Identification of botanical biomarkers in Argentinean Diplotaxis honeys: flavonoids and glucosinolates.

To select and establish floral biomarkers of the botanical origin of Diplotaxis tenuifolia honeys, the flavonoids and glucosinolates present in bee-deposited nectar collected from hive combs (unripe honey) and mature honey from the same hives fron which the unripe honey samples were collected were analyzed by LC-UV-PAD-ESI-MS(n). Glycosidic conjugates of the flavonols quercetin, kaempferol, and isorhamnetin were detected and characterized in unripe honey. D. tenuifolia mature honeys contained the aglycones kaempferol, quercetin, and isorhamnetin. The differences between the phenolic profiles of mature honey and freshly deposited honey could be due to hydrolytic enzymatic activities. Aliphatic and indole glucososinolates were analyzed in unripe and mature honeys, this being the first report of the detection and characterization of glucosinolates as honey constituents. Moreover, these honey samples contained different amounts of propolis-derived flavonoid aglycones (1765-3171 μg/100 g) and hydroxycinnamic acid derivatives (29-1514 μg/100 g). Propolis flavonoids were already present in the freshly deposited nectar, showing that the incorporation of these compounds to honey occurs at the early steps of honey production. The flavonoids quercetin, kaempferol, and isorhamnetin and the glucosinolates detected in the samples could be used as complementary biomarkers for the determination of the floral origin of Argentinean Diplotaxis honeys.

[1]  F. Ferreres,et al.  Flavonoids from Apis mellifera Beeswax , 1993 .

[2]  Barbara Ann Halkier,et al.  Biology and biochemistry of glucosinolates. , 2006, Annual review of plant biology.

[3]  F. Tomás-Barberán,et al.  Liquid chromatography-tandem mass spectrometry reveals the widespread occurrence of flavonoid glycosides in honey, and their potential as floral origin markers. , 2009, Journal of chromatography. A.

[4]  M. Battino,et al.  Antioxidant characterization of native monofloral Cuban honeys. , 2010, Journal of agricultural and food chemistry.

[5]  S. Lamberto,et al.  A melissopalynological map of the South and Southwest of the Buenos Aires Province, Argentina , 2007 .

[6]  E. Bruneau,et al.  Sensory analysis applied to honey: state of the art , 2004 .

[7]  L. P. Oddo,et al.  Physico-chemical methods for the characterisation of unifloral honeys: a review , 2004 .

[8]  S. McNaughton,et al.  Development of a food composition database for the estimation of dietary intakes of glucosinolates, the biologically active constituents of cruciferous vegetables , 2003, British Journal of Nutrition.

[9]  F. Tomás-Barberán,et al.  Flavonoid composition of Tunisian honeys and propolis , 1997 .

[10]  G. Schmeda-Hirschmann,et al.  Main flavonoids, DPPH activity, and metal content allow determination of the geographical origin of propolis from the Province of San Juan (Argentina). , 2009, Journal of agricultural and food chemistry.

[11]  F. Tomás-Barberán,et al.  Floral nectar phenolics as biochemical markers for the botanical origin of heather honey , 1996 .

[12]  P. Andrade,et al.  Analysis of Honey Phenolic Acids by HPLC, Its Application to Honey Botanical Characterization , 1997 .

[13]  J. Louveaux,et al.  Methods of Melissopalynology , 1978 .

[14]  M. Claeys,et al.  Structure characterization of flavonoid O-diglycosides by positive and negative nano-electrospray ionization ion trap mass spectrometry. , 2001, Journal of mass spectrometry : JMS.

[15]  T. Mabry,et al.  The Systematic Identification of Flavonoids , 1970, Springer Berlin Heidelberg.

[16]  F. Tomás-Barberán,et al.  Identification of flavonoid markers for the botanical origin of Eucalyptus honey. , 2000, Journal of agricultural and food chemistry.

[17]  F. Tomás-Barberán,et al.  Plant Phenolic Metabolites and Floral Origin of Rosemary Honey , 1995 .

[18]  C. Gardana,et al.  Analysis of the polyphenolic fraction of propolis from different sources by liquid chromatography-tandem mass spectrometry. , 2007, Journal of pharmaceutical and biomedical analysis.

[19]  R. Llorach,et al.  Identification of new flavonoid glycosides and flavonoid profiles to characterize rocket leafy salads (Eruca vesicaria and Diplotaxis tenuifolia). , 2007, Journal of agricultural and food chemistry.

[20]  J. K. Kundu,et al.  Nrf2 as a Master Redox Switch in Turning on the Cellular Signaling Involved in the Induction of Cytoprotective Genes by Some Chemopreventive Phytochemicals , 2008, Planta medica.

[21]  L. Debrauwer,et al.  Characterisation of glucosinolates using electrospray ion trap and electrospray quadrupole time-of-flight mass spectrometry. , 2007, Phytochemical analysis : PCA.

[22]  S. Rabot,et al.  The nutritional significance, biosynthesis and bioavailability of glucosinolates in human foods , 2000 .

[23]  Á. Gil-Izquierdo,et al.  A comparative study of flavonoid compounds, vitamin C, and antioxidant properties of baby leaf Brassicaceae species. , 2008, Journal of agricultural and food chemistry.

[24]  A. Valle,et al.  Mieles de la región periserrana del Sistema de Ventania, Argentina , 2001 .

[25]  P. Kroon,et al.  Ontogenic profiling of glucosinolates, flavonoids, and other secondary metabolites in Eruca sativa (salad rocket), Diplotaxis erucoides (wall rocket), Diplotaxis tenuifolia (wild rocket), and Bunias orientalis (Turkish rocket). , 2006, Journal of agricultural and food chemistry.

[26]  P. Kroon,et al.  Screening crucifer seeds as sources of specific intact glucosinolates using ion-pair high-performance liquid chromatography negative ion electrospray mass spectrometry. , 2004, Journal of agricultural and food chemistry.

[27]  J. Fahey,et al.  The chemical diversity and distribution of glucosinolates and isothiocyanates among plants. , 2001, Phytochemistry.

[28]  Federico Ferreres,et al.  Flavonoids in honey of different geographical origin , 1993 .

[29]  Á. Gil-Izquierdo,et al.  Characterization of the interglycosidic linkage in di-, tri-, tetra- and pentaglycosylated flavonoids and differentiation of positional isomers by liquid chromatography/electrospray ionization tandem mass spectrometry. , 2004, Journal of mass spectrometry : JMS.

[30]  A. Allende,et al.  Microbial, nutritional and sensory quality of rocket leaves as affected by different sanitizers , 2006 .

[31]  L. P. Oddo,et al.  Botanical species giving unifloral honey in Europe , 2004 .

[32]  A. Sabatini,et al.  Nectar Flavonol rhamnosides are floral markers of acacia (Robinia pseudacacia) honey. , 2008, Journal of agricultural and food chemistry.

[33]  M. L. Ibargoitia,et al.  Identification and quantification of glucosinolates in rapeseed using liquid chromatography–ion trap mass spectrometry , 2009, Analytical and bioanalytical chemistry.

[34]  M. E. Cartea,et al.  Simultaneous identification of glucosinolates and phenolic compounds in a representative collection of vegetable Brassica rapa. , 2009, Journal of chromatography. A.

[35]  Federico Ferreres,et al.  HPLC flavonoid profiles as markers for the botanical origin of European unifloral honeys , 2001 .

[36]  Elke Anklam,et al.  A review of the analytical methods to determine the geographical and botanical origin of honey , 1998 .