Mass fragmentation study of the trimethylsilyl derivatives of arctiin, matairesinoside, arctigenin, phylligenin, matairesinol, pinoresinol and methylarctigenin: their gas and liquid chromatographic analysis in plant extracts

Abstract

The mass fragmentation patterns and the characteristic behavior of the trimethylsilyl (TMS) derivatives of the dibenzylbutyrolactone-type (arctiin, arctigenin, methylarctigenin, matairesinoside, matairesinol) and those of the diphenylperhydrofurotetrahydrofurane-type (phylligenin, pinoresinol) lignans, obtained by gas chromatography-mass spectrometry (GC-MS), were presented. It was shown that upon acidic hydrolysis the dibenzylbutyrolactone-type lignans are stable while the diphenylperhydrofurotetrahydrofurane-type ones decompose. As a novelty to the field we confirmed that the fragment species of the derivatized lignan glycosides, in the presence of excess hexamethyldisilazane, leaded to their in situ derivatization. Quantification of the selective fragment ions of the TMS derivatives by GC-MS, in respect of the ions found one by one, and concerning the selective fragment ions {SFI(s)} in total, provided acceptable reproducibilities, suitable for quantitation purposes: varying between 1.20% and 6.6% relative standard deviation percentages (RSD%). For characterization of the behavior of various type of lignans, analyses were performed with the untreated and with the trifluoroacetic acid hydrolyzed plant extracts, from the same sample, in parallel, both by GC-MS and by high performance liquid chromatography-mass spectrometry, working in the positive electron ionization mode (HPLC-ESPI-MS). The analysis of lignans in fruit and leaf extracts (obtained from the Arctium, Centaurea and Forsythia plants) was confirmed both by GC-MS and by HPLC-ESPI-MS. Our multicomponent system (including the identification and quantification of sugars, sugar alcohols, and several members of various homologous series of acids, anthraquinones and flavonoids) has been extended to the analysis of lignan glycosides and to the free lignans. Reproducibilities in the quantitation of lignans in plant matrices, as averages on GC and HPLC basis, varied between 0.9% and 11% (RSD). The distribution of the lignan constituents was presented for 5 Arctium, for 8 Centaurea and for 4 Forsythia plant extracts: the total of lignan contents varied between 0.42 and 87.9 mg/g, respectively.