## 3 Materials and Methods
### Saponins
\begin{table}
\begin{tabular}{c c c c c c} \hline \hline
**Compound** & \begin{tabular}{c} **Precursor \(mlz\)** \\ **(M \(-\) H)** \\ \end{tabular} & \begin{tabular}{c} **MRM Transitions \(mlz\)** \\ **(Q\({}_{1}\)\(\rightarrow\) Q\({}_{3}\))** \\ \end{tabular} & \begin{tabular}{c} **Q\({}_{1}\) Pre Bias** \\ **(V)** \\ \end{tabular} & \
\begin{tabular}{c} **Collision** \\ **Energy** \\ \end{tabular} &
\begin{tabular}{c} **Q\({}_{3}\) Pre Bias** \\ **(V)** \\ \end{tabular} \\ \hline \multirow{4}{*}{Ferulic acid} & \multirow{4}{*}{193.400} & 193.400 \(\rightarrow\) 134.000 & 12.0 & 14.0 & 26.0 \\ \cline{3-6}  & & 193.400 \(\rightarrow\) 177.950 & 12.0 & 15.0 & 30.0 \\ \cline{3-6}  & & 193.400 \(\rightarrow\) 149.050 & 12.0 & 13.0 & 14.0 \\ \hline \multirow{4}{*}{Cryptochlorogenic acid (4-O-Caffeoylquinic acid)} & \multirow{4}{*}{353.00} & 353.000 \(\rightarrow\) 191.300 & 17.0 & 15.0 & 19.0 \\ \cline{3-6}  & & 353.000 \(\rightarrow\) 85.000 & 16.0 & 43.0 & 15.0 \\ \cline{3-6}  & & 353.000 \(\rightarrow\) 93.050 & 17.0 & 46.0 & 17.0 \\ \hline \multirow{4}{*}{Neochlorogenic acid (5-O-Caffeoylquinic acid)} & \multirow{4}{*}{353.000} & 353.000 \(\rightarrow\) 191.300 & 17.0 & 15.0 & 19.0 \\ \cline{3-6}  & & 353.000 \(\rightarrow\) 85.000 & 16.0 & 43.0 & 15.0 \\ \cline{3-6}  & & 353.000 \(\rightarrow\) 93.050 & 17.0 & 46.0 & 17.0 \\ \hline \multirow{4}{*}{Chlorogenic acid (3-O-Caffeoylquinic acid)} & \multirow{4}{*}{353.000} & 353.000 \(\rightarrow\) 85.000 & 16.0 & 43.0 & 15.0 \\ \cline{3-6}  & & 353.000 \(\rightarrow\) 93.050 & 17.0 & 46.0 & 17.0 \\ \hline \multirow{4}{*}{3,5-di-O-Caffeoylquinic acid} & \multirow{4}{*}{515.000} & 515.000 \(\rightarrow\) 353.250 & 24.0 & 16.0 & 24.0 \\ \cline{3-6}  & & 515.000 \(\rightarrow\) 191.300 & 24.0 & 31.0 & 18.0 \\ \cline{3-6}  & & 515.000 \(\rightarrow\) 179.300 & 24.0 & 30.0 & 17.0 \\ \hline \multirow{4}{*}{4,5-di-O-Caffeoylquinic acid} & \multirow{4}{*}{515.300} & 515.300 \(\rightarrow\) 353.300 & 24.0 & 18.0 & 12.0 \\ \cline{3-6}  & & 515.300 \(\rightarrow\) 179.100 & 24.0 & 30.0 & 17.0 \\ \cline{3-6}  & & 515.300 \(\rightarrow\) 191.350 & 40.0 & 34.0 & 11.0 \\ \hline \multirow{4}{*}{Rutin} & \multirow{4}{*}{609.300} & 609.300 \(\rightarrow\) 300.150 & 30.0 & 39.0 & 19.0 \\ \cline{3-6}  & & 609.300 \(\rightarrow\) 301.100 & 22.0 & 30.0 & 19.0 \\ \cline{1-1} \cline{3-6}  & & 609.300 \(\rightarrow\) 271.250 & 22.0 & 55.0 & 17.0 \\ \hline \hline \end{tabular}
\end{table} 
Table 7: _Cont._the column was set at 0.3 mL min\({}^{-1}\). Water (eluent A) and acetonitrile (eluent B) slightly acidified with 0.1% formic acid were used for elution at 30 \({}^{\circ}\)C. The gradient was set as follows: 0-1 min (2-30% of B in A), 1-31 min (30-60% of B in A), 31-31.5 min (60-100% of B in A), and 31.5-35.5 min (60-100% of B in A). Later, the column was reconditioned. The detector was calibrated with sodium formate prior to each run. The detector was used in the negative mode. The general parameters of the instrument were set as follows: scanning range 50-2200 \(m/z\), nebuliser pressure 1.5 bar, dry gas-nitrogen 7.0 L*min\({}^{-1}\), temperature 200 \({}^{\circ}\)C, capillary voltage 2.2 kV, ion energy 5 eV, collision energy 10 eV vs. 30 eV, and low mass set 200 \(m/z\). Analysis of the obtained mass spectra was carried out using Bruker Daltonics 4.1 data analysis software.