Determination of glucosinolate profiles in Chinese vegetables by precursor ion scan and multiple reaction monitoring scan mode (LC-MS/MS)

Skutlarek, Dirk; Färber, Harald; Lippert, F.; Ulbrich, Andreas; Wawrzun, Andreas; Büning‐Pfaue, Hans

doi:10.1007/s00217-004-1014-2

Cited by 11 publications

(9 citation statements)

References 19 publications

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“…11;and gluconasturtiin,No. 12) are consistent with those reported in previous studies (Rosa et al 1997;Ciska et al 2000;Skutlarek et al 2004;Kang et al 2006;Padilla et al 2007). Kang et al (2006) studied in 23 accessions of Chinese cabbage the factors affecting the phenotypic variation of gsl content in two different environments.…”

Section: Natural Variation Of Glucosinolate Compositionsupporting

confidence: 92%

“…A few major genes involved in the aliphatic, methionine-derived gsl biosynthesis in B. oleracea have been genetically characterized and cloned Li and Quiros 2003;Gao et al 2004). Gsl content have been surveyed in several crops such as broccoli, broccoli sprouts, cauliflower and oilseed rape among others (Barillari et al 2005;Windsor et al 2005;Font et al 2005;Tian et al 2005;Skutlarek et al 2004;Branca et al 2002).…”

Section: Introductionmentioning

confidence: 99%

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Survey of glucosinolate variation in leaves of Brassica rapa crops

Yang

Quirós

2010

Genet Resour Crop Evol

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The breakdown products of glucosinolates (gsl) are biologically active secondary metabolites involved in plant defense and human nutrition. We identified and quantified 14 different gsl present in the young leaves of 82 different varieties of Brassica rapa, including the following crops: Chinese cabbage, broccoleto, Pak choi and other leafy vegetables, turnip, sarson and rapeseed. We did not find crop specific gsl, but their quantity varied extensively among varieties and crops, except that the Chinese cabbage accessions tended to have similar gsl profile and amount. Gluconapin, glucobrassicanapin (aliphatic), neoglucobrassicin, glucobrassicin (indolic), and gluconaturtiin (aromatic) are the predominant gsl in most of the varieties surveyed. We also found two gsl not commonly found in B. rapa, 2-methyl-2-propenyl and n-butyl. Their identities were confirmed by HPLC-MS. Most of the Chinese cabbages contain lower amount of aliphatic than indolic gsl, whereas broccoleto, turnip and rapeseed all have much higher aliphatic gsl content than indolic gsl content. The predominant aliphatic gsl in most of the varieties contain 4-carbon side-chains. The lack of significant correlation observed between the conversion of 3-to 4-carbon side-chain gsl and the conversion of 4-to 5-carbon side-chain gsl suggests that these two elongation cycles are probably under the control of two independent genes in B. rapa. The absence of glucoraphanin in all accessions indicates that only functional Brgsl-Alk alleles are present in B. rapa.

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Section: Natural Variation Of Glucosinolate Compositionsupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Survey of glucosinolate variation in leaves of Brassica rapa crops

Yang

Quirós

2010

Genet Resour Crop Evol

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“…The current state-of-the-art in the analytical measurement of GLS is for HPLC-MS analysis of the intact glucosinolates reconstituted in water. 15,22,106,107 This approach has yet to be cross-validated against any of the validated official methods. While the change of detection systems from UV to mass spectrometry (MS) detection has been a natural progression, the most important change is arguably in the choice of the chromatographic stationary phase.…”

Section: Chromatographymentioning

confidence: 99%

“…15,116 Separations of intact GLS is difficult to achieve without ion-pair buffers, and the use of an acetonitrile/water mixture without any buffer has been reported, 32 as well as the use of 30 mM ammonium acetate pH 5.0 (formic acid), 75 10 mM ammonium formate (formic acid), 60 and 5 mm NH 4 $acetate. 107,119 The use of formic acid mobile phase modifier coupled with 100% aqueous compatible columns, shows great promise as a viable alternative without the involvement of nonvolatile ion-pair agents or TFA, and modern separations are now directly comparable with the earlier separations; e.g. water (0.1% HCOOH)/acetonitrile, with Luna C 18 column, 21 water/acetonitrile each with 0.1% formic acid.…”

Section: Chromatographymentioning

confidence: 99%

Glucosinolates, structures and analysis in food

2010

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Glucosinolates (GLS) are sulfur rich, anionic secondary metabolites found principally in the plant order Brassicales. This review focuses on identifying the range of GLS structures identified to date and summarises the current state of taxonomic reclassifications of GLS producing plants. Those Brassica species that are available to growers in the UK are highlighted and progress in the aspects of analytical chemistry relevant to conducting accurate determinations of GLS content of foods is reviewed. The degradation and derivatisation workflows that have been utilized for conducting ''glucosinolate analysis'' are summarized. A review is made of aspects of extraction, isolation, determination of purity, ultraviolet (UV) and mass spectrometry (MS) parameters, extinction coefficients, UV response factors, quantification procedures, and the availability of stable isotope labeled internal standards, and certified reference materials. An electronic database of structures, formulae and accurate masses of both the 200 known, and a further 180 predicted GLS, is provided for use in mass spectrometry.

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“…A range of mass spectrometric ionization methods have been explored, including fast‐atom bombardment,15 thermospray,16 atmospheric pressure chemical ionization,17 matrix‐assisted laser desorption/ionization,18 and electrospray ionization (ESI). Determination of intact, non‐desulfated GLSs by reversed‐phase ion‐pairing liquid chromatography/mass spectrometry (LC/MS) with trifluoroacetic acid (TFA) or triethylamine as ion‐pairing reagents19–22 in crude plant extracts has been described. Ion‐pairing LC with formic acid and triethylamine in a water/MeOH gradient has been used to analyze glucosinolates by negative ion LC/ESI‐MS 23, 24.…”

mentioning

confidence: 99%

Naturally occurring glucosinolates in plant extracts of rocket salad (Eruca sativa L.) identified by liquid chromatography coupled with negative ion electrospray ionization and quadrupole ion‐trap mass spectrometry

Cataldi

Rubino

Lelario

et al. 2007

Rapid Comm Mass Spectrometry

101

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A method for the comprehensive profiling of intact glucosinolates (GLSs), major and minor, occurring in leaves and seeds of rocket salad (Eruca sativa L.) is presented using optimized reversed-phase liquid chromatography (RP-LC) with electrospray ionization (ESI) ion trap mass spectrometry (ITMS). ESI-ITMS in the negative mode was confirmed to be very suitable to analyze these compounds in crude extracts. After extraction from the plant material with methanol/water (70:30 v/v) at 70 degrees C, the analytes of interest were separated on a C18 column using an eluent acidified with formic acid (0.1%) and modified with acetonitrile. All the GLSs found in leaves of rocket salad gave good signals corresponding to the deprotonated precursor ion, [M-H]-. Although the mass spectra also exhibited an analytically important non-covalent adduct ion at [2M-H]-, the structures of glucosinolates were confirmed by extensive sequential MS analysis, thereby substantially improving the identification of unknown compounds. The results obtained not only revealed in leaves of E. sativa at least twelve species of GLSs including seven aliphatic compounds (glucoraphanin with [M-H]- at m/z ratio of 436, glucoerucin at m/z 420, 4-mercaptobutyl-GLS at m/z 406, progoitrin/epiprogoitrin at m/z 388, sinigrin at m/z 358, 4-methylpentyl- and n-hexyl-GLS at m/z 402) and three indole glucosinolates (i.e., three N-heterocyclic compounds: 4-hydroxyglucobrassicin and 5-hydroxyglucobrassicin at m/z 463, and 4-methoxy-glucobrassicin at m/z 477), but also two structurally related compounds containing one intermolecular disulfide linkage (4-(beta-D-glucopyranosyldisulfanyl)butyl-GLS at m/z 600 and a dimeric 4-mercaptobutyl-GLS at m/z 811). This latter symmetric disulfide was previously considered as an artefact formed during extraction of GLSs from vegetative tissues. Glucosinolates were detected in the leaves with a wide range of contents (10-200 micromol/g) and a great variation in the composition. Only three GLSs were identified in seeds of rocket salad, namely glucoraphanin, glucoerucin and 4-methoxyglucobrassicin. As expected, the most abundant GLS in seeds is glucoerucin. The feasibility of the strategy was also demonstrated using a rapeseed extract of certified reference material (BCR367R). The results indicated the usefulness of this method for a rapid, sensitive and comprehensive profiling of the GLS family naturally occurring in extracts of crude plant matter.

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Determination of glucosinolate profiles in Chinese vegetables by precursor ion scan and multiple reaction monitoring scan mode (LC-MS/MS)

Cited by 11 publications

References 19 publications

Survey of glucosinolate variation in leaves of Brassica rapa crops

Survey of glucosinolate variation in leaves of Brassica rapa crops

Glucosinolates, structures and analysis in food

Naturally occurring glucosinolates in plant extracts of rocket salad (Eruca sativa L.) identified by liquid chromatography coupled with negative ion electrospray ionization and quadrupole ion‐trap mass spectrometry

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