## 2 Materials and Methods
### Chromatographic System and Operating Conditions
#### 2.6.2 UHPLC-MS/MS Triple Quadrupole Method for Melatonin
\begin{table}
\begin{tabular}{c l c c c c c c} \hline
**No.** & **Compounds** & **Precursor** & **Product Ion,** & **Fragm-** & **Collision** & **Polarity** & **Retention** & **Delta** \\
**Ion,** & **\(m/z\)** & **\(m/z\)** & **entor, V** & **Energy, V** & & **(Rt, min)** & **Time (\(\Delta\)Rt)** \\ \hline
1 & Gallic acid & 169 & 125.2 * & 97 & 12 & Negative & 6.96 & 2 \\
2 & Neochlorogenic acid & 353 & 191.2 *,179 & 82 & 12, 12 & Negative & 9.52 & 2 \\
3 & Delphindin-3-galactoside & 465.01 & 303 * & 121 & 20 & Positive & 11.36 & 2 \\
4 & (+)Catechin & 289 & 245.2 *,109.2 & 131 & 8,20 & Negative & 11.44 & 2 \\
5 & Procyaridin B2 & 576.99 & 576.99 *,321.2 & 160 & 0,32 & Negative & 12.41 & 2 \\
6 & Chlorogenic acid & 353 & 191.2 *,127.5 & 82 & 12, 20 & Negative & 12.42 & 2 \\
7 & P-Hydrocyclohex acid & 137 & 93.2 * & 92 & 16 & Negative & 12.86 & 2 \\
8 & (+)Epictacchin & 289 & 245.1 *,109.1 & 126 & 8,20 & Negative & 13.03 & 2 \\
9 & Cyanidin-3-glucoside & 449 & 287.3 *,255.6 & 121 & 20, 20 & Positive & 13.14 & 2 \\
10 & Petunidin-3-glucoside & 479.01 & 317 *,302 & 121 & 20, 44 & Positive & 13.26 & 2 \\
11 & 3-Hydrooxybenzoic acid & 137 & 93.2 * & 88 & 8 & Negative & 13.59 & 2 \\
12 & Caffe acid & 179 & 135.2 *,134.1 & 92 & 12, 24 & Negative & 13.65 & 2 \\
13 & Vanillic acid & 167 & 152.4 *,108.1 & 88 & 12, 20 & Negative & 14.32 & 2 \\
14 & Resveratrol & 227 & 185 * & 131 & 12 & Negative & 14.40 & 2 \\
15 & Pelargondin-3-glucose & 433.01 & 271 *,121 & 116 & 24, 50 & Positive & 14.52 & 2 \\
16 & Pelargondin-3-rutinoside & 579.01 & 271 * & 145 & 32 & Positive & 14.56 & 2 \\
17 & Malvidin-3-galactosidaseoside & 493.01 & 331 *,315.1 & 121 & 20, 50 & Positive & 14.64 & 2 \\
18 & Syringic acid & 196.9 & 182.2 *,121.2 & 93 & 8, 12 & Negative & 15.28 & 2 \\
19 & Procyaridin A2 & 575 & 575 *,285 & 170 & 0, 20 & Negative & 16.18 & 2 \\
20 & P-Coumaric acid & 163 & 119.2 *,93.2 & 83 & 12, 36 & Negative & 16.70 & 2 \\
21 & Ferulic acid & 193 & 134.2 *,131.6 & 83 & 12, 8 & Negative & 17.10 & 2 \\
22 & 3,5-Dicaffeoylquinic acid & 514.9 & 353.1 *,191 & 117 & 8, 28 & Negative & 17.61 & 2 \\
23 & Rutin & 609 & 300.2 *,271.2 & 170 & 32, 50 & Negative & 17.73 & 2 \\
24 & Hyperoside & 465.01 & 303 *,61.1 & 97 & 8, 50 & Positive & 18.33 & 2 \\
25 & Isoquercitin & 463 & 271.2 *,300.2 & 155 & 44, 24 & Negative & 18.36 & 2 \\
26 & Delphindin-3-5-diglucoside & 462.9 & 300.1 * & 165 & 24 & Negative & 18.38 & 2 \\
27 & Phloridin & 435.39 & 273 *,167 & 155 & 8, 28 & Negative & 18.83 & 2 \\
28 & Quercitin & 446.99 & 300.2 *,301.2 & 160 & 24, 16 & Negative & 19.61 & 2 \\
29 & Myricetin & 316.99 & 179.1 *,182 & 150 & 16, 24 & Negative & 19.61 & 2 \\
30 & Naringin & 578.99 & 271.3 *,151.3 & 170 & 32, 44 & Negative & 19.62 & 2 \\
31 & Kaempfer-3-glucoside & 447 & 284.2 *,255.2 & 170 & 24, 40 & Negative & 19.77 & 2 \\
32 & Hesperidin & 611.01 & 303 *,334.8 & 112 & 20, 12 & Positive & 20.19 & 2 \\
33 & Ellagic acid & 301 & 301 *,229 & 170 & 0, 24 & Negative & 21.41 & 2 \\
34 & trans-cinnamic acid & 149 & 131.2 & 74 & 4 & Positive & 21.44 & 2 \\
35 & Quercitin & 300.99 & 151.2 *,179.2 & 145 & 16, 12 & Negative & 21.87 & 2 \\
36 & Phloretin & 272.99 & 167 *,123 & 116 & 8, 20 & Negative & 22.30 & 2 \\
37 & Kaempfer & 287.01 & 153 *,69.1 & 60 & 36, 50 & Positive & 23.84 & 2 \\
38 & Isorhamnetin & 314.99 & 300.2 *,196.1 & 145 & 16, 4 & Negative & 24.57 & 2 \\ \hline \end{tabular}  
* These product ions were used for quantification.  
\end{table} 
Table 1: HPLC-MS/MS acquisition parameters (dynamic-MRM mode) used for the analysis of the 38 marker compounds.