Table 2 Structural information of compounds characterized in the Leonuri Herba by negative-UHPLC-QTOF-MS/MS
|  | tR (min) | MF | Product ion | Mass | Mass (Tgt) | Diff (ppm) | (−)-ESI–MS/MS Fragment Ions (m/z) | Identification [Reference] |
|---|---|---|---|---|---|---|---|---|
1 | 2.630 | C9H11NO2 | [M-H]− | 165.0797 | 165.0790 | 4.50 | 57.0355 | Phenylalanine [6] |
2 | 3.838 | C11H12N2O2 | [M+COOH]− | 204.0908 | 204.0899 | 4.43 |  | Tryptophan [6] |
3 | 4.14 | C7H6O3 | [M-H]− | 138.0324 | 138.0317 | 5.32 |  | Salicylic acid [9] |
4 | 4.548 | C9H10O3 | [M+COOH]− | 166.0640 | 166.0630 | 5.97 | 150.0330, 72.9938 | Ethyl 4-hydroxybenzoate [10] |
5 | 4.764 | C14H20O9 | [M-H]− | 332.1118 | 332.1107 | 3.25 | 316.0867, 197.0473, 61.9892 | 2,6-Dimethoxy-4-hydroxyphenol-1-O-β-d-glucopyranoside [11] |
6 | 4.989 | C27H42O17 | [M-H]− | 638.2439 | 638.2422 | 2.60 | 578.2197, 461.2364, 255.2342, 89.025 | Leonoside F [12] |
7 | 5.223 | C7H6O2 | [M-H]− | 122.0376 | 122.0368 | 6.49 | 167.0335, 108.0221 | Benzoic acid [13] |
8 | 5.340 | C8H8O3 | [M+COOH]− | 152.0483 | 152.0473 | 6.41 | 123.0096 | Vanillin [14] |
9 | 5.341 | C9H10O5 | [M-H]− | 198.0538 | 198.0528 | 5.02 | 123.0096 | Syringic acid [13] |
10 | 5.660 | C11H14O5 | [M+COOH]− | 226.0859 | 226.0841 | 7.82 | 256.0593, 123.0099, 59.0140 | 3-Hydroxyl-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone [1] |
11 | 5.865 | C19H32O8 | [M+COOH]− | 388.2109 | 388.2097 | 3.10 | 401.1477, 197.0454, 61.9893 | Staphylionoside E [12] |
12 | 6.533 | C8H8O4 | [M-H]− | 168.0430 | 168.0423 | 4.45 | 108.0221 | Vanillic acid [14] |
13 | 6.542 | C7H6O2 | [M-H]− | 122.0376 | 122.0368 | 6.51 | 167.0335, 108.0221 | 4-Hydroxybenzaldehyde [11] |
14 | 6.563 | C19H30O8 | [M-H]− | 386.1948 | 386.1941 | 1.91 | 189.1284, 85.0309 | Citroside A [12] |
15 | 6.617 | C14H21N3O5 | [M-H]− | 311.1497 | 311.1481 | 4.96 | 280.0956, 95.0148 | Leonurine [15] |
16 | 6.646 | C27H30O16 | [M-H]− | 610.1556 | 610.1534 | 3.69 | 447.0039, 300.0293, 151.0054 | Quercetin-3-O-robinoside [16] |
17 | 6.746 | C13H20O3 | [M+COOH]− | 224.1426 | 224.1412 | 5.96 |  | (2S,5S)-2-Hydroxy-2,6,10,10-tetramethyl-1-oxaspiro-[4.5]dex-6-en-8-one [1] |
18 | 6.884 | C21H20O11 | [M+COOH]− | 448.1027 | 448.1006 | 4.73 | 284.0341, 61.9894 | Kaempferol-3-O-β-d-glucopyranoside [16] |
19 | 6.968 | C27H30O16 | [M-H]− | 610.1558 | 610.1534 | 3.94 | 447.1139, 300.0294, 151.0055 | Rutin [13] |
20 | 6.997 | C10H10O4 | [M-H]− | 194.0591 | 194.0579 | 5.97 | 134.0387, 58.0307 | Trans-ferulic acid [11] |
21 | 7.173 | C21H20O12 | [M-H]− | 464.0978 | 464.0955 | 4.93 | 300.0293, 61.9891 | Hyperoside [16] |
22 | 7.306 | C21H20O12 | [M-H]− | 464.0976 | 464.0955 | 4.67 | 300.0293, 151.0048, 61.9891 | Quercetin-3-O-β-d-glucopyranoside [16] |
23 | 7.335 | C27H30O15 | [M-H]− | 594.1607 | 594.1585 | 3.76 | 463.0907, 284.0344, 61.9891 | Kaempferol-3-neohesperidoside [16] |
24 | 7.494 | C34H44O19 | [M-H]− | 756.2495 | 756.2477 | 2.37 | 593.2095, 461.1679, 357.1262, 223.0608, 161.0254 | Lavandulifolioside [12] |
25 | 7.507 | C27H30O15 | [M-H]− | 594.1607 | 594.1585 | 3.79 | 387.1094, 284.0344, 61.9891 | Kaempferol-3-O-β-robinobinoside [13] |
26 | 7.832 | C27H30O15 | [M-H]− | 594.1606 | 594.1585 | 3.56 | 387.1094, 284.0344, 61.9891 | Kaempferol-3-O-rutinoside [11] |
27 | 8.083 | C21H20O11 | [M-H]− | 448.1026 | 448.1006 | 4.66 | 284.0341, 61.9894 | Kaempferol-3-O-β-d-galactopyranoside [16] |
28 | 8.493 | C15H20O3 | [M-H]− | 248.1427 | 248.1412 | 6.00 |  | Arteannuin B [17] |
29 | 8.903 | C36H38O20 | [M-H]− | 790.1983 | 790.1956 | 3.42 | 609.1483, 473.1289, 379.1785, 127.0408 | 2'''-syringylrutin [18] |
30 | 9.635 | C12H20O5 | [M-H]− | 244.1327 | 244.1311 | 6.47 | 207.1044, 71.0506 | (E)-4-Hydroxy-dodec-2-enedioic acid [1] |
31 | 9.693 | C21H32O8 | [M+COOH]− | 412.2116 | 412.2097 | 4.67 | 327.1466, 61.9893 | 7α(H)-Eudesmane-4,11(12)-diene-3-one-2β-hydroxy-13-β-D-glucopyranoside [12] |
32 | 10.16 | C17H30O3 | [M+COOH]− | 282.2207 | 282.2195 | 4.37 |  | (-)-(1S*,2S*,3R*)-3-Ethoxycupar-5-ene-1,2-diol [1] |
33 | 10.191 | C15H10O7 | [M-H]− | 302.0441 | 302.0427 | 4.93 | 151.0046 | quercetin [19] |
34 | 10.308 | C30H26O13 | [M-H]− | 594.1395 | 594.1373 | 3.66 | 447.0934, 285.0418, 145.0305 | tiliroside [16] |
35 | 10.542 | C30H26O13 | [M-H]− | 594.1396 | 594.1373 | 3.84 | 447.0630, 285.0417, 145.0304 | Kaempferol-3-O-( 6''-O-cis-p-coumaroyl) -β-d-glucopyranoside [11, 18] |
36 | 11.216 | C15H10O6 | [M-H]− | 286.0493 | 286.0477 | 5.49 | 65.0044 | Kaempferol [20] |
37 | 11.333 | C10H18O2 | [M+COOH]− | 170.1319 | 170.1307 | 6.98 | 153.1285, 68.9956 | 2,6-dimethyl-2E,7-octadiene-1,6-diol [16] |
38 | 11.45 | C15H10O5 | [M+COOCH3]− | 270.0545 | 270.0528 | 6.24 |  | Apigenin [11] |
39 | 12.036 | C13H16O | [M+COOCH3]− | 188.1192 | 188.1201 | -5.09 | 185.9999, 75.0097 | 2-(1-Oxopentyl)-benzoic acid methyl ester [16] |
40 | 12.241 | C15H30O2 | [M+COOH]− | 242.2261 | 242.2246 | 6.09 |  | Methyl tetradecanoate [16] |
41 | 12.563 | C16H12O5 | [M-H]− | 284.0698 | 284.0685 | 4.58 | 268.0395, 117.0356 | Wogonin [20] |
42 | 13.244 | C16H12O5 | [M-H]− | 284.0700 | 284.0685 | 5.51 | 268.0395, 117.0356 | 4',5-Dihydroxy-7-methoxyflavone [18] |
43 | 13.444 | C15H10O4 | [M+COOH]− | 254.0593 | 254.0579 | 5.61 | 284.0342, 133.0305 | Daidzein [18] |
44 | 13.978 | C21H32O6 | [M+COOH]− | 380.2201 | 380.2199 | 0.50 | 263.1668, 61.9892 | (-)-(5S,7R,8R,9R,10S,13S,15R)-7-hydroxy-15-methoxy-9,13;15,16-diepoxylabdan-6,16-dione [1] |
45 | 15.502 | C15H24O4 | [M-H]− | 268.1687 | 268.1675 | 4.72 |  | 7α(H),10α-eudesm-4-en-3one-2β,11,12-triol [14] |
46 | 18.29 | C20H28O4 | [M+COOCH3]− | 332.1981 | 332.1988 | -2.01 |  | (-)-3α-Acetoxy-6β-hydroxy-15,16-dinorlabd-8(9)-ene-13-yne-7-one [18] |
47 | 19.769 | C30H48O4 | [M-H]− | 472.3571 | 472.3553 | 3.80 | 409.3488, 171.1035, 61.9893 | Messagenic acid [21] |
48 | 19.881 | C29H46O2 | [M+COOH]− | 426.3516 | 426.3498 | 4.25 | 409.3488, 171.1035, 61.9893 | (24S)-Stigmast-4,28-diene-24-ol-3-one [21] |
49 | 20.276 | C20H40O | [M+COOCH3]− | 296.3097 | 296.3079 | 6.14 |  | Phytol [21] |