<p>Top: Localization of p-coumaroylagmatine (CA) as representative for hydroxycinnamic acid amides and hordatine B as representative for hordatines that co-localized to hordatine B when occurring in the same modification state. Intensity maps depict the non-glycosylated (<i>m/z</i> 581), glycosylated (<i>m/z</i> 743), and disaccharide-modified form (<i>m/z</i> 905) at three time points during germination (0d: non-germinated barley, G3d: three days germinated, G5d: five days germination) in longitudinal and transversal section plane. Hordatines were not detected in cross sections in non-germinated barley. The last panel shows an overlay of the three modification forms. Ion intensities were normalized to the TIC, the highest relative intensity was set to 100%. Middle panel: Average mass spectra from annotated embryo measurement regions (right) in non-germinated (green), three days (blue) and five days (red) germinated barley. Bottom: Mass spectrum with indicated peaks of hydroxycinnamic acid amides as hordatine precursors (<i>m/z</i> 250–350) and of hordatine A, B, C, and D (D not detected, grey font), hydroxylated hordatines (-OH), and hexose-modified derivates (Hex / 2 Hex) at <i>m/z</i> 550–1000. CA: coumaroylagmatine, FA: feruloylagmatine, CA-OH / FA-OH: hydroxylated CA and FA.</p
