Table 3 Metabolites identified in the methanol extracts of Murcott leaves (MTL), Merav leaves (MVL), Murcott fruits (MTF), and Merav fruits (MVF) in positive ionization mode [M + H]+ and negative ionization mode [M-H]−.
Peak ID | Rt (min) | Compound name | MTL | MVL | MTF | MVF | Molecular formula | Error (ppm) | [M + H]+ (m/z ) | MS2 Fragments (m/z ) | [M-H]− (m/z ) | MS2 Fragments (m/z ) |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
Flavonoids: | ||||||||||||
• Flavanones | ||||||||||||
1 | 6.530 | Naringenin 7-O-glucoside | √ | √ | √ | √ | C21H22O10 | 9.6 | 435.1262 | 273.0559 | 433.185 | 151.0019, 271.0610 |
2 | 7.408 | Eriodictyol 7-O-neohesperidoside | √ | √ | √ | √ | C27H32O15 | 0.1 | − | − | 595.1640 | 287.0571, 449.1302, |
3 | 7.851 | Isookanin 7-glucoside (Flavanomarein) | - | - | √ | - | C21H22O11 | -5.9 | − | − | 449.1027 | 269.0427, 287.0549, |
4 | 8.197 | Hesperetin 7-O-neohesperidoside | - | - | √ | - | C28H34O15 | 4.1 | − | − | 609.1738 | 301.0613 |
5 | 8.438 | Hesperidin | √ | √ | √ | √ | C28H34O15 | -0.2 | 611.2517 | 303.11199 | 609.1814 | 301.0713 |
6 | 9.893 | Isosakuranetin 7-O-neohesperidoside | √ | √ | √ | √ | C28H34O14 | -3.1 | 595.2019 | 195.0290, 263.0552, 287.0906 | 593.1902 | 285.0609 |
7 | 11.061 | Naringenin | √ | √ | √ | √ | C15H12O5 | 0.7 | 273.0745 | 121.0524, 153.02046, | 271.0605 | 119.0498, 151.0036 |
8 | 11.485 | Hesperetin | √ | √ | √ | √ | C16H14O6 | 1 | 303.0844 | 288.1534 | 301.0720 | 286.0478 |
9 | 18.860 | 5,7,3’,4’ tetrahydroxyflavanone | √ | - | - | - | C15H12O6 | -0.6 | − | − | 287.1661 | 251.0660, 269.2064 |
• Flavones | ||||||||||||
10 | 5.742 | Luteolin 7,3’-di-O-glucoside | √ | - | - | √ | C27H30O16 | 0.1 | − | − | 609.0918 | 283.09683 |
11 | 7.020 | Luteolin 8-C-glucoside (Orientin) | √ | - | √ | - | C21H20O11 | 3.2 | 449.1772 | 329.09913 | 447.0936 | 327.0678, 357.0684 |
12 | 7.049 | Luteolin 6-C-glucoside (Isoorientin) | - | √ | √ | √ | C21H20O11 | -0.1 | 449.1086 | 329.08692 | 447.0912 | 327.0698, 357.0664 |
13 | 7.292 | Vitexin 2’’-O-rhamnoside | √ | - | √ | √ | C27H30O14 | 5.8 | − | − | 577.1512 | 431.1573 |
14 | 7.496 | Apigenin 8-C-glucoside (Vitexin) | √ | √ | √ | √ | C21H20O10 | 9 | 433.1492 | 285.1294, 343.1141 | 431.0981 | 283.0634, 311.0588, 341.0755 |
15 | 8.081 | Rhoifolin (Apigenin 7-O-neohesperidoside) | √ | √ | √ | √ | C27H30O14 | 2.2 | 579.1668 | 271.0946 | 577.1533 | 269.0453 |
16 | 8.277 | Diosmin | - | - | √ | √ | C28H32O15 | 1.3 | 609.1791 | 301.05007 | − | − |
17 | 8.438 | Baicalein 7-O-glucuronide (Baicalin) | √ | √ | - | - | C21H18O11 | 2.6 | − | − | 445.1099 | 265.0979, 309.2156, 399.0928 |
18 | 8.476 | Apigenin 7-O-glucoside | √ | - | - | - | C21H20O10 | 6.2 | − | − | 431.0963 | 268.0388 |
19 | 9.031 | Acacetin | - | √ | √ | - | C16H12O5 | 0.1 | 285.1271 | 270.9302 | 283.0620 | 196.0467, 239.1632, 247.14557, 268.0359 |
20 | 9.647 | Acacetin 7-O-neohesperidoside | - | - | - | √ | C28H32O14 | 1.6 | − | − | 591.1755 | 149.04949, 161.02716, 267.16993, 283.06346, 573.18067, 591.1755 |
21 | 9.731 | Acacetin 7-O-rutinoside | √ | - | √ | √ | C28H32O14 | 0.8 | 593.15 | 285.1078 | 591.3115 | 283.0629 |
22 | 9.909 | Luteolin 4’-O-glucoside | - | - | √ | √ | C21H20O11 | 3.9 | 449.1597 | 287.0989 | − | − |
23 | 11.236 | Apigenin | √ | √ | - | - | C15H10O5 | 6.7 | − | − | 269.0452 | 117.0344, 151.0038 |
24 | 13.789 | Luteolin | √ | √ | √ | √ | C15H10O6 | 2.3 | 287.0881 | 153.1242 | 285.0768 | 151.0042 |
• Isoflavones | ||||||||||||
25 | 1.155 | Daidzein | - | - | - | √ | C15H10O4 | -9.5 | 255.1450 | 122.9401, 165.9184, 236.9890 | − | − |
26 | 4.679 | Ononin | - | - | √ | - | C22H22O9 | -2 | 431.1562 | 226.9483, 269.1088, | − | − |
27 | 5.483 | Genistein | - | - | √ | √ | C15H10O5 | 5.9 | 271.1186 | 242.9196, 252.9485 | − | − |
28 | 5.755 | Daidzein 8-C-glucoside | √ | √ | √ | √ | C21H20O9 | -7.7 | − | − | 415.1227 | 371.1811 |
29 | 11.540 | Sissotrin (5-hydroxy ononin) | - | - | √ | √ | C22H22O10 | -5.8 | 447.1677 | 285.1139 | − | − |
30 | 12.672 | Formononetin | - | √ | - | - | C16H12O4 | 0.3 | − | − | 267.1938 | 195.0514, 211.0458, 224.0521, 252.046 |
• Flavonols | ||||||||||||
31 | 0.984 | Myricetin | √ | √ | - | √ | C15H10O8 | 3.2 | 319.0969 | 124.9584 | 317.0550 | 122.9862, 273.00216, |
32 | 1.362 | Taxifolin | - | - | √ | - | C15H12O7 | -1 | 305.1297 | 287.1295 | − | − |
33 | 5.865 | Kaempferol 3-Glucuronide | √ | - | √ | - | C21H18O12 | -9.9 | − | − | 461.1724 | 285.09616, 415.19103 |
34 | 6.089 | Kaempferol 7-neohesperidoside | √ | √ | √ | √ | C27H30O15 | 0.2 | − | − | 593.1493 | 285.0437 |
35 | 6.227 | Quercetin 3-D-xyloside | √ | - | - | - | C20H18O11 | 0.5 | − | − | 433.1754 | 301.10762 |
36 | 6.272 | Gossypin | - | - | √ | - | C21H20O13 | 2.9 | 481.1274 | 319.0977 | − | − |
37 | 6.278 | Isorhamnetin 3-O-rutinoside | √ | √ | √ | √ | C28H32O16 | 4.6 | 625.1587 | 317.0988 | 623.1601 | 315.1159 |
38 | 6.419 | Kaempferol 3-O-robinoside-7-O-rhamnoside | - | - | √ | √ | C33H40O19 | -2.8 | 741.2368 | 433.1183, 595.1691 | − | − |
39 | 6.539 | Quercetin 3-O-β-D-galactopyranoside (Hyperoside) | - | - | √ | √ | C21H20O12 | 0.7 | 465.1707 | 303.14627 | − | − |
40 | 6.610 | Quercitrin | - | √ | - | - | C21H20O11 | 3.3 | − | − | 447.1960 | 301.1678 |
41 | 6.618 | Quercetin 3,4’-O-di-β-glucopyranoside | √ | - | √ | √ | C27H30O17 | -2.7 | − | − | 625.1803 | 301.0446 |
42 | 7.209 | Kaempferol 3-O-α-L-rhamnoside | √ | √ | √ | - | C21H20O10 | 1.4 | − | − | 431.1905 | 265.0933, 285.1485 |
43 | 7.362 | Rutin | - | - | √ | √ | C27H30O16 | 4.3 | 611.1714 | 303.0598 | − | − |
44 | 7.662 | Kaempferol 3-O-rutinoside | - | - | √ | √ | C27H30O15 | 2.5 | 595.1741 | 287.0784 | − | − |
45 | 7.886 | Kaempferol 3-O-(6-p-coumaroyl)-glucoside | √ | - | - | - | C30H26O13 | 0.5 | − | − | 593.1507 | 285.0403 |
46 | 7.972 | Kaempferol 3-O-glucoside | - | - | - | √ | C21H20O11 | 0 | 449.1830 | 287.1305 | − | − |
47 | 8.018 | Myricitrin | √ | - | - | - | C21H20O12 | 3.6 | − | − | 463.1173 | 317.0910 |
48 | 8.043 | Syringetin 3-O-galactoside | √ | √ | √ | - | C23H24O13 | -0.9 | − | − | 507.1148 | 345.0618 |
49 | 8.088 | Syringetin 3-O-glucoside | - | √ | - | - | C23H24O13 | 2.6 | − | − | 507.1167 | 344.0563 |
50 | 8.342 | Isorhamnetin 3-O-glucoside | - | √ | √ | - | C22H22O12 | -3.2 | − | − | 477.1062 | 315.0541 |
51 | 8.424 | Isoquercitrin | - | - | √ | - | C21H20O12 | -5.3 | 465.1398 | 303.0920 | − | − |
52 | 8.963 | Quercetin 4’-glucoside | - | √ | - | - | C21H20O12 | 7.6 | − | − | 463.2537 | 301.0728 |
53 | 11.260 | Quercetin | √ | - | √ | - | C15H10O7 | -6.2 | 303.1436 | 119.0423, 125.06459, 153.0238 | 301.0736 | 117.0197, 149.0611, 151.0038 |
54 | 11.534 | 3,5,7-trihydroxy-4’-methoxyflavone (Kaempferide) | √ | √ | √ | √ | C16H12O6 | 1.2 | 301.1431 | 286.0360 | 299.0562 | 284.0330 |
55 | 12.633 | 3’-methoxy-4’,5,7-trihydroxyflavonol (Isorhamnetin) | √ | - | √ | - | C16H12O7 | 8.3 | 317.0682 | 270.0245, 287.0478 | 315.0877 | 268.0450, 285.0424 |
56 | 14.076 | 3,5,3’,4’-tetrahydroxy-7-methoxyflavone | √ | √ | √ | √ | C16H12O7 | -3.8 | 317.1238 | 231.9871, 249.0785, | 315.0906 | 229.0174, 247.0620, |
• Flavanol | ||||||||||||
57 | 19.045 | L-Epicatechin | √ | √ | - | - | C15H14O6 | 0.7 | 291.2321 | 205.9864, 247.2654 | − | − |
• Aurones | ||||||||||||
58 | 5.625 | Maritimetin 6-O-glucoside | - | - | √ | √ | C21H20O11 | 0.5 | 449.1412 | 287.08304 | − | − |
• Anthocyanidins | ||||||||||||
59 | 7.382 | Delphinidin 3-O-(6’’-O-α-rhamnopyranosyl-β-glucopyranoside) | √ | √ | √ | √ | C27H31O16 | -5.5 | − | − | 609.1468 [M-2 H]− | 151.0025, 163.06029, 271.0573, 299.1257, 300.0286, 301.0354, |
60 | 7.414 | Cyanidin 3-O-rutinoside (keracyanin) | - | - | √ | √ | C27H31O15 | 1.6 | 595.1634 [M]+ | 287.19833 | − | − |
61 | 7.882 | Delphinidin | - | √ | - | √ | C15H11O7 | -0.6 | − | − | 301.0749 [M-2 H]− | 255.2276, 283.1827 |
62 | 8.085 | Malvidin 3-galactoside | - | - | √ | - | C23H25O12 | -5.1 | 493.1328 [M]+ | 331.1293 | 491.1202 [M-2 H]− | 329.0817, 330.9201 |
63 | 8.425 | Malvidin 3, 5-di-O-glucoside chloride | - | - | √ | - | C29H35O17 | 6.1 | 655.1688 [M]+ | 331.21144, | − | − |
64 | 8.649 | Peonidine 3-O-glucoside chloride | √ | √ | √ | √ | C22H23O11 | -6.2 | 463.1289 [M]+ | 301.1236 | 461.1078 [M-2 H]− | 299.8789 |
65 | 8.888 | Malvidin 3-O-glucoside chloride | - | - | √ | - | C23H25O12 | 0.2 | − | − | 491.1162 [M-2 H]− | 329.0908 |
• Chalcones | ||||||||||||
66 | 7.869 | Okanin 4’-O-glucoside | - | √ | - | √ | C21H22O11 | 1.1 | 451.117 | 289.1178 | 449.0889 | 287.2334 |
67 | 8.888 | Neohesperidin dihydrochalcone | - | - | √ | - | C28H36O15 | 3.9 | − | − | 611.1354 | 303.0517, 345.0949, 405.0437, 449.0966, 465.1055, 491.1552 |
68 | 13.288 | Phlorizin | √ | - | √ | - | C21H24O10 | 0.9 | 437.1937 | 275.0933 | 435.2028 | 273.1481 |
Phenolic acid conjugates | ||||||||||||
69 | 0.972 | Chlorogenic acid | √ | - | √ | - | C16H18O9 | 0.1 | 355.1735 | 181.0518, 193.0435, | 353.1095 | 179.04203, 191.0895 |
70 | 1.945 | 1-O-b-D-glucopyranosyl sinapate | √ | √ | √ | √ | C17H22O10 | -1.1 | 387.1826 | 225.9061 | 385.0780 | 223.04486 |
71 | 5.911 | trans-Cinnamate | - | √ | - | √ | C9H8O2 | 5.5 | − | − | 147.0397 | 103.04567, 119.03396, 147.0438 |
72 | 5.961 | 3-(4-Hydroxyphenyl) prop-2-enoic acid (p- coumaric acid) | - | - | √ | - | C9H8O3 | 0.8 | 165.0587 | 103.0584, 120.9609 | − | − |
73 | 6.361 | 3-(4-hydroxy-3,5-dimethoxyphenyl)-2-propenoic acid (sinapic acid) | - | - | √ | √ | C11H12O5 | 3.3 | 225.0932 | 151.0554, 195.0495, 210.1461 | − | − |
74 | 9.440 | Caffeic acid | √ | √ | - | √ | C9H8O4 | 4.5 | 181.1223 | 137.1266 | 179.0305 | 135.0468 |
75 | 10.040 | Rosmarinic acid | √ | - | - | - | C18H16O8 | 1.2 | − | − | 359.1731 | 135.0345, 161.0424, 179.0981, 197.1208 |
Fatty acid and their conjugates | ||||||||||||
76 | 0.953 | 3-Hydroxy-3-Methylglutaric acid | - | √ | - | - | C6H10O5 | 9.1 | − | − | 161.0429 | 117.1311, 143.0422 |
77 | 1.185 | D-(+)-Malic acid | √ | √ | √ | √ | C4H6O5 | 0.7 | − | − | 133.014 | 89.0261, 115.0116 |
78 | 1.236 | 2-Isopropylmalic acid | √ | √ | √ | - | C7H12O5 | 7.3 | − | − | 175.0592 | 131.0785, 157.0466, |
79 | 15.542 | 4-(4-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanyl β-D-glucopyranoside | - | √ | - | - | C19H34O7 | 0 | 397.2 | 212.1024, 233.1284 | − | − |
80 | 22.296 | gamma-Linolenic acid | √ | √ | √ | - | C18H30O2 | 1.6 | − | − | 277.2171 | 233.25313, 259.2215 |
81 | 23.662 | 3-ethyl-4-hydroxy-4-methylpentyl 6-O-[(2 S,3R,4R)-tetrahydro-3,4-dihydroxy-4-(hydroxymethyl)-2-furanyl] β-D-Glucopyranoside | - | √ | - | - | C19H36O11 | -4.7 | 463.2849 [M + Na]+ | 303.1417 | − | − |
Coumarins | ||||||||||||
82 | 7.993 | Scopoletin | √ | √ | √ | - | C10H8O4 | 1.3 | 193.0473 | 133.0237, 150.0272, 178.0350 | 191.0349 | 148.0174, 176.0123 |
83 | 10.875 | Daphnetin | √ | √ | √ | - | C9H6O4 | 2.2 | − | − | 177.0566 | 133.02692 |
84 | 13.595 | 7-hydroxy-4-methylcoumarin | - | - | √ | - | C10H8O3 | 5.5 | − | − | 174.9582 | 130.5520, 156.9518 |
85 | 16.441 | Esculin | - | √ | √ | √ | C15H16O9 | 2 | 341.1190 | 179.0878 | 339.2768 | 131.0757, 177.15072 |
Nitrogenous compounds | ||||||||||||
86 | 1.273 | 1-methylpyridinio-3-carboxylate | - | - | √ | - | C7H7NO2 | 0 | 138.0528 | 80.0437, 94.0741 | − | − |
87 | 6.073 | Ferrioxamine | - | √ | - | - | C27H45FeN6O9 | -0.9 | 654.2676 | 601.2931, 636.2343 | − | − |
88 | 21.887 | Octocrylene | - | √ | - | - | C24H27NO2 | -0.2 | 362.213 | 291.2485, 317.1709 | − | − |
Terpenes and terpenoids | ||||||||||||
89 | 12.222 | (6,6-Dimethylbicyclo[3.1.1] hept-2-yl)methyl 6-O-[(2R,3R,4R)-3,4-dihydroxy-4-(hydroxymethyl)tetrahydro-2-furanyl]-β-D-glucopyranoside | √ | √ | - | - | C21H36O10 | -0.7 | 471.1636 [M + Na]+ | 289.9070, 307.1324 | − | − |
90 | 14.167 | 4-[4-(β-D-glucopyranosyloxy)-2-hydroxy-2,6,6-trimethylcyclohexylidene]-3-Buten-2-one | √ | √ | - | - | C19H30O8 | 0.5 | 409.1627 [M + Na]+ | 245.1423 | − | − |
91 | 14.781 | 1-Acetoxy-7-isopropylidene-1,4a-dimethyl-6-oxodecahydro-2-naphthalenyl 2,3-dimethyl-2-oxiranecarboxylate | √ | √ | - | - | C22H32O6 | 0.9 | 415.2122 [M + Na]+ | 306.9146, 350.1746 | − | − |
92 | 15.530 | 7b,9-Dihydroxy-3-(hydroxymethyl)-1,1,6,8-tetramethyl-5-oxo-1,1a,1b,4,4a,5,7a,7b,8,9-decahydro-9aH-cyclopropa[3,4]benzo[1,2-e]azulen-9a-yl acetate | √ | √ | - | - | C22H30O6 | 2.2 | 432.237 [M + ACN + H]+ | 354.1479, 372.1671 | − | − |
93 | 15.530 | 3-(acetoxymethyl)-5-(2-formyl-4-hydroxy-5,5,8a-trimethyl-1,4,4a,6,7,8-hexahydronaphthalen-1-yl)pent-2-enoic acid | √ | √ | - | - | C22H32O6 | -1.1 | 415.2124 [M + Na]+ | 355.2124 | − | − |
94 | 17.544 | Hetisine | √ | √ | - | - | C20H27NO3 | -1 | 330.338 | 286.2968, 295.2156 | − | − |
95 | 20.281 | 1-Naphthalenepentanol, decahydro-2-hydroxy-gamma,2,5,5,8a-pentamethyl-, α-acetate | - | √ | - | - | C22H40O3 | -3.4 | 375.1954 [M + Na]+ | 275.18255, | − | − |
Miscellaneouse compounds | ||||||||||||
96 | 0.897 | Mucate | √ | √ | - | - | C6H10O8 | 0.3 | − | − | 209.0296 | 165.0320, 191.0381 |
97 | 0.972 | E-3,4,5’-Trihydroxy-3’-glucopyranosylstilbene | √ | √ | √ | √ | C20H22O9 | -0.6 | 407.1649 | 245.1125 | 405.1029 | 243.0556 |
98 | 1.311 | D-(-)-Quinic acid | √ | √ | √ | √ | C7H12O6 | -6.5 | − | − | 191.0577 | 127.04993, 173.94166 |
99 | 1.590 | Resveratrol | - | √ | √ | √ | C14H12O3 | -3.2 | 229.0318 | 145.09193,187.97542 | 227.1308 | 143.07954, 185.1308 |
100 | 12.214 | Benzyl 6-O-β-D-glucopyranosyl-β-D-glucopyranoside | √ | √ | - | - | C19H28O11 | -0.4 | 455.1904 [M + Na]+ | 293.8922 | − | − |
101 | 13.807 | 2-Phenylethyl 2-O-[(2 S,3R,4R)-3,4-dihydroxy-4-(hydroxymethyl)tetrahydro-2-furanyl]-β-D-glucopyranoside | √ | - | - | - | C19H28O10 | -2.7 | 439.1969 [M + Na]+ | 275.0986 | − | − |
102 | 14.121 | Phenylmethyl 6-O-[(2R,3R,4R)-tetrahydro-3,4-dihydroxy-4-(hydroxymethyl)-2-furanyl]-β-D-glucopyranoside | - | √ | - | - | C18H26O10 | -0.1 | 425.1375 | 261.9109 | − | − |
103 | 14.716 | Cascaroside D | √ | - | - | - | C27H32O13 | -0.9 | 587.2112 [M + Na]+ | 407.1388, 425.1842, | − | − |
104 | 15.507 | 1,5-Anhydro-2-O-(6-O-benzoyl-α-D-galactopyranosyl)-D-glucitol | √ | √ | - | - | C19H26O11 | 3.9 | 453.1649 [M + Na]+ | 289.2938 | − | − |
105 | 21.584 | Avobenzone | √ | √ | - | - | C20H22O3 | -0.2 | 311.2564 | 219.1414, 266.2041 | − | − |
106 | 22.076 | (2,6,6-Trimethyl-4-oxo-2-cyclohexen-1-yl)methyl β-D-glucopyranoside | √ | √ | - | - | C16H26O7 | -3.9 | 353.2682 [M + Na]+ | 191.0987 | − | − |
107 | 25.607 | 2-Acetoxy-4-pentadecylbenzoic acid | - | √ | - | - | C24H38O4 | -0.1 | 413.269 [M + Na]+ | 351.2435, 395.2117, | − | − |
