Table 1.
Phytochemical profiling of EVME via LC–MS/MS (negative mode) analysis.
| No. | Error | Metabolite Name | Rt Min | Molecular Formula | Identification | Fragments or MS2 Ions m/z |
Precursor m/z
[M–H]− |
Theoretical Mass | Ref. | |
|---|---|---|---|---|---|---|---|---|---|---|
| Phenolic or Organic Acids Derivatives | ||||||||||
| 1 | −4.7 | D-Malic acid | 1.098 | C4H6O5 | Beta hydroxy acids and derivatives | 59.01, 71.01, 115.00 133.01 | 133.0150 | 134.0230 | [22] | |
| 2 | −2.1 | Shikimic acid | 1.111 | C7H10O5 | Shikimic acids and derivatives | 73.02, 137.04, 173.04 | 173.0460 | 174.0540 | [23] | |
| 3 | −0.1 | Maleic acid | 1.112 | C4H4O4 | Dicarboxylic acids and derivatives | 71.01, 115.01 | 115.0032 | 116.0112 | ||
| 4 | −0.2 | D-Quinic acid | 1.136 | C7H12O6 | Quinic acids and derivatives | 85.02, 145.04, 173.04, 191.05 | 191.0562 | 192.0642 | ||
| 5 | −0.9 | 3,4-Dihydroxy benzoic acid |
1.257 | C7H6O4 | Hydroxybenzoic acid derivatives | 109.03, 153.01 | 153.0187 | 154.0267 | [24] | |
| 6 | 3.1 | Caffeic acid | 1.344 | C9H8O4 | Hydroxycinnamic acids | 59.02, 89.02, 135.04, 179.05 | 179.0545 | 180.0625 | ||
| 7 | 4.4 | 3-(4-Hydroxy-3-methoxy-phenyl) prop-2-enoic acid | 2.076 | C10H10O4 | Hydroxycinnamic acids | 134.03, 193.05 | 193.0524 | 194.0604 | ||
| 8 | 0.8 | Salicylic acid | 4.442 | C7H6O3 | Salicylic acid | 91.02, 108.01, 136.01, 137.02 | 137.0238 | 138.0318 | [25] | |
| 9 | 0.8 | (+/−)-cis,trans-abscisic acid | 5.286 | C15H20O4 | Abscisic acids and derivatives | 151.07, 219.13, 263.11 | 263.1278 | 264.1358 | [25] | |
| 10 | −0.7 | 5-Methoxy salicylic acid | 6.857 | C8H8O4 | M-Methoxybenzoic acids and derivatives | 108.02, 152.01, 167.03 | 167.0352 | 168.0432 | ||
| 11 | 6.0 | Rosmarinic acid | 7.136 | C18H16O8 | Coumaric acids and derivatives | 181.04, 329.09, 359.11 | 359.1105 | 360.1185 | [26] | |
| 12 | −3.1 | Isocitrate | 27.721 | C6H8O7 | Tricarboxylic acids and derivatives | 150.96, 190.95 | 191.1050 | 192.1130 | ||
| Flavonoids and related metabolites | ||||||||||
| 13 | −3.7 | Baicalein-7-O-glucuronide | 1.293 | C21H18O11 | 445.07 | Flavonoid-7-O-glucuronides | 102.95, 191.05, 269.02 377.07, 445.14 | 445.1807 | 446.1887 | [27] |
| 14 | −2.1 | Isorhamnetin-3-O-rutinoside | 4.930 | C28H32O16 | 623.12 | Flavonoid-3-O-glycosides | 285.03, 470.87, 579.00, 623.12 | 623.1269 | 624.1349 | [28] |
| 15 | −3.1 | Procyanidin B2 | 5.006 | C30H26O12 | 577.13 | Biflavonoids and polyflavonoids | 407.07, 425.08, 577.13 | 577.1369 | 578.1449 | [28] |
| 16 | 5.0 | Kaempferol-3-O-alpha-L-rhamnoside | 5.223 | C21H20O10 | 431.18 | Flavonoid-3-O-glycosides | 151.04, 179.05, 362.88, 431.19 | 431.1890 | 432.1970 | |
| 17 | −3.6 | Daidzein-8-C-glucoside | 5.452 | C21H20O9 | 415.15 | Isoflavonoid C-glycosides | 210.92, 286.92, 415.16 | 415.1572 | 416.1652 | [29, 30] |
| 18 | −0.1 | Naringenin-7-O-glucoside | 6.170 | C21H22O10 | 433.20 | Flavonoid-7-O-glycosides | 271.06, 387.18, 433.10 | 433.2068 | 434.2148 | |
| 19 | −2.2 | (+−)-Taxifolin | 6.492 | C15H12O7 | 303.05 | Flavanonols | 125.02, 179.00, 1990.95, 285.04, 303.04 | 303.0520 | 304.0600 | |
| 20 | 2.5 | Hyperoside | 6.542 | C21H20O12 | 463.08 | Flavonoid-3-O-glycosides | 218.94, 286.94. 300.02, 326.92, 394.90, 463.08 | 463.0858 | 464.0938 | |
| 21 | 0.5 | Apigenin 8-C-glucoside | 6.542 | C21H20O10 | 431.09 | Flavonoid 8-C-glycosides | 269.04,311.05, 362.89, 431.20 | 431.0956 | 432.1036 | |
| 22 | −0.1 | Formononetin | 6.734 | C16H12O4 | 267.08 | 4’-O-methylisoflavones | 133.02, 193.04, 252.06, 267.08 | 267.0875 | 268.0955 | |
| 23 | 0.9 | Procyanidin B1 | 6.785 | C30H26O12 | 577.14 | Biflavonoids and polyflavonoids | 245.04, 425.08, 577.12 | 577.1337 | 578.1417 | [31] |
| 24 | 0.6 | Luteolin-7-O-glucoside | 6.913 | C21H20O11 | 447.09 | Flavonoid-7-O-glycosides | 285.03, 327.04, 447.09 | 447.0923 | 448.1003 | |
| 25 | 8.9 | Isookanin-7-glucoside | 6.926 | C21H22O11 | 449.09 | Flavonoid-7-O-glycosides | 151.00, 287.04, 449.09 | 449.0952 | 450.1032 | |
| 26 | 0.4 | Isorhamnetin-3-O-glucoside | 7.417 | C22H22O12 | 477.10 | Flavonoid-3-O-glycosides | 285.03, 299.01, 315.04, 477.09 | 477.1033 | 478.1113 | |
| 27 | −0.1 | Kaempferol-7-neohesperidoside | 7.539 | C27H30O15 | 593.14 | Flavonoid-7-O-glycosides | 269.04, 593.13, | 593.1483 | 594.1563 | |
| 28 | −0.9 | Apigenin-7-O-glucoside | 7.700 | C21H20O10 | 431.09 | Flavonoid-7-O-glycosides | 268.03, 311.06, 431.09 | 431.0988 | 432.1068 | |
| 29 | 10.9 | Kaempferol-3-Glucuronide | 7.893 | C21H18O12 | 461.10 | Flavonoid-3-O-glucuronides | 256.92, 299.09, 392.89, 461.09 | 461.1031 | 462.1111 | |
| 30 | −3.7 | 3’ 4’ 5 7-Tetrahydroxy flavanone |
8.678 | C13H12O6 | 287.05 | Flavanones | 135.04, 151.00, 218.94, 287.06 | 287.0984 | 288.1064 | |
| 31 | −0.2 | Kaempferol-3-O-alpha-L-arabinoside | 8.751 | C20H18O10 | 417.11 | Flavonoid-3-O-glucuronides | 179.05, 362.88, 431.19 | 417.1194 | 418.1274 | |
| 32 | −0.1 | Naringenin | 9.744 | C15H12O5 | 271.09 | Flavanones | 228.07, 255.05, 271.09 | 271.0985 | 272.1065 | [32] |
| 33 | −2.6 | 3’-Methoxy-4’,5,7-trihydroxy flavonol | 10.368 | C16H12O7 | 315.05 | Flavonols | 257.04, 300.02, 315.04 | 315.0528 | 316.0608 | |
| 34 | −3.0 | Apigenin | 10.428 | C15H10O5 | 269.04 | Flavones | 117.03, 151.00, 181.06, 225.05, 269.04 | 269.0467 | 270.0547 | [32] |
| 35 | 0.8 | Luteolin | 11.175 | C15H10O6 | 285.07 | Flavones | 151.00, 270.06, 263.11 | 285.0763 | 286.0843 | [32] |
| 36 | 0.7 | Rhoifolin | 11.421 | C27H30O14 | 577.13 | Flavonoid-7-O-glycosides | 291.19, 464.94, 577.13 | 577.1346 | 578.1426 | |
| 37 | −4.0 | 3 5 7-Trihydroxy-4’-methoxyflavone | 12.886 | C16H12O6 | 299.09 | Flavonols | 119.04, 179.03, 193.05, 299.09 | 299.0558 | 300.0638 | |
| 38 | −0.1 | 4’,5,7-Trihydroxy flavonol | 13.890 | C15H10O6 | 285.11 | Flavonols | 119.04, 149.99, 165.02, 285.07 | 285.1115 | 286.1195 | |
| 39 | −0.4 | Hesperetin | 14.598 | C16H14O6 | 301.10 | 4’-O-methylated flavonoids | 138.03, 151.03, 286.08, 301.10 | 301.0692 | 302.0772 | [33] |
| 40 | −0.2 | Luteolin-3’, 7-di-O-glucoside | 17.799 | C27H30O16 | 609.13 | Flavonoid-7-O-glycosides | 564.90, 594.11, 609.13 | 609.1440 | 610.1520 | |
| Fatty acids | ||||||||||
| 41 | −0.8 | 3-Hydroxy-3-Methyl glutaric acid | 1.159 | C6H10O5 | 161.04 | Hydroxy fatty acids | 57.03, 99.04, 161.04 | 161.0452 | 162.0532 | |
| 42 | −2.7 | 2-Isopropyl malic acid | 1.331 | C7H12O5 | 175.05 | Hydroxy fatty acids | 101.02, 113.05, 175.06 | 175.0599 | 176.0679 | |
| 43 | −0.5 | Citraconic acid | 1.394 | C5H6O4 | 129.01 | Methyl-branched fatty acids | 84.99, 129.01 | 129.0189 | 130.0269 | |
| 44 | 1.5 | Citramalate | 1.407 | C5H8O5 | 147.06 | Hydroxy fatty acids | 72.98, 87.00, 129.01, 147.06 | 147.0647 | 148.0727 | |
| 45 | −4.0 | Gamma-Linolenic acid | 18.900 | C18H30O2 | 277.14 | Linoleic acids and derivatives | 141.09, 233.15, 277.13 | 277.1465 | 278.1545 | |
| Others | ||||||||||
| 46 | −0.3 | E-3,4,5’-Trihydroxy-3’-glucopyranosyl stilbene | 1.123 | C20H22O9 | 405.01 | Stilbene glycosides | 190.96, 191.05, 243.02, 369.03, 405.09 | 405.1208 | 406.1288 | |
| 47 | −0.6 | Esculin | 1.172 | C15H16O9 | 339.12 | Coumarin glycosides | 149.01, 175.02, 202.90, 295.10, 339.11 | 339.1296 | 340.1376 | |
| 48 | 0.2 | Catechin | 5.452 | C15H14O6 | 289.07 | Catechins | 109.02, 125.02, 179.03, 203.03, 245.07, 289.06 | 289.0711 | 290.0791 | [31] |
| 49 | 3.0 | Hinokitiol | 6.815 | C10H12O2 | 163.07 | Tropolones | 119.08, 135.08, 163.07 | 163.0751 | 164.0831 | |
| 50 | −0.4 | Daphnetin | 7.295 | C9H6O4 | 177.01 | 7,8-Dihydroxycoumarins | 117.09, 133.03, 149.02, 163.01, 177.01 | 177.018 | 178.0260 | |
| 51 | 1.0 | E-4,5’-Dihydroxy-3-methoxy-3’-glucopyranosyl stilbene | 9.547 | C21H24O9 | 419.07 | Stilbene glycosides | 257.02, 343.01, 363.12, 419.06 | 419.0748 | 420.0828 | |