# Anti-Inflammatory and Antioxidant Effects Induced by
## 3 Results and Discussion
### Phytochemical Analyses
#### 3.1.2 HS-SPME-GC-MS and DI-ESI-MS Analysis  
The compounds identified through the HS-SPME-GC-MS were clustered in three main classes (Table 2), namely the monoterpenes and their oxygen derivatives (61.2%), the sulfur-containing-compounds (SCC, 22.8%) and finally the aldehydes (3%). Thymol and carvacrol, two monoterpenoids, are the most abundant species (22.4% and 36.1%, respectively), followed by allyl disulfide (9.52%) and the 3-vinyl-1,2-dithiacyclohexene isomers (7.14%) belonging to the SSC class. The DI-ESI-MS full spectrum was dominated by the regular repetition of two monocharged species differing by 16 mass units (Figure 2), that suggests the presence of species complex Na\({}^{+}\) and K\({}^{+}\) cations. The 162 Da intervals correspond to the difference of one -C\({}_{6}\)H\({}_{10}\)O\({}_{5}\)- unit, typical of a homologous series of polysaccharides. The MS/MS spectrum of the 1029 \(m\)/\(\varepsilon\) ion, reported in Figure 3 as representative ion of the series, showed the sequential loss of 162 Da (=C\({}_{6}\)H\({}_{10}\)O\({}_{5}\)) and 18 Da (=H\({}_{2}\)O) according to the MS2 fragmentation of a polysaccharide. The detected oligosaccharides, most probably fructans [41], are characterized by a wide degree of polymerization (DP), namely in the 2-11 DP range (Table 3). The Na\({}^{+}\) and K\({}^{+}\) ions distribution emerging from the fructans series indicates a larger content of the latter, despite what one should expect considering the ubiquitous presence of Na\({}^{+}\) cation in the ESI-MS experiments. In addition to the fructans, the full scan showed two intense signals at \(m/z\) 175 and 214, corresponding to the protonated L-arginine and to N-butylbenzene sulfonamide (a plasticizer contaminant), respectively (Table 3). \begin{table}
\begin{tabular}{c c c} \hline
**Compound** & **GHE** & **GWE** \\ \hline Gallic acid & 17.21 \(\pm\) 0.17 & 16.88 \(\pm\) 0.12 \\
3-Hydrocytrosol & 10.13 \(\pm\) 0.15 *** & 12.86 \(\pm\) 0.22 \\ Caftaric acid & 0.93 \(\pm\) 0.06 & n.d. \\ Catechin & 37.40 \(\pm\) 1.25 *** & 21.38 \(\pm\) 0.72 \\
4-Hydroxybenzoic acid & n.d. & n.d. \\ Loganic acid & n.d. & n.d. \\ Chlorogenic acid & 13.54 \(\pm\) 0.72 & 12.14 \(\pm\) 0.53 \\ Vanillic acid & n.d. & n.d. \\ Caffe acid & 10.91 \(\pm\) 0.95 & 10.19 \(\pm\) 0.58 \\ Epicatechin & 8.94 \(\pm\) 0.23 * & 7.23 \(\pm\) 0.40 \\ Syringaldehyde & 9.53 \(\pm\) 0.12 & 9.54 \(\pm\) 0.23 \\ \(p\)-Coumaric acid & 13.33 \(\pm\) 0.17 & 12.73 \(\pm\) 0.15 \\ \(t\)-Ferulic acid & 15.82 \(\pm\) 0.26 ** & 13.43 \(\pm\) 0.21 \\ Benzoic acid & 22.66 \(\pm\) 0.35 * & 21.51 \(\pm\) 0.18 \\ Rutin & 13.68 \(\pm\) 0.22 & 13.08 \(\pm\) 0.23 \\ Resveratrol & 16.18 \(\pm\) 0.27 ** & 13.97 \(\pm\) 0.15 \\ \(t\)-Cinnamic acid & 11.83 \(\pm\) 0.09 & 11.59 \(\pm\) 0.12 \\ Quercetin & 15.86 \(\pm\) 0.20 * & 14.76 \(\pm\) 0.21 \\ Naringenin & 17.93 \(\pm\) 0.21 * & 16.02 \(\pm\) 0.37 \\ Hesperetin & 17.06 \(\pm\) 0.58 ** & 12.72 \(\pm\) 0.31 \\ Kaempfer & n.d. & n.d. \\ Carvacrol & n.d. & n.d. \\ Thymol & n.d. & n.d. \\ Flavone & 20.43 \(\pm\) 0.15 & 19.83 \(\pm\) 0.19 \\
3-Hydroxyflavone & 10.27 \(\pm\) 0.29 ** & 13.46 \(\pm\) 0.25 \\ Emodin & n.d. & n.d. \\ \hline \end{tabular} Values expressed are the means \(\pm\) S.D. of three parallel measurements. n.d., not detected. \(t\)-test, * \(p\) \(<\) 0.05, ** \(p\) \(<\) 0.01, and *** \(p\) \(<\) 0.001 vs. vehicle.  
\end{table} 
Table 1: Quantification of the investigated phenolic compounds detected in garlic hydroalcoholic extract (GHE) and garlic water extract (GWE) (\(\mu\)g/mL).