Table 1.
HPLC-UV-MS/MS (ESI-) analyses of polar phenols in EVOO extracts.
| Compound | RT (min) | [M-H]−(m/z) | MS/MS Experiments m/z (% Base Peak) |
Cor | CM/Cor | Cas |
|---|---|---|---|---|---|---|
| 3-hydroxytyrosol a | 2.918 ± 0.012 | 153.0 | 123.4 (100), 95.4 (7) | 53 (5) a,f,g | 4.4 (0.4) b | 1.37 (0.14) b |
| Decarboxymethyl-elenolic acid derivative b | 3.512 ± 0.014 | 185.1 | 111.5 (100), 95.2 (66), 69.2 (8) | 1.56 (0.15) a | 0.026 (0.003) b | n.d. |
| Decarboxymethyl elenolic acid b | 4.19 ± 0.02 | 199.0 | 111.4 (91), 95.1 (28), 85.2 (56), 69.4 (81), 59.2 (100) | 7.8 (0.8) a | 0.065 (0.006) b | n.d. |
| Tyrosol b | 4.63 ± 0.03 | 137.0 | 119.2 (100) | 0.020 (0.002) | n.d. | n.d. |
| Oleacinic acid Open Forms II a | 15.418 ± 0.014 | 335.1 | 199.6 (100), 155.3 (14), 111.3 (11), 59.4 (6) | 10.8 (1.1) a | 10.1 (1.0) a | 2.3 (0.2) b |
| Oleuropein aglycone carboxylic acid Open Forms I or II a | 15.46 ± 0.04 | 393.2 | 257.5 (27), 169.4 (100), 111.4 (66) | 0.33 (0.03) a | 0.172 (0.017) b | 0.170 (0.017) b |
| Oleuropein isomer 1 a | 15.51 ± 0.02 | 539.1 | 113.2 (100) | 1.28 (0.13) a | 0.65 (0.06) b | 0.47 (0.05) b |
| Pinoresinol c | 15.53 ± 0.02 | 357.0 | 221.6 (100) | 0.53 (0.05) a | 0.62 (0.06) a | 0.125 (0.013) b |
| Oleuropein aglycone enolic-aldehydic Open Form I a | 15.75 ± 0.04 | 377.1 | 275.7 (27), 149.4 (22), 139.3 (100), 121.4 (9), 111.1 (20), 101.2 (8), 95.2 (41) | 3.6 (0.4) b | 3.6 (0.4) b | 5.8 (0.6) a |
| Oleuropein aglycone enolic-aldehydic Open Form I a | 16.50 ± 0.04 | 377.1 | 275.8 (15), 149.4 (50), 139.3 (100), 121.3 (9), 111.2 (25), 101.2 (10), 95.2 (75) | 10.8 (1.1) b | 10.0 (1.0) b | 15.1 (1.5) a |
| Oleuropein aglycone carboxylic acid Open Forms I or II a | 16.60 ± 0.03 | 393.2 | 257.5 (77), 169.4 (100), 111.4 (66) | 0.30 (0.03) a | 0.174 (0.017) b | 0.153 (0.015) b |
| Oleuropein isomer 2 a | 16.650 ± 0.019 | 539.1 | 113.2 (100) | 0.77 (0.08) a | 0.43 (0.04) b | 0.45 (0.04) b |
| Oleocanthalic acid Open Forms II b | 18.48 ± 0.05 | 319.1 | 199.6 (87), 181.7(10), 155.4(11), 139.3(7), 121.4 (14), 111.3 (100), 85.2 (9) | 7.5 (0.7) a | 7.4 (0.7) a | 1.59 (0.16) b |
| Oleuropein aglycone dialdehydic Open Form I a | 18.64 ± 0.04 | 377.1 | 275.6 (16), 149.3 (43), 139.5 (100), 111.2 (16), 101.3 (13), 95.4 (37) | 2.6 (0.3) a | 1.28 (0.13) b | 1.64 (0.16) b |
| Ligstroside aglycone enolic-aldehydic Open Form I b | 18.69 ± 0.04 | 361.0 | 291.8 (12), 171.3 (21), 139.3 (57), 127.2 (36), 101.3(100), 69.2 (18) | 5.0 (0.5) a,b | 4.5 (0.4) b | 6.2 (0.6) a |
| Luteolin d | 18.99 ± 0.05 | 285.2 | 217.1 (8), 199.0 (39), 175.0 (18), 133.2 (100) | 1.32 (0.13) b | 1.35 (0.13) b | 1.83 (0.18) a |
| Oleuropein aglycone carboxylic acid Open Forms I or II a | 19.30 ± 0.04 | 393.2 | 257.5 (77), 169.4 (100), 111.4 (66) | 0.29 (0.03) a | 0.109 (0.011) b | 0.139 (0.014) b |
| Acetoxy pinoresinol c | 19.43 ± 0.03 | 415.1 | 264.9 (43), 204.9 (18), 136.2 (100) | 0.21 (0.02) b | 0.29 (0.03) b | 0.70 (0.07) a |
| Hydroxy-methyl decarboxymethyl ligstroside aglycone isomer 1 b | 19.50 ± 0.03 | 333.0 | 181.5 (31), 111.3 (100), 99.1 (50), 94.9 (34), 69.4 (33) | 2.2 (0.2) a,b | 1.69 (0.17) b | 2.5 (0.2) a |
| Ligstroside aglycone enolic-aldehydic Open Form I b | 19.50 ± 0.03 | 361.0 | 291.7 (40), 259.7 (12), 171.4 (17), 139.3 (33), 127.4 (37), 101.3 (100), 69.2 (10) | 7.8 (0.8) a,b | 6.6 (0.7) b | 9.0 (0.9) a |
| Oleuropein aglycone carboxylic acid Open Forms I or II a | 19.80 ± 0.03 | 393.2 | 257.5 (77), 169.4 (100), 111.4 (66) | n.q. | n.q. | n.q. |
| Hydroxy-methyl decarboxymethyl ligstroside aglycone isomer 2 b | 19.92 ± 0.04 | 333.0 | 181.6 (28), 153.4 (8), 111.3 (100), 99.1 (50), 94.9 (34), 69.4 (33) | 0.30 (0.03) b | 0.47 (0.05) a | 0.34 (0.03) b |
| Oleuropein aglycone dialdehydic Open Form I a | 20.14 ± 0.03 | 377.1 | 275.7 (19), 149.4 (50), 139.4 (100), 111.2 (23), 101.2 (19), 95.4 (43) | 6.2 (0.6) a | 3.4 (0.3) b | 5.4 (0.5) a |
| Hydroxy-methyl decarboxymethyl ligstroside aglycone isomer 3 b | 20.28 ± 0.04 | 333.0 | 181.6 (28), 153.4 (8), 111.3 (100), 99.1 (50), 94.9 (34), 69.4 (33) | 0.22 (0.02) b | 0.42 (0.04) a | 0.24 (0.02) b |
| Oleuropein aglycone dialdehydic Open Form I a | 20.86 ± 0.02 | 377.1 | 275.7 (28), 149.4 (52), 139.4 (100), 111.3 (41), 101.2 (18), 95.4 (64) | 16.5 (1.6) a | 11.9 (1.2) b | 17.8 (1.8) a |
| Ligstroside aglycone dialdehydic Open Form I b | 21.00 ± 0.02 | 361.1 | 291.8 (37), 259.6 (21), 139.4 (47), 127.3 (46), 101.3 (100), 69.2 (12) | 1.86 (0.19) a | 0.90 (0.09) b | 0.56 (0.06) c |
| Apigenin d | 21.23 ± 0.04 | 269.2 | 150.8 (12), 117.0 (100), 107.1 (35) | 0.54 (0.05) b | 0.66 (0.06) b | 1.02 (0.10) a |
| Methoxyluteolin d | 21.58 ± 0.03 | 299.1 | 227.0 (100), 199.1 (13) | 0.39 (0.04) b | 0.24 (0.02) c | 0.55 (0.05) a |
| Mono enolic-aldehydic oleuropein aglycone Closed FormI a | 21.94 ± 0.03 | 377.1 | 275.7 (30), 149.4 (43), 139.4 (100), 111.2 (44), 101.2 (16), 95.4 (69) | 95 (9) a | 69 (7) b | 96 (10) a |
| Ligstroside aglycone dialdehydic Open Form I b | 22.07 ± 0.07 | 361.1 | 291.7 (44), 171.3 (19), 139.3 (56), 127.3 (41), 101.2 (100), 69.1 (35) | 7.3 (0.7) | 6.4 (0.6) | 6.5 (0.6) |
| Ligstroside aglycone dialdehydic Open Form I b | 22.80 ± 0.02 | 361.1 | 291.7 (45), 171.3 (19), 139.3 (42), 127.3 (63), 101.2 (100), 69.5 (12) | 4.8 (0.5) a | 3.6 (0.4) b | 4.4 (0.4) a,b |
| Mono enolic-aldehydic dihydropyranic ligstroside aglycone Closed FormI b | 24.08 ± 0.03 | 361.1 | 291.7 (32), 259.6 (10), 171.5 (12), 139.4 (38), 127.3 (55), 101.3 (100), 69.3 (15) | 27 (3) a | 18.1 (1.8) b | 16.2 (1.6) b |
| Total polyphenols e | 280 (30) a | 169 (17) b | 200 (20) a,b |
a Expressed as 3-hydroxytyrosol equivalents; b expressed as tyrosol equivalents; c expressed as pinoresinol equivalents; d expressed as apigenin equivalents; e sum of identified polar phenols; f values are expressed as mg/g of oil. Standard deviation is reported in parentheses (n = 3); g values followed by the same letters between columns did not differ significantly at p < 0.05, using Tukey’s HSD post hoc test. RT: retention time; [M-H]−: deprotonated molecule; MS/MS: product ions; n.d.: not detected, signal under the LOD; n.q.: not quantified, signal under the LOQ. Cor: Coratina; CM/Cor: blended of Cima di Mola and Coratina; Cas: Casaliva.