## 2 Results and Discussion
### Phenolic Compounds Profile and Quantification
\begin{table}
\begin{tabular}{c c c c c c c c} \hline \hline \multirow{2}{*}{**Proposed Compound**} & **Rt (Min)** & **m/z [M-HI]\({}^{-}\)** & **MS/MS Fragments (w/z, \% Base Peak Intensity)** & \multicolumn{4}{c}{**Bavo de Esmolfe Apple Extracts**} \\ \cline{3-8}  & & & & **CET** & **CE** & **MAE** & **UAE** \\ \hline \multicolumn{8}{c}{Hydrooxycrimamic acids} \\ \hline
5-Caffeytoplasmic acid trans & 8.7 & 353.1 & 191(100) & + & + & + & + \\
4-Caffeytoplasmic acid trans & 8.9 & 353.1 & 191(82), 1790(81), 1739(76), 1352(1) & + & + & + \\
5-Caffeytoplasmic acid cis & 9.6 & 353.1 & 191(100) & + & - & + & - \\ \(p\)-Cumamic acid & 8.9 & 163.0 & 191(100) & + & - & + & + \\
5-Cumarytoplasmic acid trans & 8.5 & 337.1 & 163(100), 191(20), 191(3) & + & - & + & - \\
4-Cumarytoplasmic acid & 9.6 & 337.1 & 173(100), 163(21), 191(14), 119(7) & + & - & + & - \\
5-Cumarytoplasmic acid & 10.8 & 337.1 & 191(100), 173(163), 163(24),119(4) & + & - & + & - \\ Caffey alcohol 3/4-Oneoside & 8.3 & 327.1 & 165(100) & + & + & + & + \\ Ferudyl hexose & 10.2 & 355.1 & 295(100), 2357(4), 193(57), 265(3),175(27) & + & + & + & + \\ \hline \multicolumn{8}{c}{Hydrooxybenzoic acids} \\ \hline Protocatechic acid glycoside & 6.8 & 315.1 & 315(100), 109(5), 135(14) & + & + & + & + \\ \hline \multicolumn{8}{c}{Favavants} \\ \hline (+)-Catechin & 8.7 & 289.1 & 289(100), 245(41) & + & - & + & - \\ (-)-pjeticanth & 9.7 & 289.1 & 289(100), 245(42) & + & + & + & + \\ Epicatchin derivatives & 12.2 & 289.1 & 245(100), 203(274) & + & - & + & - \\ Epicatchin-3-gallate & 12.8 & 441.1 & 395(100), 263(81), 441(6) & + & + & + & + \\ Epigallecuchin gallate & 8.4 & 457.2 & 457(100), 277(85), 94(9) & + & + & + & + \\ Proxyacillin dimer by type & 8 & 577.1 & 289(100), 407(34), 245(5) & + & - & + & - \\ Procyanidin B2 & 9.2 & 577.1 & 2899(8), 407(76), 425(65) & + & - & + & - \\ Procyanidin C1 & 9.8 & 865.2 & 287(100), 289(8), 407(54), 425(65), 577(59), 713(33), 695(27) & + & - & + & - \\ Flavours & & & & & & & - \\ \hline Quercetin-3-O-nitroside & 11.5 & 609.1 & 609(100), 300(19), 301(16) & + & - & + & - \\ Quercetin-3-O-glucoside & 11.8 & 463.1 & 463(100), 300(78), 301(46) & + & - & + & + \\ Quercetin-3-Onesoside & 12 & 463.1 & 463(100), 300(78), 301(46) & + & - & + & - \\ \hline \multicolumn{8}{c}{Dihydrochalcone} \\ \hline Phonotin & 13.1 & 567.2 & 273(100), 167(5) & + & - & + & - \\ Pholorizin & 14.4 & 435.1 & 273(100), 294(2), 167(11) & + & - & + & - \\ \hline \multicolumn{8}{c}{Abbreviations R, retention time +, compound identified - compound not identified.} \\ \end{tabular}
\end{table} 
Table 2: Phenolic compounds identified (or tentatively identified) by LC-ESI-UHR-Q/TOF-MS in different ‘Bravo de Esmolfe’ apple extracts. The flavanols are the major class of apple phenolic compound [28], a total of eightwere identified in BE apple extracts. In the extracts produced by CE and UAE only five flavanols were detected. (+)-Catechin and (--)-epicatechin (_m/z_ 289.1) were identified by comparison of retention time and fragmentation spectra with authentic standards. Epicatechin-3-gallate and epicatechin-gallate (_m/z_ 441.1 and 457.2, respectively) were identified based on their MS/MS fragmentation and by comparison with the literature [31]. Two B-type C-type (epi)catechin dimers were identified regarding the procyanids at _m/z_ 577.1 and _m/z_ 865.2, respectively. The fragmentation pattern of these molecules is consistent with previously reported data indicating the possibility of one of these dimers being procyanidin B2 and the C-type being procyanidin C1 [3]. These procyanids have been consistently reported as the most representative in apples. Furthermore, works of [PERSON] et al. [3] with dried BE apple identified, in methanolic extracts, these compounds and other B-type dimers, trimers and one tetramer, and works of [PERSON] et al. [1] with fresh BE apple identified only two B-type of procyanids (B1 and B2).