Table 3 Identification information of the selected peaks

1

587.1347 [M+Na]⁺ (30), 565.1537 [M+H]⁺ (100)

565.1522 [M+H]⁺(59), 547.1419 [M+H–H₂O]⁺(100), 529.1325 [M+H–2H₂O]⁺(47), 511.1227 [M+H–3H₂O]⁺(28), 499.1208 [M+H–2H₂O–CH₂O]⁺(42), 493.1086 [M+H–4H₂O]⁺(13), 481.1106 [M+H–3H₂O–CH₂O]⁺(17), 469.1112 [M+H–2H₂O–C₂H₄O₂]⁺(31), 457.1105 [M+H–H₂O–C₃H₆O₃]⁺(33), 445.1118 [M+H–5H₂O–CH₂O]⁺(40)

Schaftoside

C₂₆H₂₈O₁₄

2

587.1347 [M+Na]⁺ (24), 565.1538 [M+H]⁺ (100)

565.1538 [M+H]⁺(100), 547.1428 [M+H–H₂O]⁺(71). 529.1332 [M+H–2H₂O]⁺(64), 511.1213[M+H–3H₂O]⁺ (56), 499.1217 [M+H–2H₂O–CH₂O]⁺(28), 481.1108 [M+H–3H₂O–CH₂O]⁺(17), 445.1111 [M+H–5H₂O–CH₂O]⁺(14), 427.1012 [M+H–H₂O–C₄H₈O₄]⁺(86), 409.0906 [M+H–2H₂O–C₄H₈O₄]⁺(38)

Isoschaftoside

C₂₆H₂₈O₁₄

3

387.1765 [M+Na]⁺ (100), 365.1949 [M+H]⁺ (70), 347.1843 [M+H–H₂O]⁺ (35)

347.1843 [M+H–H₂O]⁺ (100), 329.1744 [M+H–2H₂O]⁺(46), 311.1631 [M+H–3H₂O]⁺ (84), 299.1637 [M+H–2H₂O–CH₂O]⁺(64), 283.1685 [M+H–3H₂O–CO]⁺(37), 281.1524 [M+H–3H₂O–CH₂O]⁺(61), 265.1568 [M+H–4H₂O–CO]⁺(21), 253.1568 [M+H–3H₂O–CH₂O–CO]⁺(14)

Lasiodonin

C₂₀H₂₈O₆

4

629.1450 [M+Na]⁺ (2), 607.1645 [M+H]⁺ (100)

607.1634[M+H]⁺ (100), 589.1527 [M+H–H₂O]⁺(54), 571.1417 [M+H–2H₂O]⁺(35), 553.1315 [M+H–3H₂O]⁺(29), 541.1323 [M+H–2H₂O–CH₂O]⁺(14), 523.1222[M+H–3H₂O–CH₂O]⁺(13), 469.1110 [M+H–H₂O–C₄H₈O₄]⁺ (12), 427.1011 [M+H–2H₂O–C₂H₄O₂]⁺(45), 409.0902 [M+H–3H₂O–C₂H₄O₂]⁺ (22)

Glycoside

C₂₈H₃₀O₁₅

5

383.0724 [M+Na]⁺ (20), 343.0805 [M+H–H₂O]⁺ (11), 163.0385 [M+H–C₉H₁₀O₅]⁺ (100)

163.0385 [M+H–C₉H₁₀O₅]⁺(100), 145.0287 [M+H–C₉H₁₂O₆]⁺(6)^a

Rosmarinic acid

C₁₈H₁₆O₈

6

387.1765 [M+Na]⁺ (100), 365.1950 [M+H]⁺ (49), 347.1841 [M+H–H₂O]⁺ (22)

347.1838 [M+H–H₂O]⁺(16), 329.1739 [M+H–2H₂O]⁺(30), 311.1631 [M+H–3H₂O]⁺(100), 299.1637 [M+H–2H₂O–CH₂O]⁺(23), 283.1680 [M+H–3H₂O–CO]⁺(23), 281.1528 [M+H–3H₂O–CH₂O]⁺(30)

C-20 oxygenated ent-kaurane diterpenoids

C₂₀H₂₈O₆

7

387.1771 [M+Na]⁺ (100), 365.1942 [M+H]⁺ (7), 347.1847 [M+H–H₂O]⁺ (73)

347.1834 [M+H–H₂O]⁺(14), 329.1740 [M+H–2H₂O]⁺(22), 311.1630 [M+H–3H₂O]⁺ (20), 301.1789 [M+H–2H₂O–CO]⁺(100), 299.1630 [M+H–2H₂O–CH₂O]⁺(23), 283.1685 [M+H–3H₂O–CO]⁺(68), 281.1528 [M+H–3H₂O–CH₂O]⁺(59)^a

Oridonin

C₂₀H₂₈O₆

8

747.3332 [2 M+Na]⁺ (100), 385.1610 [M+Na]⁺ (85), 363.1794 [M+H]⁺ (44)

363.1788 [M+H]⁺(18), 345.1686 [M+H–H₂O]⁺(32), 327.1577 [M+H–2H₂O]⁺(58), 309.1490 [M+H–3H₂O]⁺(25), 299.1627 [M+H–2H₂O–CO]⁺(73), 281.1529 [M+H–2H₂O–COOH]⁺(100), 253.1569 [M+H–2H₂O–COOH–CO]⁺(20)^a

Ponicidin

C₂₀H₂₆O₆

9

385.1613 [M+Na]⁺ (100), 367.1510 [M–H₂O + Na]⁺ (11), 345.1688 [M+H–H₂O]⁺ (52)

345.1681 [M+H–H₂O]⁺(100), 327.1576 [M+H–2H₂O]⁺(13), 309.1474 [M+H–3H₂O]⁺(35), 299.1620 [M+H–2H₂O–CO]⁺(23), 281.1530 [M+H–2H₂O–COOH]⁺(67), 271.1678 [M+H–2H₂O–2CO]⁺(15), 253.1559 [M+H–2H₂O–COOH–CO]⁺(12)

ent-kaurane diterpenoids

C₂₀H₂₆O₆

10

429.1878 [M+Na]⁺ (100), 407.2065 [M+H]⁺ (23), 389.1957 [M+H–H₂O]⁺ (3)

389.1956 [M+H–H₂O]⁺(18), 329.1725 [M+H–H₂O–AcOH]⁺(36), 311.1162 [M+H–2H₂O–AcOH]⁺(13), 299.1629 [M+H–H₂O–AcOH–CH₂O]⁺ (100), 281.1529 [M+H–2H₂O–AcOH–CH₂O]⁺ (30),253.1572 [M+H–2H₂O–AcOH–CH₂O–CO]⁺(45)

Lasiokaurin

C₂₂H₃₀O₇

11

429.1875 [M+Na]⁺ (100), 407.2058 [M+H]⁺ (3), 389.1956 [M+H–H₂O]⁺ (42)

371.8261 [M+H–2H₂O]⁺(14), 343.1874 [M+H–2H₂O–CO]⁺ (11), 329.1751 [M+H–H₂O–AcOH]⁺(85), 311.1630 [M+H–2H₂O–AcOH]⁺(64), 299.1615 M+H–H₂O–AcOH–CH₂O]⁺(72), 283.1686 [M+H–2H₂O–AcOH–CO]⁺(89), 281.1526 [M+H–2H₂O–AcOH–CH₂O]⁺(100), 265.1580 [M+H–3H₂O–AcOH–CO]⁺(46), 253.1576 [M+H–2H₂O–AcOH–CH₂O–CO]⁺ (61)

C-20 oxygenated ent-kaurane diterpenoids

C₂₂H₃₀O₇

12

471.1983 [M+Na]⁺ (100), 449.2159 [M+H]⁺ (47)

389.1948 [M+H–AcOH]⁺(12), 371.1841 [M+H–H₂O–AcOH]⁺(21), 329.1743 [M+H–2AcOH]⁺(22), 311.1633 [M+H–H₂O–2AcOH]⁺(100), 293.1531 [M+H–2H₂O–2AcOH]⁺(15), 283.1688 [M+H–H₂O–2AcOH–CO]⁺(24), 281.1527 [M+H–H₂O–2AcOH–CH₂O]⁺(66)

Shikokianin

C₂₄H₃₂O₈

13

353.1714 [M+Na]⁺ (100), 313.1794 [M+H–H₂O]⁺ (14)

295.1669 [M+H–2H₂O]⁺ (4), 277.1590 [M+H–3H₂O]⁺(23), 237.1273 [M+H–3H₂O–C₃H₄]⁺(100), 209.0948 [M+H–3H₂O–C₅H₈] (17)

Abietane diterpenoids

C₂₀H₂₆O₄

14

353.1714 [M+Na]⁺ (38), 331.1889 [M+H]⁺ (4), 313.1798 [M+H–H₂O]⁺ (100)

253.1219 [M+H–2H₂O–C₃H₆]⁺(9), 227.1056 [M+H–2H₂O–C₅H₈]⁺(100), 212.0822[M+H–2H₂O–C₅H₈–CH₃]⁺(14), 209.0955 [M+H–3H₂O–C₅H₈]⁺(16), 199.1114 M+H–2H₂O–C₅H₈–CO]⁺(21)

Abietane diterpenoids

C₂₀H₂₆O₄

15

413.1925 [M+Na]⁺ (100), 391.2103 [M+H]⁺ (16), 373.1998 [M+H–H₂O]⁺ (10)

391.2000 [M+H]⁺(6), 373.2000 [M+H–H₂O]⁺(50), 313.1781 [M+H–H₂O–AcOH]⁺(66), 295.1673 [M+H–2H₂O–AcOH]⁺(50), 283.1678 [M+H–H₂O–AcOH–CH₂O]⁺(100), 267.1730 [M+H–2H₂O–AcOH–CO]⁺(57), 265.1576 [M+H–2H₂O–AcOH–CH₂O]⁺(22)

C-20 oxygenated ent-kaurane diterpenoids

C₂₂H₃₀O₆

16

417.2266 [M+H]⁺ (100), 357.2056 [M+H–AcOH]⁺ (91)

315.1940 [M+H–AcOH–CH₂=CO]⁺(100), 297.1841 [M+H–2AcOH]⁺(75), 279.1726 [M+H–H₂O–2AcOH]⁺(26), 255.1369 [M+H–2AcOH–C₃H₆]⁺(48), 229.1214 [M+H–2AcOH–C₅H₈]⁺(26)

Abietane diterpenoids

C₂₄H₃₂O₆

17

375.2161 [M+H]⁺ (100), 315.1947 [M+H–AcOH]⁺ (27)

315.1946 [M+H–AcOH]⁺(87), 297.1846 [M+H–H₂O–AcOH]⁺(68), 287.1998 [M+H–AcOH–CO]⁺(22), 279.1723 [M+H–2H₂O–AcOH]⁺(13), 273.1468 [M+H–AcOH–C₃H₆](16), 255.1369 [M+H–3H₂O–AcOH]⁺(19), 229.1220 [M+H–H₂O–AcOH–C₅H₈]⁺(100), 205.1215 [M+H–AcOH–C₇H₁₀O]⁺(48)

Abietane diterpenoids

C₂₂H₃₀O₅

18

513.2076 [M+Na]⁺ (100), 508.2521 [M+NH4]⁺ (4), 491.2253 [M+H]⁺ (3)

431.2025 [M+H–AcOH]⁺(8), 389.1976 [M+H–AcOH–CH₂=CO]⁺(22), 371.1830 [M+H–2AcOH]⁺(49), 329.1740 [M+H–2AcOH–CH₂=CO]⁺(100), 311.1634 [M+H–H₂O–2AcOH–CH₂=CO]⁺(38), 283.1708 [M+H–H₂O–2AcOH–CH₂=CO–CO]⁺(29)^b

Shikokianidin

C₂₆H₃₄O₉

19

411.1765 [M+Na]⁺ (17), 389.1946 [M+H]⁺ (100)

371.1847 [M+H–H₂O]⁺(15), 311.1633[M+H–H₂O–AcOH]⁺ (38), 269.1164 [M+H–H₂O–AcOH–C₃H₆]⁺ (34), 243.1015 [M+H–H₂O–AcOH–C₅H₈]⁺(100), 225.0903[M+H–2H₂O–AcOH–C₅H₈]⁺ (11)

Abietane diterpenoids

C₂₂H₂₈O₆

20

455.2022 [M+Na]⁺ (13), 433.2203 [M+H]⁺ (100)

331.1889 [M+H–AcOH–CH₂=CO]⁺(19), 313.1785 [M+H–2AcOH]⁺(100), 271.1332 [M+H–2AcOH–C₃H₆]⁺(13), 245.1164 [M+H–2AcOH–C₅H₈]⁺(19), 219.1012[M+H–2AcOH–C₇H₁₀]⁺(37), 205.0855[M+H–2AcOH–C₈H₁₂]⁺ (37)

Abietane diterpenoids

C₂₄H₃₂O₇

21

353.1716 [M+Na]⁺ (22), 331.1894 [M+H]⁺ (100)

313.1793 [M+H–H₂O]⁺(100), 257.1168 [M+H–H₂O–C₄H₈]⁺(11), 243.1014 [M+H–H₂O–C₅H₁₀]⁺(74)

Abietane diterpenoids

C₂₀H₂₆O₄

22

395.1816 [M+Na]⁺ (26), 373.2015 [M+H]⁺ (100), 355.1896 [M+H–H₂O]⁺ (10)

355.1892 [M+H–H₂O]⁺ (9), 337.1791 [M+H–2H₂O]⁺(14), 295.1684 [M+H–2H₂O–CH₂=CO]⁺(42), 277.1578 [M+H–2H₂O–AcOH]⁺(26), 253.1219 [M+H–2H₂O–CH₂=CO–C₃H₆]⁺(87), 239.1059 [M+H–2H₂O–CH₂=CO–C₄H₈]⁺(34), 227.1066 [M+H–2H₂O–CH₂=CO–C₅H₈]⁺(100), 211.1112 [M+H–2H₂O–CH₂=CO–C₄H₈–CO]⁺(24), 209.0956 [M+H–2H₂O–AcOH–C₅H₈]⁺(50)

Abietane diterpenoids

C₂₂H₂₈O₅

23

381.2025 [M+Na]⁺ (100), 359.2210 [M+H]⁺ (20)

299.1999 [M+H–AcOH]⁺(100), 271.1680 [M+H–AcOH–C₂H₄]⁺(25)

Diterpenoids

C₂₂H₃₀O₄

24

435.1745 [M + 2Na]⁺ (7), 413.1926 [M+Na]⁺ (100), 373.2005 [M+H–H₂O]⁺ (8), 313.1793 [M+H–H₂O–AcOH]⁺ (10)

355.1857 [M+H–2H₂O]⁺(7), 313.1798 [M+H–H₂O–AcOH]⁺(93), 295.1678 [M+H–2H₂O–AcOH]⁺(25), 285.1827 [M+H–H₂O–CO]⁺(9), 280.1427 [M+H–2H₂O–AcOH–CH₃]⁺(13), 271.1673 [M+H–H₂O–AcOH–CH₂=CO]⁺(61), 253.1232 [M+H–2H₂O–AcOH–C₃H₆]⁺(44), 243.1749 (13), 227.1038 [M+H–2H₂O–AcOH–C₅H₈]⁺(17)^a

Abietane diterpenoids

C₂₂H₃₀O₆

25

647.3333 [2 M+Na]⁺ (100), 335.1610 [M+Na]⁺ (94), 313.1794 [M+H]⁺ (17)

295.1685 [M+H–H₂O]⁺(13), 277.1583 [M+H–2H₂O]⁺(43), 237.1271 [M+H–2H₂O–C₃H₄]⁺(100), 227.1062[M+H–H₂O–C₅H₈]⁺ (25), 209.0953 [M+H–2H₂O–C₅H₈]⁺(15)

Abietane diterpenoids

C₂₀H₂₄O₃

26

337.1765 [M+Na]⁺ (40), 315.1950 [M+H]⁺ (2), 297.1856 [M+H–H₂O]⁺ (100)

297.1843 [M+H–H₂O]⁺(17), 279.1736 [M+H–2H₂O]⁺ (10), 227.1061 [M+H–H₂O–C₅H₁₀]⁺(100), 212.0830 [M+H–H₂O–C₅H₁₀–CH₃]⁺(18), 199.1117 [M+H–H₂O–C₅H₁₀–CO]⁺(19)

Diterpenoids

C₂₀H₂₆O₃

27

455.2033 [M+Na]⁺ (100), 450.2478 [M+NH4]⁺ (8)

373.1997 [M+H–AcOH]⁺ (8), 313.1788 [M+H–2AcOH]⁺(100), 295.1682 [M+H–H₂O–2AcOH]⁺(31), 253.1201 [M+H–H₂O–2AcOH–C₃H₆]⁺ (4)^b

Abietane diterpenoids

C₂₄H₃₂O₇