Rationale: The main feature of the fragmentation of [M − H] − ions of methoxylated flavonoids is the loss of methyl radical (formation of the [M − H − CH 3 ] −• product ion). Subsequent decomposition of [M − H − CH 3 ] −• product ions may be useful for identification of a given compound by HPLC/MS. This paper describes how the selected diagnostic fragment ions can be useful during HPLC/MS(−) analysis of methoxylated flavonoids. Methods: Product ion spectra (ESI-CID-MS/MS spectra) of [M − H] − ions of 17 methoxylated flavonoids (flavones, isoflavones and flavonols) were obtained with a Q-TOF mass spectrometer. Full scan mass spectra (ESI-MS) were obtained with a single quadrupole type of instrument. Results: A number of product ions were recognized as useful from the point of view of structural elucidation. In most cases they were diagnostic product ions, formed as a result of C ring breaking. Conclusions: The most important conclusions drawn from this study are: the product ion at m/z 132 indicates that the analysed compound is an isoflavone; the product ion at m/z 117 indicates the presence of one hydroxy group at ring B or at the 3-position; biochanin A and prunetin can be differentiated by their 'in-source' fragmentation, by the relative abundances of product ions at m/z 195, 183 and 167; loss of mass 102 from the [M − H − CH 3 ] −• ion indicates that ring B is not substituted and there is no hydroxy group at the 3-position; and rhamnetin can be detected using three diagnostic product ions, namely at m/z 121, 165 and 193.

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Ethoxylated fatty alcohols, C(12)E(1), C(12)E(2), C(18)E(1) and C(18)E(2), were studied by electrospray ionization mass spectrometry (E is the ethoxylene unit OCH(2)CH(2)). For compounds containing two ethoxylene units, which form quite stable adducts with sodium cation, the abundances of [M + Na](+) ions were not affected by alkyl chain, so the hydrophobic effect was not observed. For the compounds containing one ethoxylene unit, forming rather unstable adducts with sodium, the hydrophobic effect was clearly seen since the [C(18)E(1) + Na](+) ion was more abundant than the [C(12)E(1) + Na](+) ion. Two ethoxylene units are not able to form stable adducts with potassium cations, therefore the hydrophobic effect was observed for the [C(12)E(2) + K](+) and [C(18)E(2) + Na](+) ions, the latter being more abundant than the former. For lithium cation adducts with C(12)E(1) and C(18)E(1), the hydrophobic effect was observed, but was less manifested than for sodium cations since lithium adducts are more stable than sodium ones. C(18)E(1) and C(18)E(2) gave more intense signals at higher cone voltage values than C(12)E(1) and C(12)E(2), respectively. However, this is not related to the hydrophobic effect but to the collisions being less effective for the former.