## 3 Results
### Phenolic Compounds  
The HPLC-MS/MS analysis of the CS extracts highlighted the presence of seven compounds belonging to CGAs (Table 6), a family of natural hydroxycinnamic acid esters, displaying antimicrobial, antifungal [54], and oxidative and inflammatory stress control activity [55]. Of these, three were isomers of caffeoylquinic acid, namely 3-O-caffeoylquinic (3-O-CQA), 5-O-caffeoylquinic (5-O-CQA), and 4-O-caffeoylquinic acid (4-O-CQA); two were isomers of feruloylquinic acids (FQAs); and two were isomers of dicaffeoylquinic acids (di-CQA) (Table 6). 5-O-CQA was identified by comparison with analytical standards, whereas 3-O-CQA, 4-O-CQA, FQAs, and di-CQAs were identified based on data reported in the literature [56; 57]. Typically, CGAs are abundant in coffee, in different concentrations and isomeric mixtures, and determine the phenolic composition of CS. [PERSON] et al. [13] analysed different C. _Arabica_ extracts and reported the presence of only three caffeoylquinic acids (3-CQA, 5-CQA, and 3,5-diCQA); however, [PERSON] et al. [14] detected nine different CGAs, including caffeoylquinic lactones and coumaroylquinic acids. In general, caffeoylquinic acid isomers are the most abundant group [14; 43]. In our CS extracts, 5-O-CQA was the most abundant CGA acid, whereas 3-O-CQA was detected only in dark- and medium-roasted washed _Arabica_ CS (Table 7). The 5-O-CQA content was in the range of 0.41-2.96 mg/g, with the maximum amount in the dark-roasted washed _Arabica_ CS. On the contrary, _Caneophora_ CS is characterised by the lowest 5-O-CQA amount independently to roasting intensity or post-harvest treatment. The content of 4-O-CQA varied from a minimum of 0.08 mg/g in washed _Caneophora_ CS obtained from a medium or dark roasting to a maximum of 0.50 mg/g in washed _Arabica_ CS obtained with a dark roasting. Again, a significant effect of the roasting degree was detected only in washed _Arabica_ CS, with an increase in 4-O-CQA with the level of roasting. This trend was unexpected because, as the degree of roasting increases, caffeoylquinic acids were generally thermally degraded to their corresponding lactones [55]. However, many factors are involved in the roasting process as the roasting profile (time and temperature conditions), together with the type of roaster and the roasting speed, can affect the CGAs' content. For the same roasting degree, the higher the roasting speed, the lower the CGAs' loss [58]. In the same samples, as the degree of roasting increased, a decrease in SDF was observed, likely leading to a lower formation of fibre-antioxidant complexes. \begin{table}
\begin{tabular}{c c c c c c} \hline \hline
**Peak** & **Rt (min)** &
\begin{tabular}{c} **\(\lambda\)max** \\ **(nm)** \\ \end{tabular} & **[M-H]\({}^{-}\)**_(m/z)_** & **MS/MS (m/z)** & **Identification** \\ \hline
1 & 6.01 & 324 & 353 & 191, 135, 179 & 3-O-CQA \({}^{\circ}\) \\
2 & 6.46 & 325 & 353 & 191, 179, 135 & 5-O-CQA \({}^{\circ}\) \\
3 & 6.56 & 325 & 353 & 135 & 4-O-CQA \({}^{\circ}\) \\
4 & 8.59 & 324 & 367 & 191, 173 & FQA1 \({}^{\circ}\) \\
5 & 9.04 & 325 & 367 & 191 & FQA2 \({}^{\circ}\) \\
6 & 13.52 & 327 & 349 & - & di-CQA1 \({}^{\circ}\) \\
7 & 16.42 & 326 & 515 & 353, 335, 173, 191, 135 & di-CQA2 \({}^{\circ}\) \\ \hline \hline \end{tabular}  
* not present; \({}^{\circ}\) comparison with reference standards; \({}^{\circ}\) tentative identification with literature data.  
\end{table} 
Table 6: Chromatographic and spectroscopic characteristics (retention times, Rt; UV maxima, \(\lambda\)max; negative pseudomolecular ions, [M-H]\({}^{-}\); product ions, MS/MS) of phenolic acids detected in CS samples.