## 3 Results and Discussion
The positive MN was composed of 1002 nodes and 1451 edges, in which the clusters of interest included cluster A: lignans, cluster B: flavonoids, cluster C: amino acid derivatives, singleton D: alkaloid, and cluster E: fatty acids/amides (Figure S1). The detection of alkaloids in positive mode versus phenolic acids in negative mode is expected considering the improved sensitivity for each class in respective mode and highlighting the importance of acquiring in different ionization types. Glycoses were detected based on the neutral loss of the attached \(O\)-sugar moieties at 162 amu (C\({}_{6}\)H\({}_{10}\)O\({}_{5}\)) for hexoses, 146 amu (C\({}_{6}\)H\({}_{10}\)O\({}_{4}\)) for rhamnose, 176 amu (C\({}_{6}\)H\({}_{9}\)O\({}_{6}\)) for glucuronide and 132 amu (C\({}_{5}\)H\({}_{8}\)O\({}_{4}\)) for pentoses. In some spectra, peaks detected at \(m/z\) 113 (C\({}_{5}\)H\({}_{5}\)O\({}_{3}\)\({}^{-}\)), \(m/z\) 101 (C\({}_{4}\)H\({}_{5}\)O\({}_{3}\)\({}^{-}\)), \(m/z\) 71 (C\({}_{3}\)H\({}_{3}\)O\({}_{2}\)\({}^{-}\)) and/or \(m/z\) 59 (C\({}_{2}\)H\({}_{3}\)O\({}_{2}\)\({}^{-}\)) correspond to hexose fragments [13]. Acylation of glycosides with acetylyl or malonyl moieties was recognized by additional mass and/or neutral loss of 42 amu (C\({}_{2}\)H\({}_{2}\)O) or 86 amu (C\({}_{3}\)H\({}_{2}\)O\({}_{3}\)), respectively, while \(C\)-glycoses showed significant neutral losses of 90 amu and 120 amu resulting from 0,2 and 0,3-sugar ring cleavage [14]. \begin{table}
\begin{tabular}{l l c c c c c c c} \hline \hline
**Peak** & **Identification** & **[M-HI]-** & **[M+HI]\({}^{+}\)** & **Elemental Composition** & **Error (ppm)** & **MSn ions** & **Rt (min)** & _C. sativons_ & _L. sicraria_ \\ \hline
**Sugars** & & & & & & & & \\
1 & Dissaccharide & 377,0853 & & C\({}_{18}\)H\({}_{2}\)O\({}_{5}\)\({}^{-3}\) & 4 & 341,215,179 & 5.1 & + & + \\
**Amino acids/amines** & & & & & & & & \\
2 & Lysine-O-hexosyl & 307,1508 & & C\({}_{12}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 1 & 217,187,145,127 & 4.6 & + & + \\
3 & N-trimethyl-lysine & & 189,1597 & C\({}_{18}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 0 & 144,130,84 & 4.7 & + & + \\
4 & Pyropulamic acid & & 130,499 & C\({}_{18}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 2 & 84 & 5 & + & + \\
5 & N-hexosyl-pyropulamate & 290,0895 & & C\({}_{11}\)H\({}_{23}\)N\({}_{0}\)\({}^{-3}\) & 4.8 & 128 & 6.8 & + & + \\
6 & Pyrylroline & & 72,0806 & C\({}_{11}\)H\({}_{23}\)N\({}_{0}\)\({}^{-3}\) & 1.9 & 56,55 & 5.4 & + & + \\
7 & Nicotinamide & & 123,0555 & C\({}_{18}\)H\({}_{23}\)N\({}_{0}\)\({}^{-1}\) & 1.7 & 96,80 & 6.6 & + & + \\
8 & Piperidine & & 86,0962 & C\({}_{1}\)H\({}_{23}\)N\({}^{+}\) & 2 & 57,56 & 6.7 & + & + \\
9 & Cyclo(teacy/prolyl) & & 211,1437 & C\({}_{11}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 1.7 & 192,183,154,138,149,48 & 7 & + & + \\
10 & N-(deoxy/heosyl) phenylalanine & & & & & & & \\
11 & N-(deoxy/heosyl)-iso/teo & 292,1402 & & C\({}_{19}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 0 & 172,130,128,101,73 & 7.8 & + & + \\
12 & Pant Pant Pantine acid (out. US) & 218,1032 & C\({}_{11}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 1 & 146,169,98 & 9.1 & + & + \\
13 & Methyl-pyrophulamic acid & 144,066 & C\({}_{14}\)H\({}_{23}\)N\({}_{0}\)\({}^{-2}\) & 2 & 98,84 & 9.5 & + & + \\
14 & N-(methoxybenzyl)glutamine & & 267,1337 & C\({}_{13}\)H\({}_{23}\)N\({}_{0}\)\({}^{-4}\) & 0.7 & 250,237,222,211,203 & 9.9 & - & + \\
15 & Iso/Leacy-Iso/Leucine & & 245,1859 & C\({}_{12}\)H\({}_{23}\)N\({}_{0}\)\({}^{-3}\) & 0.4 & 228,210,132,120,86,69 & 11.3 & - & + \\ Alkalids & & & & & & & & \\
16 & N,N,N-Trimeth  
\begin{table}
\begin{tabular}{c c c c c c c c c} \hline
**Peak** & **Identification** & **[M-H]-** & **[M+H]\({}^{*}\)** & **Elemental** & **Error (ppm)** & **MSn ions** & **Rt (min)** & _C. sativens_ & _L.