, 2001 and Lin and Harnly,

2007) and for the standard analysed under the same conditions. Peaks 8, 9, 10 and Lapatinib cell line 11 were identified as myricetin glucoside, myricetin pentoside, myricetin rhamnoside and myricetin acetyl-rhamnoside, respectively. The following elution order is expected on reversed phase for the same aglycone: hexoside < pentoside < deoxyhexoside, and acylated derivatives elute after their non-acylated flavonoids (Lin and Harnly, 2007 and Wu and Prior, 2005). In addition, the λmax values at 349–355 nm, about 20 nm lower than the λmax of myricetin (371 nm), indicate the typical hypsochromic effect of flavonol glycosides in relation to its aglycone ( Lin & Harnly, 2007). The mass spectra indicated the presence of the aglycone at m/z 319 (ESI+) and at m/z 317 (ESI-), which corresponds to myricetin. In addition, the MS/MS fragmentation pattern obtained from these ions (m/z at 319 and m/z at 317) showed the same fragments at m/z 301, 273, 245, 165 and 153 as those found for myricetin. In the case of myricetin glucoside (peak 8), the loss of 162 u, both in positive and negative modes, indicated the presence of an hexose in the molecule, whereas the loss of 132 u indicated

the presence of a pentose in peak 9 (myricetin pentoside). However, the analysis by MS itself does not allow distinguishing whether the sugar Romidepsin is xylose or arabinose, which are the most commonly pentoses found in fruits. For myricetin rhamnoside (peak 10), the loss of 146 u from [M−H]− (m/z at 463) is characteristic of a deoxyhexose

unit, and rhamnose is the only deoxyhexose found in fruit flavonoids. Finally, the MS/MS spectrum of myricetin acetyl-rhamnoside (peak 11) showed a loss of 188 u, corresponding to an acetylated rhamnose unit (146 + 42 u) ( Cuyckens and Claeys, 2004 and Mahmoud et al., 2001). The C3 position is the most likely location for all these glycosides ( Cuyckens & Claeys, medroxyprogesterone 2004). For flavanonols, considering the biosynthetic flavonoid pathway (proposed in Fig. S4 from Supplementary data), the aglycones at m/z 321 (ESI+, peak 3) and at m/z 305 (ESI+, peak 5) were identified as dihydromyricetin and dihydroquercetin, respectively, since these flavanonols are precursors of myricetin (peak 12). Considering that simple flavonoids with a hydroxyl in ring B may be modified during biosynthesis through hydroxylation and methylation reactions ( Heller & Forkmann, 1994), the aglycones at m/z 335 (ESI+, peak 6) and at m/z 349 (ESI+, peak 7) were identified as methyl and dimethyl derivatives of dihydromyricetin diglucoside (peak 3) ( Fig. S3 from Supplementary data).