Chemistry of indole glucosinolates: intermediacy of indol-3-ylmethyl isothiocyanates in the enzymic hydrolysis of indole glucosinolates

Hanley, A. Bryan; Parsley, K. R.; Lewis, Jenny; Fenwick, G. R.

doi:10.1039/p19900002273

Cited by 48 publications

(48 citation statements)

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“…11 Based on mass-spectrometric analysis Hanley et al postulated the transient formation of 1-MIM isothiocyanate in the myrosinasemediated breakdown of 1-MIM glucosinolate. 15 This intermediate appeared to react with the nucleophile water leading to the formation of 1-MIM alcohol. We suspect that an analogous reaction with DNA underlies the mutagenic effects observed with 1-MIM glucosinolate in the presence of myrosinase.…”

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Detection of DNA Adducts Originating from 1-Methoxy-3-indolylmethyl Glucosinolate Using Isotope-Dilution UPLC-ESI-MS/MS

et al. 2012

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1-Methoxy-3-indolylmethyl (1-MIM) glucosinolate, present at substantial levels in several food crops (e.g., broccoli and cabbage), forms DNA adducts in vitro and is mutagenic to bacterial and mammalian cells after activation by the plant enzyme myrosinase. Moreover, a breakdown product, 1-MIM alcohol, is metabolized to a secondary reactive intermediate by some mammalian sulfotransferases (SULTs). First, we incubated herring-sperm DNA with 1-MIM glucosinolate in the presence of myrosinase. We identified and synthesized the predominant adducts, N(2)-(1-MIM)-dG and N(6)-(1-MIM)-dA, and developed an UPLC-ESI-MS/MS method for their specific detection using isotopic dilution. Second, we demonstrated both DNA adducts in target cells (Salmonella typhimurium TA100 and Chinese hamster V79) of standard mutagenicity tests treated with 1-MIM glucosinolate/myrosinase as well as in 1-MIM alcohol-treated Salmonella and V79 cells engineered for expression of human SULT1A1. Similar excesses of N(2)-(1-MIM)-dG over N(6)-(1-MIM)-dA adducts were found in all cellular models independent of the test compound (1-MIM glucosinolate or alcohol), whereas dA adducts predominated in the cell-free system. Finally, we detected both DNA adducts in colon tissue of a mouse orally treated with 1-MIM glucosinolate. We are going to use this specific and sensitive method for investigating genotoxic risks of food-borne exposure to 1-MIM glucosinolate in animal and human studies.

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Detection of DNA Adducts Originating from 1-Methoxy-3-indolylmethyl Glucosinolate Using Isotope-Dilution UPLC-ESI-MS/MS

et al. 2012

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“…Three species of mustard seeds have commercial value: black (Brassica nigra), white or yellow (Brassica alba), and brown (Brassica juncea) seeds. In the present study, we focused on evaluating black mustard (B. nigra) EO, because this type of mustard seed has a significant amount of the characteristic volatile compound allyl-isothiocyanate (AITC) (7). Isothiocyanates display a wide antimicrobial spectrum; aromatic isothiocyanates, such as AITC, are more effective than those with an aliphatic side chain (2).…”

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Composition, Diffusion, and Antifungal Activity of Black Mustard (Brassica nigra) Essential Oil When Applied by Direct Addition or Vapor Phase Contact

Mejía-Garibay

Palou

López‐Malo

2015

Journal of Food Protection

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In this study, we characterized the essential oil (EO) of black mustard (Brassica nigra) and quantified its antimicrobial activity, when applied by direct contact into the liquid medium or by exposure in the vapor phase (in laboratory media or in a bread-type product), against the growth of Aspergillus niger, Aspergillus ochraceus, or Penicillium citrinum. Allyl-isothiocyanate (AITC) was identified as the major component of B. nigra EO with a concentration of 378.35 mg/ml. When B. nigra EO was applied by direct contact into the liquid medium, it inhibited the growth of A. ochraceus and P. citrinum when the concentration was 2 μl/ml of liquid medium (MIC), while for A. niger, a MIC of B. nigra EO was 4 μl/ml of liquid medium. Exposure of molds to B. nigra EO in vapor phase showed that 41.1 μl of B. nigra EO per liter of air delayed the growth of P. citrinum and A. niger by 10 days, while A. ochraceus growth was delayed for 20 days. Exposure to concentrations ≥ 47 μl of B. nigra EO per liter of air (MIC) inhibited the growth of tested molds by 30 days, and they were not able to recover after further incubation into an environment free of EO (fungicidal effect). Adsorbed AITC was quantified by exposing potato dextrose agar to B. nigra EO in a vapor phase, exhibiting that AITC was retained at least 5 days when testing EO at its MIC or with higher concentrations. Mustard EO MIC was also effective against the evaluated molds inhibiting their growth for 30 days in a bread-type product when exposed to EO by vapor contact, demonstrating its antifungal activity.

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“…Furthermore, IAOx has been shown to be a precursor of the phytohormone indole-3-acetic acid (IAA) as evidenced by enzyme studies with radiolabeled IAOx (16) and the high-auxin phenotype of knockout mutants in postoxime enzymes in glucosinolate biosynthesis, such as sur1 (17) and sur2 (14,18). Based on structural similarity, it has been suggested that brassinin and possibly other cruciferous phytoalexins were derived from the indole glucosinolate glucobrassicin (5). However, in a recent in vivo feeding study in turnip (Brassica rapa) roots with deuterated IAOx and glucobrassicin, IAOx, and not glucobrassicin, was incorporated into brassinin and brassinin-derived phytoalexins, indicating that IAOx is an intermediate in brassinin biosynthesis (19).…”

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“…Very little is known about the biosynthetic pathway of the S-containing indole phytoalexins. Their similar structure with N-and S-containing side chains at C-3 of the indole ring suggests a biogenetic relationship (5). Camalexin (3-thiazol-2Ј-yl-indole) is produced in the model plant Arabidopsis thaliana (6).…”

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Camalexin is synthesized from indole-3-acetaldoxime, a key branching point between primary and secondary metabolism in Arabidopsis

Glawischnig¹,

Hansen²,

Olsen³

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

286

287

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Characteristic for cruciferous plants is their production of N-and S-containing indole phytoalexins with disease resistance and cancer-preventive properties, previously proposed to be synthesized from indole independently of tryptophan. We show that camalexin, the indole phytoalexin of Arabidopsis thaliana, is synthesized from tryptophan via indole-3-acetaldoxime (IAOx) in a reaction catalyzed by CYP79B2 and CYP79B3. Cyp79B2͞cyp79B3 double knockout mutant is devoid of camalexin, as it is also devoid of indole glucosinolates [Zhao, Y., Hull, A. K., Gupta, N. R., Goss, K. A., Alonso, J., Ecker, J. R., Normanly, J., Chory, J. & Celenza, J. L. (2002) Genes Dev. 16, 3100 -3112], and isotope-labeled IAOx is incorporated into camalexin. These results demonstrate that only CYP79B2 and CYP79B3 contribute significantly to the IAOx pool from which camalexin and indole glucosinolates are synthesized. Furthermore, production of camalexin in the sur1 mutant devoid of glucosinolates excludes the possibility that camalexin is derived from indole glucosinolates. CYP79B2 plays an important role in camalexin biosynthesis in that the transcript level of CYP79B2, but not CYP79B3, is increased upon induction of camalexin by silver nitrate as evidenced by microarray analysis and promoter-␤-glucuronidase data. The structural similarity between cruciferous indole phytoalexins suggests that these compounds are biogenetically related and synthesized from tryptophan via IAOx by CYP79B homologues. The data show that IAOx is a key branching point between several secondary metabolic pathways as well as primary metabolism, where IAOx has been shown to play a critical role in IAA homeostasis.C haracteristic for cruciferous plants is the synthesis of a wide range of species-specific phytoalexins that structurally are sulfur-containing indole alkaloids (1) and the synthesis of glucosinolates (reviewed in ref.2). Both groups of natural products are involved in plant defense and have cancer-preventive properties (3, 4). Very little is known about the biosynthetic pathway of the S-containing indole phytoalexins. Their similar structure with N-and S-containing side chains at C-3 of the indole ring suggests a biogenetic relationship (5). Camalexin (3-thiazol-2Ј-yl-indole) is produced in the model plant Arabidopsis thaliana (6). It is induced by a variety of microorganisms, e.g., Pseudomonas syringae (6) and Alternaria brassisicola (7), and by abiotic factors, such as AgNO 3 (8). These findings make camalexin a good model compound for studying biosynthesis and regulation of cruciferous indole phytoalexins. In vivo feeding experiments where radiolabeled anthranilate and tryptophan were applied on leaves treated with AgNO 3 led to the suggestion that tryptophan was not a precursor in camalexin biosynthesis because tryptophan was much less efficiently incorporated into camalexin compared with anthranilate (8, 9). The data were further supported by labeling studies performed in three tryptophan mutants (8), where reduced levels of camalexin accumulated in ...

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Chemistry of indole glucosinolates: intermediacy of indol-3-ylmethyl isothiocyanates in the enzymic hydrolysis of indole glucosinolates

Abstract: The hydrolysis of (I) proceeds via the isothiocyanate (II) yielding (III) and (IV).

Cited by 48 publications

References 10 publications

Detection of DNA Adducts Originating from 1-Methoxy-3-indolylmethyl Glucosinolate Using Isotope-Dilution UPLC-ESI-MS/MS

Detection of DNA Adducts Originating from 1-Methoxy-3-indolylmethyl Glucosinolate Using Isotope-Dilution UPLC-ESI-MS/MS

Composition, Diffusion, and Antifungal Activity of Black Mustard (Brassica nigra) Essential Oil When Applied by Direct Addition or Vapor Phase Contact

Camalexin is synthesized from indole-3-acetaldoxime, a key branching point between primary and secondary metabolism in Arabidopsis

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