## 2 Materials and Methods
### Determination of Free Phenolic Compounds with HPLC-ESI-QqQ-Ms
\begin{table}
\begin{tabular}{c c c c} \hline \hline
**Compounds** & **[M \(-\) H]–** & **Fragment Ions** & **Quantification** \\  & **(_m/z_)** & **Transition** \\ \hline Vanillic acid & 167 & 108 & 167\(\rightarrow\)108 \\ Caffe acid & 179 & 135-107 & 179\(\rightarrow\)135 \\ Syringic acid & 197 & 123 & 197\(\rightarrow\)123 \\ \(p\)-Hydroxybenzoic acid & 137 & 93 & 137\(\rightarrow\)93 \\
4-Feruloylquinic acid & 367 & 173 & 367\(\rightarrow\)173 \\ Vanillin & 153 & 93 & 153\(\rightarrow\)93 \\ \(p\)-Coumaric acid & 163 & 119 & 163\(\rightarrow\)119 \\ Ferulic acid & 193 & 178-149-134 & 193\(\rightarrow\)178 \\ Ferulic acid isomer 1 & 193 & 178-149-134 & 193\(\rightarrow\)178 \\ Sinapic acid & 223 & 164 & 223\(\rightarrow\)164 \\ Diferulic acid & 385 & 341 & 385\(\rightarrow\)341 \\ Dicaffeoylquinic acid & 515 & 353-335-191-173 & 515\(\rightarrow\)353 \\ Tricafeoylquinic acid 1 & 677 & 515-353-191 & 677\(\rightarrow\)515 \\ Tricafeoylquinic acid 2 & 677 & 515-353-173 & 677\(\rightarrow\)515 \\ Diferulic acid isomer 1 & 385 & 341 & 385\(\rightarrow\)341 \\ Diferulic acid isomer 2 & 385 & 341 & 385\(\rightarrow\)341 \\ \hline \multicolumn{3}{c}{_Flavores_-C-_glyvoside_} \\ \hline Apigenin-6-C-arabinoside-8-C-hexoside isomer 1 & 563 & 473-443 & 563\(\rightarrow\)473 \\ Apigenin-6-C-arabinoside-8-C-hexoside isomer 2 & 563 & 443 & 563\(\rightarrow\)443 \\ \hline \multicolumn{3}{c}{_Cumarins (lactone)_} \\ \hline Coumarin & 145 & 89-101 & 145\(\rightarrow\)89 \\ \hline \multicolumn{3}{c}{_Flavores_} \\ \hline Naringenin-C-diglycoside & 595 & 475-385-355 & 595\(\rightarrow\)475 \\ Naringenin-O-hexoside & 433 & 271 & 433\(\rightarrow\)271 \\ Naringenin-C-hexoside & 433 & 343-313 & 433\(\rightarrow\)343 \\ Naringenin-7-O-glucose (prunin) & 433 & 271-151 & 433\(\rightarrow\)271 \\ Naringenin & 271 & 151-119 & 271\(\rightarrow\)151 \\
3,4,5-Trihydroxy-3,7-dimethylflavone & 329 & 197 & 329\(\rightarrow\)197 \\ \hline \multicolumn{3}{c}{_Flavorols_} \\ \hline Rutin-O-hexoside & 771 & 609-300 & 771\(\rightarrow\)609 \\ Spinacetin-3-glucosyll-(1-6)-[apiosyl-(1-2)]-glucose & 801 & 655-345 & 801\(\rightarrow\)655 \\ Patuletin-3-glucosyll-(1-6)-[apiosyl-(1-2)]-glucose & 787 & 655-331 & 787\(\rightarrow\)655 \\ Rutin-O-pentoside & 741 & 609-300 & 741\(\rightarrow\)609 \\ Patuletin-diglucoside & 655 & 331 & 655\(\rightarrow\)331 \\ Rutin & 609 & 301-151 & 609\(\rightarrow\)301 \\ Patuletin-3-O-\(\beta\)-D-(2\({}^{\prime\prime}\)-coumaroglucosyll)-(1-6)-[apiosyl-(1-2)]-glucose & 933 & 603-495-333 \\ Spinacetin-3-O-\(\beta\)-D-glucose/poranyl-[-6]-glucose/poranyloside & 963 & 333 & 963\(\rightarrow\)333 \\ Spinacetin-3-(2\({}^{\prime\prime}\)-coumaroglucosyll)-(1-6)-glucose/ & 669 & 507-345 & 669\(\rightarrow\)507 \\ Spinacetin-3-(2\({}^{\prime\prime}\)-feruloylglucosyll)-(1-6)-glucose & 947 & 347-309-177 & 947\(\rightarrow\)347 \\ Kaempfer-3-O-rutinoside & 847 & 509-347-309 & 847\(\rightarrow\)509 \\ Spinacetin-3-(2\({}^{\prime\prime}\)-feruloylglucoseosyll)-(1-6)-glucose & 593 & 285-255 & 593\(\rightarrow\)285 \\ Spinacetin-3-(2\({}^{\prime\prime}\)-feruloylglucoseosyll)-(1-6)-[apiosyl-(1-2)]-glucose & 977 & 669-345 & 977\(\rightarrow\)669 \\ Patuletin-3-O-\(\beta\)-D-(2\({}^{\prime\prime}\)-p-coumaroglucosyll)-(1-6)-glucose & 801 & 681-333-309 & 801\(\rightarrow\)681 \\ Patuletin-3-O-\(\beta\)-D-(2\({}^{\prime\prime}\)-feruloylglucoseosyll)-(1-6)-glucose/ & 831 & 501-457-333 & 831\(\rightarrow\)501 \\ Patuletin derivative & 799 & 505-455-333 & 799\(\rightarrow\)505 \\ Patuletin derivative & 829 & 691-493-333 & 829\(\rightarrow\)691 \\ Spinacetin glucuronide & 521 & 345-330 & 521\(\rightarrow\)345 \\ Jaceidin glucuronide & 535 & 359 & 535\(\rightarrow\)359 \\ Quercetin & 301 & 151-121 & 301\(\rightarrow\)151 \\
5,3\({}^{\prime}\),4\({}^{\prime}\)-Trihydroxy-3-methoxy-6-7-methoxyenedioxyflavone-4\({}^{\prime}\)-glucoronide & 519 & 343-328 & 519\(\rightarrow\)343 \\
5,4\({}^{\prime}\)-Dihydroxy-3-methoxy-6-7-methoxyenedioxyflavone-4\({}^{\prime}\)-glucoronide & 503 & 327-283 & 503\(\rightarrow\)327 \\
5,4\({}^{\prime}\)-Dihydroxy-3,3’-dimethoxy-6-7-methoxyenedioxyflavone-4\({}^{\prime}\)-glucoronide & 533 & 357-342 & 533\(\rightarrow\)357 \\ \hline \hline \end{tabular}
\end{table}