of mustard oils in vitro . In: Journal of Phytotherapy . tape 29 , S 1, 2008, doi : 10.1055 / s-2008-1047852 .
  8. ↑ V. Dufour et al .: The antibacterial properties of isothiocyanates. In: Microbiology 161: 229-243 (2015).
  9. ↑ A. Borges et al .: Antibacterial activity and mode of action of selected glucosinolates hydrolysis products against bacterial pathogens. In: J Food Sci Technol 52 (8): 4737-4748 (2015).
  10. ^ A. Marzocco et al .: Anti-inflammatory activity of horseradisch (Armoracia rusticana) root extracts in LPS-stimulated macrophages. In: Food Func. 6 (12): 3778-88 (2015)
  11. ↑ H. Tran et al .: Nasturtium (Indian cress, Tropaeolum majus nanum) dually blocks the COX an LOX pathway in primary human immune cells. In: Phytomedicine 23: 611-620 (2016).
  12. ↑ ML Lee et al .: Benzyl isothiocyanate exhibits anti-inflammatory effects in murine macrophages and in mouse skin. In: J Mol Med 87: 1251-1261 (2009).
  13. ↑ S3 guideline uncomplicated urinary tract infections - update 2017 (interdisciplinary S3 guideline "Epidemiology, diagnostics, therapy, prevention and management of uncomplicated, bacterial, community-acquired urinary tract infections in adult patients", AWMF register no. 043/044).
  14. ↑ Werner Stingl: Fight Influenza Viruses with Phytotherapy. In: Ärzte Zeitung , December 16, 2010.
  15. ↑ Winter, AG, Willeke, L .: Studies on the influence of mustard oils on the multiplication of the influenza virus in exembryonated hen's eggs , Arch. Mikrobiol . 31, pp. 311-318 (1958).
  16. ↑ Jihad Attieh Biochemical characterization of a novel halide / bisulfide methyltransferase purified from Brassica oleracea
  17. ↑ Genyi Li, Carlos F. Quiros: Genetic Analysis, Expression and Molecular Characterization of BoGSL-ELONG, a Major Gene Involved in the Aliphatic Glucosinolate Pathway of Brassica Species . In: Genetics . tape 162 , no. 4 , December 1, 2002, p. 1937-1943 .
  18. ↑ Patent US6716827 : Complexes for immobilizing isothiocyanate natural precursors in cyclodextrins, preparation and use. ‌
  19. ^ Complexes Isothiocyanates from Cruciferous Vegetables: Kinetics, Biomarkers and Effects .
  20. ↑ Patrick Kabouw, Arjen Biere, Wim H. van der Putten, Nicole M. van Dam: Intra-specific Differences in Root and Shoot Glucosinolate Profiles among White Cabbage (Brassica oleracea var. Capitata) Cultivars . In: Journal of Agricultural and Food Chemistry . tape 58 , no. 1 , January 13, 2010, p. 411-417 , doi : 10.1021 / jf902835k .
  21. ↑ Barbara Kusznierewicz, Renato Iori, Anna Piekarska, Jacek Namieśnik, Agnieszka Bartoszek: Convenient identification of desulfoglucosinolates on the basis of mass spectra obtained during liquid chromatography – diode array – electrospray ionization mass spectrometry analysis: Method verification for sprouts of different Brassicaceae extracts . In: Journal of Chromatography A . tape 1278 , February 22, 2013, p. 108–115 , doi : 10.1016 / j.chroma.2012.12.075 .
  22. ↑ a b c d e f g h i j k l m Steven F. Vaughn, Mark A. Berhow: Glucosinolate hydrolysis products from various plant sources: pH effects, isolation, and purification . In: Industrial Crops and Products . tape 21 , no. 2 , March 2005, p. 193-202 , doi : 10.1016 / j.indcrop.2004.03.004 .
  23. ↑ a b c d e Federica Pasini, Vito Verardo, Lorenzo Cerretani, Maria Fiorenza Caboni, Luigi Filippo D'Antuono: Rocket salad (Diplotaxis and Eruca spp.) Sensory analysis and relation with glucosinolate and phenolic content . In: Journal of the Science of Food and Agriculture . tape 91 , no. December 15 , 2011, p. 2858-2864 , doi : 10.1002 / jsfa.4535 .
  24. ↑ a b c Aaron J. Windsor et al .: Geographic and evolutionary diversification of glucosinolates among near relatives of Arabidopsis thaliana (Brassicaceae) . In: Phytochemistry . tape 66 , no. June 11 , 2005, p. 1321-1333 , doi : 10.1016 / j.phytochem.2005.04.016 .
  25. ↑ a b Flowering plants, Dicotyledons: Malvales, Capparales, and non-betalain Caryophyllales . In: The Families and Genera of Vascular Plants . Springer, Berlin; New York 2003, ISBN 3-540-42873-9 ( limited preview in Google Book Search).
  26. Jump up ↑ Inga A. Zasada, Jerry E. Weiland, Ralph L. Reed, Jan F. Stevens: Activity of Meadowfoam (Limnanthes alba) Seed Meal Glucolimnanthin Degradation Products against Soilborne Pathogens . In: Journal of Agricultural and Food Chemistry . tape 60 , no. 1 , January 11, 2012, p. 339-345 , doi : 10.1021 / jf203913p .
  27. ↑ Sabine Montaut, Jessica Barillari, Renato Iori, Patrick Rollin: Glucoraphasatin: Chemistry, occurrence, and biological properties . In: Phytochemistry . tape 71 , no. 1 , January 2010, p. 6-12 , doi : 10.1016 / j.phytochem.2009.09.021 .
  28. Jump up ↑ Niels Agerbirk, Carl Erik Olsen, Frances S. Chew, Marian Ørgaard: Variable Glucosinolate Profiles of Cardamine pratensis (Brassicaceae) with Equal Chromosome Numbers . In: Journal of Agricultural and Food Chemistry . tape 58 , no. 8 , April 28, 2010, p. 4693-4700 , doi : 10.1021 / jf904362m .
  29. ↑ De-Xing Hou et al: Dynamics of Nrf2 and Keap1 in ARE-Mediated NQO1 Expression by Wasabi 6- (Methylsulfinyl) hexyl Isothiocyanate . In: Journal of Agricultural and Food Chemistry . tape 59 , no. 22 , 23 November 2011, pp. 11975-11982 , doi : 10.1021 / jf2032439 .

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