Th -almost the an 18:3n-2,4,six 16.six 18:1n-9 19.5 four.five [86,87,89,935] same intensity, supplying a double
Th -almost the an 18:3n-2,four,six 16.six 18:1n-9 19.5 four.5 [86,87,89,935] exact same intensity, giving a double peak m/z 194/195 (Figure 10A). Analogous fragmen20:1n-9 30.1 0.8 [86,89] tation behavior was also observed for other FAMEs with cumulated double bonds and [87,93] helped us 14:0 interpret allenic motifs in FAMEs. As an illustration, -the compound eluting in 18.9 min 16:0 [86,87,89,935] was interpreted as FAME 19:2n-12,13. Its MS/MS spectrum supplied m/z 208.1 ( n-12), 18:0 – ( n-13), corresponding to an MBR of 93 (Figure 10B). [86,87,89,935] m/z 209.0 ( n-12 + 1), and m/z 248.two 18:3n-3,6,9 [95] Analogously, peak tR 22.six min displaying m/z 222.1 ( n-12), m/z 223.1 ( n-12 + 1), and 20:0 [86,87,89,95] m/z 248.two ( n-13) was consistent with 20:2n-12,13 (spectrum not shown).22:0 24:0 24:1 [93] [86,87] [86]2.3.3. FAMEs from Marrubium vulgare Seeds White horehound (Marrubium vulgare) is usually a perennial, aromatic herb native to Europe, northern Africa, and southwestern and central Asia. Like other plants in the Lamiaceae family, it contains FAs with cumulated double bonds (allenic FAs). TGs from white hore-Molecules 2021, 26, 6468 Molecules 2021, 26,12 of 21 12 ofMolecules 2021, 26,13 ofFigure 9. HPLC/APCI-MS base-peak chromatogram of FAMEs obtained from Marrubium vulgare Figure 9. HPLC/APCI-MS base-peak chromatogram of FAMEs obtained from Marrubium vulgare seeds and also the list of Streptonigrin Purity & Documentation identified species. seeds along with the list of identified species.By far the most abundant peak tR 16.1 min corresponded to FAME 18:2 with the principal fragments m/z 194.0 ( n-12) and m/z 248.1 ( n-13), Figure 10A. The MBR worth of 93 indicated two cumulated double bonds. It was interpreted as FAME 18:2n-12,13, most in all probability laballenic acid, extremely abundant in M. vulgare seeds [61]. The fragmentation spectrum of FAME 18:2n-12,13 using the allenic technique differed conspicuously from other arrangements of double bonds. The fragment was accompanied by an + 1 fragment with nearly the identical intensity, offering a double peak m/z 194/195 (Figure 10A). Analogous fragmentation behavior was also observed for other FAMEs with cumulated double bonds and helped us interpret allenic motifs in FAMEs. For example, the compound eluting in 18.9 min was interpreted as FAME 19:2n-12,13. Its MS/MS spectrum offered m/z 208.1 ( n-12), m/z 209.0 ( n-12 + 1), and m/z 248.2 ( n-13), corresponding to an MBR of 93 (Figure 10B). Analogously, peak tR 22.6 min showing m/z 222.1 ( n-12), m/z 223.1 ( n12 + 1), and m/z 248.2 ( n-13) was constant with 20:2n-12,13 (spectrum not shown). As well as allenic species, M. vulgare seeds contained FAMEs with conjugated double bonds. One example is, the chromatographic peak tR 14.six min (-)-Irofulven Biological Activity represented FAME 18:2n-11,13. Its structure was deduced working with m/z 182.1 ( n-13), m/z 208.1 ( n-11), m/z 222.1 ( n-11), and m/z 248.1 ( n-13), an MBR worth of 107 (Figure 11A). Similarly, peak tR 17.4 min corresponded to FAME 18:2n-12,14 (Figure 11B). Overall, sixteen unsaturated FAMEs were detected in M. vulgare seeds, including monounsaturated, diunsaturated with allenic and conjugated double bonds, and triunsaturated species with methyleneinterrupted double bonds (Table four).Figure ten. APCI MS/MS spectra on the [M + 55]+ adducts of allenic FAMEs from Marrubium vulgare seeds interpreted as FAME 18:2n-12,13 + 55]+19:2n-12,13 (B). Figure 10. APCI MS/MS spectra of the [M(A) andadducts of allenic FAMEs from Marrubium vulgareseeds interpreted as FAME 18:2n-12,13 (A) and 19:2n-12,13 (B).In addition to allenic spec.