Table 3. Non-Volatile Compounds Identified in Five Cultivars by UPLC-Q-Exactive Orbitrap-MS.
| peak no. | RT (min) | experimental [M + H]+ (m/z) | major secondary fragment ions (m/z) | molecular formula | identification | reference |
|---|---|---|---|---|---|---|
| Flavonoids | ||||||
| 3 | 0.39 | 595.1663 | 577.1547, 541.1345, 511.1235, 481.1129, 457.1133, 427.1026, 409.0917, 391.0814, 379.0813, 349.0707, 337.0708, 325.0707, 295.0603, 283.0601, 271.0603, 257.0441, 229.0498, 219.0291, 203.0343, 195.0288, 145.0285, 121.0287, 103.0390, 85.0291, 57.0339 | C27H30O15 | vicenin | (24) |
| 6 | 0.5 | 433.1132 | 415.1024, 397.0919, 379.0812, 367.0813, 349.0705, 337.0707, 323.0913, 313.0707, 297.0757, 283.0602, 271.0602, 271.0602, 256.0728, 243.0284, 213.0548, 183.0291, 165.0184, 145.0285, 121.0286, 109.0284, 79.0185 | C21H20O10 | vitexin | (25) |
| 9 | 0.64 | 579.1710 | 433.1128, 344.1442, 313.0717, 283.0602, 271.0601, 243.0653, 203.0698, 171.0288, 153.0183, 119.0494, 85.0290 | C27H30O14 | rhoifolin | a |
| 10 | 0.65 | 271.0599 | 253.0490, 243.0650, 225.0547, 203.0699, 187.0394, 171.0288, 163.0387, 153.0184, 145.0286, 129.0181, 119.0494, 109.0284, 91.0548, 67.0186 | C15H10O5 | apigenin | (26) |
| 11 | 0.65 | 433.1132 | 332.4244, 313.0716, 283.0602, 271.0603, 261.1127, 243.0661, 225.0536, 189.0553, 171.0291, 153.0184, 119.0494, 91.0547, 67.0187 | C21H20O10 | apigenin 7-glucoside | (27) |
| 12 | 0.66 | 273.0756 | 255.0648, 231.0651, 207.0654, 189.0545, 179.0337, 171.0287, 157.0650, 153.0182, 147.0440, 129.0182, 123.0441, 119.0493, 107.0494, 91.0547, 83.0134, 67.0186, 55.0186 | C15H12O5 | naringenin | a |
| 13 | 0.68 | 581.1873 | 527.1444, 443.1302, 417.1174, 401.1236, 383.1126, 365.1016, 339.0863, 315.0862, 285.0755, 273.0757, 263.0549, 219.0289, 195.0289, 171.0289, 153.0183, 129.0547, 119.0493, 91.0547, 85.0290, 71.0499 | C27H32O14 | naringin | a |
| 14 | 0.71 | 609.1819 | 463.1243, 361.0900, 301.0708, 286.0473, 258.0524, 229.0494, 201.0560, 153.0184, 129.0546, 85.0290 | C28H32O15 | diosmin | (28) |
| 15 | 0.72 | 303.0865 | 285.0755, 261.0773, 244.1052, 219.0647, 201.0548, 189.0548, 177.0549, 171.0290, 163.0392, 153.0185, 149.0600, 137.0598, 123.0444, 117.0339, 111.0080, 89.0392, 83.0134, 67.0187, 55.0186 | C16H14O6 | hesperitin | (29) |
| 16 | 0.72 | 611.1978 | 449.1441, 413.1235, 395.1128, 369.0969, 345.0969, 315.0864, 303.0865, 281.0660, 263.0551, 219.0292, 195.0291, 177.0548, 153.0184, 129.0548, 111.0444, 85.0291, 71.0499 | C28H34O15 | hesperidin | a |
| 22 | 1.44 | 317.0660 | 302.0424, 285.0400, 273.0391, 257.0449, 229.0499, 217.0500, 203.0341, 189.0548, 165.0184, 153.0185, 139.0390, 121.0285, 105.0340, 92.0263, 68.9980 | C14H12O7 | isorhamnetin | (30) |
| 25 | 1.94 | 257.0812 | 239.0706, 215.0707, 191.0703, 179.0348, 173.0291, 171.0291, 153.0186, 145.0656, 131.0495, 123.0444, 107.0496, 103.0548, 97.0290, 91.0549, 79.0550, 67.0187, 57.1876 | C15H12O4 | pinocembrin | (31) |
| 27 | 3.48 | 301.0709 | 286.0473, 258.0523, 240.0417, 229.0500, 213.0548, 195.0444, 184.0514, 168.0051, 147.0440, 121.0285, 91.0552, 68.9974 | C16H12O6 | tectorigenin | (32) |
| 31 | 5.16 | 331.0815 | 316.0580, 301.0346, 288.0636, 273.0396, 245.0444, 231.0498, 203.0342, 189.0550, 173.0600, 159.0442, 147.0443, 139.0028, 121.0287, 107.0492, 91.0548, 68.9977 | C17H14O7 | iristetrigenin B | (33) |
| 35 | 7.63 | 343.1180 | 328.0945, 313.0709, 299.0899, 285.0759, 270.0529, 257.0811, 243.0659, 211.0764, 199.0240, 181.0132, 171.0288, 153.0184, 144.1716, 133.0651, 125.0236, 108.8341, 90.3219, 69.0341 | C19H18O6 | 5,7,8,4′-tetramethoxyflavone | b |
| 38 | 8.21 | 361.0921 | 346.0677, 331.0439, 317.0650, 303.0493, 287.0538, 275.0546, 257.0442, 229.0489, 197.0443, 181.0130, 164.0466, 137.0596, 121.0283, 93.0337, 65.0392 | C18H16O8 | 5,7,3′-trihydroxy-6,4′,5′-trimethoxyflavone | b |
| 39 | 8.55 | 345.0972 | 330.0736, 315.0502, 301.0704, 287.0553, 272.0319, 259.0601, 231.0652, 213.0549, 189.0548, 181.0136, 153.0184, 131.0494, 121.0287, 107.0496, 85.0291, 65.0393 | C18H16O7 | lysionotin | (34) |
| 40 | 8.6 | 403.1391 | 388.1156, 373.0921, 358.0683, 345.0971, 327.0863, 313.0710, 301.0709, 287.0539, 274.0840, 258.0524, 229.0342, 211.0239, 193.0136, 183.0291, 165.0549, 148.0517, 127.0393, 99.0443, 69.0344 | C21H22O8 | nobiletin | a |
| 41 | 8.77 | 375.1077 | 360.0841, 345.0607, 330.0370, 302.0418, 274.0474, 257.0449, 229.0502, 201.0545, 181.0136, 151.0392, 137.0234, 109.0288, 74.4930 | C19H18O8 | chrysosplenetin B | (35) |
| 43 | 9.54 | 373.1284 | 358.1048, 343.0814, 328.0579, 315.0857, 297.0759, 283.0603, 271.0602, 244.0733, 229.0321, 211.0240, 193.0139, 183.0290, 168.0052, 145.0647, 135.0442, 127.0393, 99.0441, 69.0341 | C20H20O7 | tangeretin | a |
| 45 | 10.55 | 389.1236 | 373.0987, 374.0998, 343.0455, 331.0815, 301.0354, 275.0919, 257.0815, 242.0583, 217.0495, 181.0133, 165.0549, 153.0185, 137.0236, 109.0287, 79.0546 | C20H20O8 | artemetin | (36) |
| Coumarins | ||||||
| 5 | 0.48 | 191.0704 | 173.1327, 163.0755, 158.1095, 149.0599, 145.1010, 133.1013, 123.0813, 119.0495, 115.0547, 105.0703, 93.0704, 91.0548, 86.0242, 79.0549, 69.0342, 55.0551 | C11H10O3 | 7-methoxy-4-methylcoumarin | b |
| 8 | 0.61 | 247.0965 | 229.0860, 211.0756, 201.0547, 187.0753, 175.0391, 163.0390, 159.0441, 147.0441, 142.0776, 131.0493, 119.0494, 103.0546, 91.0547, 85.0651, 65.0393 | CH14H14O4 | marmesin | (37) |
| 17 | 0.78 | 193.0498 | 178.0262, 161.0598, 150.0314, 154.0782, 143.0598, 137.0598, 133.0286, 122.0365, 115.0546, 105.0703, 95.0496, 89.0391, 79.0548, 66.0472, 55.0187 | C10H8O4 | isoscopoletin | a |
| 19 | 0.91 | 409.1492 | 391.1861, 261.1112, 247.0965, 229.0859, 211.0751, 201.0547, 187.0390, 159.0441, 131.0492, 97.0289, 85.0290, 69.0343 | C20H24O9 | nodakenin | (38) |
| 20 | 1.31 | 261.1123 | 261.1123, 243.1017, 231.1023, 217.0860, 201.0548, 189.0548, 177.0547, 159.0442, 145.0648, 131.0493, 128.0625, 115.0544, 103.0547, 95.0491, 85.0655, 67.0550 | C15H16O4 | isomeranzin | a |
| 21 | 1.32 | 279.1228 | 261.1121, 243.1064, 231.1020, 217.0861, 201.0548, 189.0547, 177.0547, 159.0441, 145.0647, 131.0492, 117.0702, 103.0546, 95.0497, 77.0388, 67.0550 | C15H18O5 | meranzin hydrate | a |
| 24 | 1.92 | 305.1024 | 203.0342, 189.0550, 175.0393, 159.0443, 147.0443, 131.0494, 119.0493, 91.0549, 67.0549, 59.0500 | C16H16O6 | oxypeucedanin hydrate | (39) |
| 26 | 2.18 | 289.1073 | 261.1127, 248.1003, 243.1019, 228.0784, 213.0549, 189.0549, 185.0603, 173.0600, 159.0443, 155.0856, 145.0650, 131.0494, 127.0397, 117.0702, 103.0547, 91.0547, 81.0705, 69.0707 | C16H16O5 | columbianetin acetate | (40) |
| 28 | 3.57 | 179.0342 | 169.9784, 161.0600, 151.0388, 138.0549, 135.0443, 128.9511, 123.0441, 119.0494, 111.0443, 107.0495, 95.0495, 91.0548, 83.0496, 68.9979, 55.9353 | C9H6O4 | esculetin | (41) |
| 29 | 3.71 | 209.0448 | 194.0214, 191.0711, 181.0499, 166.0265, 163.0390, 153.0550, 149.0236, 138.0313, 131.0493, 121.0288, 110.0367, 92.0259, 82.0419, 68.9980, 55.0188 | C10H8O5 | fraxetin | a |
| 30 | 5.09 | 217.0499 | 217.0499, 202.0264, 189.0543, 178.0263, 174.0314, 161.0600, 146.0364, 131.0494, 118.0419, 115.0546, 105.0702, 91.0547, 74.0971, 55.0185 | C12H8O4 | bergapten | a |
| 32 | 5.41 | 247.0603 | 235.0233, 232.0368, 229.0856, 217.0134, 203.0692, 189.0185, 175.0392, 164.5641, 161.0235, 147.0442, 133.0288, 119.0860, 104.1075, 95.0132, 60.0816 | C13H10O5 | isopimpinellin | (42) |
| 34 | 7.06 | 231.1014 | 223.9490, 189.0543, 175.0393, 147.0443, 131.0491, 119.0491, 112.0470, 103.0547, 91.0548, 65.0392 | C14H14O3 | 7-demethylsuberosin | b |
| 37 | 7.91 | 287.0918 | 203.0343, 175.0392, 159.0444, 147.0443, 131.0494, 119.0497, 91.0548, 85.0655, 67.0549, 59.0501 | C16H14O5 | oxypeucedanin | (39) |
| 42 | 9.48 | 187.0393 | 163.9645, 159.0443, 143.0494, 135.9704, 131.0494, 118.9676, 115.0547, 103.0547, 95.0497, 81.0705, 55.9351 | C11H6O3 | isopsoralen | (43) |
| 44 | 9.72 | 193.0498 | 178.0258, 175.0384, 165.0545, 161.0229, 150.0310, 137.0595, 133.0283, 122.0362, 117.0335, 105.0335, 94.0416, 77.03912, 66.04706 | C10H8O4 | scopoletin | a |
| 47 | 10.85 | 245.1176 | 226.2699, 203.0706, 189.0549, 183.6220, 174.0308, 159.0443, 147.0438, 131.0494, 121.9895, 115.0547, 103.0547, 95.0498, 77.0392, 53.0394 | C15H16O3 | osthole | (44) |
| 49 | 11.31 | 271.0970 | 241.9205, 209.7384, 203.0342, 175.0392, 159.0443, 147.0443, 131.0494, 119.0495, 103.0548, 91.0548, 84.4042, 69.0707, 65.0393 | C16H14O4 | isoimperatorin | (39) |
| 51 | 16.93 | 163.0391 | 135.0442, 121.2155, 119.0495, 114.8570, 107.0496, 105.0451, 95.0498, 91.0548, 79.0548, 72.2852, 65.0394, 53.0394 | C14H14O3 | 7-hydroxycoumarin | a |
| 52 | 16.95 | 299.1644 | 256.9647, 231.1012, 203.0700, 189.0551, 175.0392, 163.0392, 159.0449, 137.1326, 119.0495, 107.0496, 95.0861, 91.0548, 81.0706, 69.0707 | C19H22O3 | auraptene | a |
| 53 | 17.6 | 339.1594 | 203.0342, 175.0392, 159.0444, 147.0443, 131.0494, 119.0495, 91.0548, 81.0706, 69.0707 | C21H22O4 | bergamottin | a |
| Organic acids | ||||||
| 7 | 0.6 | 225.0758 | 207.0651, 201.7923, 192.0414, 189.0544, 181.0854, 175.0389, 164.0465, 151.1117, 147.0440, 132.0207, 123.0441, 119.0493, 113.9640, 105.0701, 95.0496, 91.0547, 81.0703, 69.0340, 65.0391, 61.0403 | C11H12O5 | sinapic acid | (45) |
| 18 | 0.78 | 195.0655 | 186.0556, 180.0312, 177.0545, 163.0386, 154.0585, 149.0598, 145.0283, 135.0441, 125.0598, 117.0337, 111.0443, 107.0494, 95.0499, 91.0545, 89.0390, 79.0548, 65.0392, 57.0706 | C10H10O4 | ferulic acid | a |
| Other Compounds | ||||||
| 1 | 0.31 | 144.1019 | 128.0712, 116.1075, 102.0552, 84.0813, 81.0343, 70.0658, 58.0659, 55.0550 | C7H13NO2 | N,N-dimethyl-l-proline | a |
| 2 | 0.33 | 127.0393 | 122.4651, 109.0286, 99.0807, 97.0289, 88.7007, 85.0652, 81.0340, 79.0548, 71.0497, 67.0549, 57.0342, 53.0393 | C6H6O3 | 5-hydroxymethylfurfural | (46) |
| 4 | 0.42 | 237.1851 | 222.1535, 219.1746, 212.4210, 201.1639, 191.1796, 177.0538, 173.1326, 151.1119, 145.1013, 137.0964, 133.1014, 123.1170, 119.0859, 109.1016, 105.0704, 95.0861, 93.0705, 83.0496, 81.0706, 71.0499, 55.0551 | C15H24O2 | curdione | (47) |
| 23 | 1.7 | 134.0602 | 132.2048, 116.0498, 106.0654, 99.0060, 95.0495, 89.0391, 79.0548, 76.5491, 71.5103, 64.7083 | C8H7NO | 6-hydroxyindole | b |
| 33 | 6.06 | 153.1275 | 141.7384, 135.1169, 115.9385, 111.0806, 107.0859, 105.0705, 97.0652, 95.0860, 93.0704, 91.0546, 83.0860, 81.0705, 79.0549, 73.0656, 71.0499, 69.0706, 67.0549, 59.0500, 55.0551 | C10H16O | camphor | b |
| 36 | 7.67 | 471.2021 | 453.1918, 435.1810, 425.1965, 409.2016, 391.1884, 367.1910, 349.1818, 339.1961, 321.1861, 279.1387, 251.1058, 227.1071, 213.0914, 205.0499, 175.0756, 161.0600, 145.0651, 133.0651, 119.0860, 105.0704, 95.0134, 79.0549, 69.0707 | C26H30O8 | limonin | a |
| 46 | 10.62 | 175.0390 | 147.0443, 134.0603, 131.0496, 121.0291, 119.0495, 105.0335, 103.0549, 95.0499, 91.0549, 79.0549, 70.0659, 65.00394, 58.3657 | C10H6O3 | lawsone | (48) |
| 48 | 11 | 151.1121 | 133.1011, 131.0858, 123.1168, 121.1012, 113.9638, 109.0649, 107.0857, 105.0700, 98.5123, 97.0650, 95.0494, 93.0702, 91.0546, 87.0045, 83.0495, 81.0704, 79.0547, 71.0497, 69.0341, 67.0548, 65.0392, 57.0342, 55.0550 | C10H14O | perillene | b |
| 50 | 11.62 | 219.1745 | 201.1635, 191.1790, 177.127, 163.1115, 159.1168, 149.0959, 145.0959, 135.0803, 131.0856, 123.1168, 119.0855, 111.0805, 107.0856, 97.0651, 95.0858, 93.0702, 91.0546, 81.0704, 19.0547, 69.0705, 67.0549, 57.0704, 55.0550 | C5H22O | α-cyperone | (49) |
a
Confirmation in comparison with standard substances.
b
Refers to the database.