NO. Observed RT (min) Formula Observed m/z Mass error (ppm) Adducts Fragment (+/−) Identification Structure class Origin 1 1.63 C6 H12 O5 209.0670 1.3 [M+HCOO]− 89.0255 RAM Saccharide HQ 2 1.64 C5 H10 O5 195.0510 −0.2 [M+HCOO]− 89.0255 XLS Saccharide HQ 3 1.66 C23 H24 O11 475.1287 8.6 [M-H]− 89.0255, 179.0563, 290.0864, 341.1084 7,2′-Dihydroxy-3′,4′-dimethoxyisoflavone-7-O-β -D-glucoside Flavonoids HQ 4 1.67 C6 H12 O6 203.0522 −2.2 [M+Na]+ , [M+K]+ 127.0388 Inositol Others YYH 5 1.68 C10 H14 O3 205.0836 0.4 [M+Na]+ 127.0388 3,4,5-Trimethoxytoluene Others YYH 6 1.69 C27 H32 O12 593.1879 0.6 [M+HCOO]− 89.0255, 179.0563, 290.0864, 341.1084, 377.0850 Maohuoside A Flavonoids YYH 7 1.76 C21 H22 O7 431.1381 7.8 [M+HCOO]− 128.0362 Wanepimedoside_qt Flavonoids YYH 8 5.25 C16 H18 O9 353.0867 −3.1 [M−H]− 191.0556 Chlorogenic acid Phenylpropanoids (phenylpropionic acid) YYH C16 H18 O9 355.1041 4.9 [M+H]+ , [M+Na]+ 163.0387 Chlorogenic acid Phenylpropanoids (phenylpropionic acid) YYH 9 6.44 C19 H30 O8 431.189 −6.6 [M+HCOO]− 163.0409, 173.0463, 219.0629 Icariside B1 Terpenoids (monocyclic monoterpenoids) YYH 10 6.49 C19 H28 O10 461.1704 8.6 [M+HCOO]− 219.0629 Icariside D1 Terpenoids (monocyclic monoterpenoids) YYH 11 6.87 C26 H36 O12 539.2149 2.7 [M−H]− 317.0238, 479.0789, 491.1857 Icariside E1 Phenylpropanoids (phenylpropanols) YYH 12 6.92 C21 H20 O13 479.0807 −5.1 [M−H]− 316.0208 Isomyricitrin Flavonoids YYH 13 7.22 C32 H38 O15 697.1844 −8.8 [M+Cl]− 191.0563, 219.0647, 593.1515 Ikarisoside B Flavonoids YYH 14 7.86 C22 H22 O10 491.1183 −2.5 [M+HCOO]− 283.0601 Calycosin-7-glucoside Flavonoids HQ C22 H22 O10 447.1279 −1.4 [M+H]+ 285.0749 Calycosin-7-glucoside Flavonoids HQ 15 7.92 C21 H20 O12 463.0849 −7.1 [M−H]− 285.0396, 431.0962 Hyperoside Flavonoids YYH NX 16 8.00 C15 H10 O7 303.0520 6.8 [M+H]+ 287.0543 Robinetin Flavonoids YYH 17 8.17 C28 H34 O12 597.1798 9.1 [M+Cl]− 193.0869, 219.0659, 237.0750, 399.1276 Caohuoside D Flavonoids YYH 18 8.39 C27 H44 O7 525.3065 −0.8 [M+HCOO]− , [M+Cl]− 159.1057, 193.0869, 219.0659 Ecdysterone Steroids NX C27 H44 O7 481.3134 −5.5 [M+K]+ , [M+Na]+ 371.2244, 445.2923 Ecdysterone Steroids NX 19 8.42 C22 H32 O11 517.1889 −7.2 [M+HCOO]− , [M−H]− , [M+Cl]− 177.0907, 471.1833 Eugenol rutinoside Phenylpropanoids (Styrene) YYH 20 10.13 C29 H38 O15 625.2131 −1.1 [M−H]− 261.0762, 279.0868, 291.0852 Isomucronulatol-7,2′-di-O-glucosiole Flavonoids HQ 21 11.14 C16 H12 O5 283.0599 −4.7 [M−H]− 268.0381 Wogonin Flavonoids NX C16 H12 O5 285.0769 4.0 [M+H]+ 270.0515 Wogonin Flavonoids NX 22 12.07 C32 H38 O16 677.2074 −1.9 [M−H]− 353.0993, 514.1457, 515.1522, 557.1635 Hexandraside E Flavonoids YYH C32 H38 O16 679.2231 −0.3 [M+H]+ , [M+Na]+ 299.0524, 355.1186, 517.1787 Hexandraside E Flavonoids YYH 23 12.18 C43 H68 O14 853.4619 3.3 [M+HCOO]− , [M−H]− 96.9603, 451.3268 1-O-{(3β ,5ξ ,9ξ )-3-[(6-Methyl-β -D-glucopyranuronosyl)oxy]-28-oxoolean-12-en-28-yl}-β -D-glucopyranose Triterpenoids NX 24 12.41 C29 H50 O 453.3471 −4.8 [M+K]+ 343.3055 Sitosterol Steroids YYH NX 25 12.81 C38 H48 O20 825.2805 −0.8 [M+H]+ 299.0541, 355.1165, 517.1669, 663.2131 Diphylloside A Flavonoids YYH C38 H48 O20 869.2693 −3.2 [M+HCOO]− , [M−H]− , [M+Cl]− 146.9657, 353.1024, 514.1468, 661.2136, 807.2701 Diphylloside A Flavonoids YYH 26 13.06 C37 H46 O19 793.2564 0.4 [M−H]− , [M+Cl]− , [M+HCOO]− 285.0389, 431.0974, 631.2028 Epimedoside D Flavonoids YYH C37 H46 O19 795.2681 −3.2 [M+H]+ 287.0541, 299.0538, 355.1168, 517.1700 Epimedoside D Flavonoids YYH 27 13.29 C37 H44 O17 805.2492 −8.5 [M+HCOO]− 146.9657, 353.1024, 514.1468, 661.2136 Epimedoside Flavonoids YYH 28 13.32 C38 H48 O19 807.2703 −1.8 [M−H]− 146.9657, 353.1024, 514.1468, 661.2136 Diphylloside B Flavonoids YYH C38 H48 O19 831.2681 −0.2 [M+Na]+ 121.0269, 299.0541, 355.1166, 547.1760 Diphylloside B Flavonoids YYH 29 13.39 C32 H38 O15 707.2195 0.3 [M+HCOO]− , [M−H]− , [M+Cl]− 146.9657, 353.1024, 514.1468 Epimedoside A Flavonoids YYH C32 H38 O15 663.2275 −1.2 [M+H]+ , [M+Na]+ 121.0269, 299.0541, 355.1166, 547.1760 Epimedoside A Flavonoids YYH 30 13.41 C26 H30 O11 517.1680 −6.9 [M−H]− 219.0671, 327.1270, 383.1110 (2S,3S)-3,5-dihydroxy-2-(4-hydroxyphenyl)-8-(3-methyl-2-buten-1-yl)-4-oxo-3,4-dihydro-2H-chromen-7-yl β -D-glucopyranoside Flavonoids YYH 31 14.13 C22 H22 O9 475.1212 −7.0 [M+HCOO]− 267.0642, 353.0994 Ononin Flavonoids HQ C22 H22 O9 431.1325 −2.8 [M+H]+ 269.0797 Ononin Flavonoids HQ 32 15.81 C12 H22 O6 301.1069 6.9 [M+K]+ 167.0713 3-Hexenyl-β -glucopyranoside Saccharide YYH 33 16.05 C16 H12 O5 283.0604 −2.9 [M−H]− 148.0159, 268.0364 Calycosin Flavonoids HQ C16 H12 O5 285.0751 −2.3 [M+K]+ , [M+Na]+ 270.0508 Calycosin Flavonoids HQ 34 17.76 C39 H50 O19 883.2882 0.6 [M+HCOO]− , [M−H]− , [M+Cl]− 146.9654, 251.0307, 529.1697, 675.2292 Epimedin A Flavonoids YYH C39 H50 O19 839.2961 −0.9 [M+K]+ , [M+Na]+ 313.0700, 369.1326, 531.1852 Epimedin A Flavonoids YYH 35 18.46 C38 H48 O18 853.2774 0.2 [M+HCOO]− , [M−H]− , [M+Cl]− 146.9656, 366.1101, 551.1510, 645.2186 Epimedin B Flavonoids YYH C38 H48 O18 809.2855 −0.9 [M+H]+ , [M+K]+ 313.0698, 369.1322, 531.1849, 677.2419 Epimedin B Flavonoids YYH 36 18.88 C21 H20 O6 369.1322 −2.9 [M+H]+ 243.0640, 313.0699 Icaritin Flavonoids YYH 37 18.93 C39 H50 O19 867.2924 −0.5 [M+HCOO]− , [M−H]− , [M+Cl]− 146.9660, 366.1099, 551.1497, 659.2339 Epimedin C Flavonoids YYH C39 H50 O19 823.3014 −0.6 [M+H]+ , [M+K]+ 129.0545, 313.0699, 369.1322, 515.1931, 531.1852 Epimedin C Flavonoids YYH 38 18.99 C22 H24 O7 439.1143 −2.5 [M+K]+ , [M+Na]+ 239.0905, 301.0677 3,5,7-Trihydroxy-8-(3-methoxy-3-methylbutyl)-2-(4-methoxyphenyl)-4H-chromen-4-one Flavonoids YYH 39 19.17 C41 H52 O21 881.3114 4.6 [M+H]+ 85.0294, 135.0437, 243.0645, 313.0698, 369.1321 Hexandraside B Flavonoids YYH C41 H52 O21 879.2921 −0.8 [M−H]− 267.0300, 367.0621, 451.0672, 513.1100, 613.1210 Hexandraside B Flavonoids YYH 40 19.21 C27 H30 O11 575.1754 −2.9 [M+HCOO]− , [M−H]− 175.0025, 351.0861, 367.1169, 513.1748 Icariside I Flavonoids YYH C27 H30 O11 531.1850 −2.1 [M+H]+ , [M+Na]+ 85.0294, 135.0437, 243.0645, 313.0698, 369.1321 Icariside I Flavonoids YYH 41 19.22 C33 H40 O15 721.2337 −1.7 [M+HCOO]− , [M+Cl]− 175.0025, 281.0437, 367.1169, 451.0672, 513.1748 Icariin Flavonoids YYH C33 H40 O15 677.2433 −1.1 [M+H]+ , [M+K]+ 135.0437, 313.0698, 369.1321, 531.1851 Icariin Flavonoids YYH 42 19.23 C20 H24 O6 399.1215 2.7 [M+K]+ 135.0437 Lariciresinol Phenylpropanoids (lignans) HQ 43 19.26 C28 H24 O13 569.1236 −9.4 [M+H]+ 85.0294, 135.0437, 313.0698, 369.1321 8-Hydroxy-6-methyl-9,10-dioxo-9,10-dihydro-1-anthracenyl 6-O-(3,4,5-trihydroxybenzoyl)-β -D-glucopyranoside Anthraquinones NX 44 19.63 C25 H30 O8 481.1785 −9.9 [M+Na]+ 387.1427 Rubschisantherin Phenylpropanoids (lignans) NX 45 20.82 C36 H42 O17 747.2483 −1.5 [M+H]+ 299.0532, 355.1114 Korepimedoside A Flavonoids YYH C36 H42 O17 745.2332 −2.3 [M−H]− 121.0304, 352.0934, 367.1168, 499.1620, 583.1812 Korepimedoside A Flavonoids YYH 46 20.94 C41 H52 O21 879.2892 −4.1 [M−H]− 367.1156, 381.0964, 571.1715, 673.2076 Korepimedoside C Flavonoids YYH 47 21.01 C56 H88 O25 1199.5264 1.5 [M+K]+ 369.1320, 383.1110, 882.4549, 1059.5290 Achyranthoside D trimethyl ester Triterpenoids NX 48 21.08 C52 H84 O19 1013.5723 4.3 [M+H]+ 295.0576, 311.0891, 385.1281, 882.4549 Chikusetsusaponin V butyl ester Triterpenoids NX 49 21.09 C53 H82 O25 1117.5026 −4.1 [M−H]− 312.0607, 383.1097, 529.1652, 631.2021, 997.4956 Achyranthoside D Triterpenoids NX 50 21.11 C47 H74 O18 949.4763 −0.5 [M+Na]+ 295.0576, 311.0891, 882.4549 Chikusetsusaponin IV Triterpenoids NX C47 H74 O18 925.4757 −4.9 [M−H]− 139.1120, 171.1024, 211.1335, 229.1434, 367.1184 Chikusetsusaponin IV Triterpenoids NX 51 21.19 C48 H76 O19 955.4884 −2.5 [M−H]− , [M + HCOO]+ 352.0934, 367.1168, 631.2021, 793.4236 Ginsenoside Ro∗ Triterpenoids NX 52 21.24 C31 H36 O14 631.2021 −1.8 [M−H]− 121.0304, 352.0934, 367.1168, 583.1812 Ikarisoside F Flavonoids YYH C31 H36 O14 633.2146 −5.0 [M+H]+ 299.0526, 369.1327, 385.1281 Ikarisoside F Flavonoids YYH 53 21.28 C45 H60 O24 1023.3186 7.8 [M+K]+ 299.0526, 369.1327, 531.1847, 915.3315 Acuminatoside Flavonoids YYH 54 21.31 C27 H30 O11 529.1669 −8.8 [M−H]− 121.0304, 219.0656, 383.1102, 513.1729 Wushanicariin Flavonoids YYH 55 21.56 C35 H42 O16 763.2415 −5.2 [M + HCOO]− 367.1184, 381.0975, 555.1833, 645.2117 Sagittatoside C Flavonoids YYH C35 H42 O16 719.2591 6.3 [M+H]+ 313.0706, 369.1324, 383.1134, 385.1288, 531.1848 Sagittatoside C Flavonoids YYH 56 21.61 C46 H74 O14 873.4927 −5.0 [M+Na]+ 729.3908 Taibaienoside IV Triterpenoids NX 57 21.78 C20 H18 O6 353.1015 −4.3 [M−H]− 252.0419 8-Prenylkaempferol Flavonoids YYH C20 H18 O6 355.1173 −0.9 [M+H]+ 253.0480, 269.0803, 299.0550 8-Prenylkaempferol Flavonoids YYH 58 21.79 C16 H12 O4 267.0656 −2.4 [M−H]− 252.0419 Formononetin Flavonoids HQ C16 H12 O4 269.0803 −2.0 [M+H]+ , [M+Na]+ 118.0413, 253.0480 Formononetin Flavonoids HQ 59 22.23 C17 H16 O5 301.1080 3.3 [M+H]+ 167.0694 (6aR,11aR)-9,10-dimethoxy-6a,11a-dihydro-6H-benzofurano[3,2-c]chromen-3-ol Flavonoids HQ 60 22.33 C47 H72 O20 955.4528 −1.7 [M−H]− 382.1079, 645.2166, 835.4451, 925.4768 Achyranthoside C Triterpenoids NX C47 H72 O20 995.4167 −8.2 [M+K]+ 272.2571, 299.0537, 383.1132 Achyranthoside C Triterpenoids NX 61 23.03 C32 H38 O14 645.2190 0.2 [M−H]− , [M+Cl]− [M+HCOO]− 223.0282, 366.1100 Sagittatoside B Flavonoids YYH C32 H38 O14 647.2329 −0.7 [M+H]+ , [M+Na]+ 191.0005, 207.0315, 313.0700, 369.1321 Sagittatoside B Flavonoids YYH 62 23.54 C17 H20 O6 343.1163 3.2 [M+Na]+ 131.0491 1,2-Bis(4-hydroxy-3-methoxyphenyl)-1,3-propanediol Phenylpropanoids (phenylpropionic acid) YYH 63 23.89 C27 H30 O10 513.1762 −0.7 [M−H]− 146.9659, 217.0478, 351.0867, 366.1100 Icariside II Flavonoids YYH C27 H30 O10 515.1900 −2.2 [M+H]+ , [M+K]+ , [M+Na]+ 135.0434, 243.0638, 313.0698, 369.1322 Icariside II Flavonoids YYH 64 23.90 C21 H20 O6 369.1321 −3.2 [M+H]+ 135.0434, 243.0638, 313.0698 Anhydroicaritin Flavonoids YYH 65 24.53 C42 H66 O14 793.4358 −2.7 [M−H]− , [M+HCOO]− 209.0450, 367.1171 Zingibroside R1 Triterpenoids NX 66 24.58 C19 H30 O9 437.1603 4.3 [M+Cl]− 209.0450 Icariside B3 Terpenoids (Monocyclic monoterpenoids) YYH 67 25.14 C41 H64 O12 793.4391 1.5 [M+HCOO]− 469.3326, 487.3421 Acetylastragaloside I_qt Triterpenoids HQ 68 25.55 C20 H18 O5 337.1068 −4.0 [M−H]− 282.0493 Yinyanghuo D Flavonoids YYH C20 H18 O5 339.1227 0.0 [M+H]+ 283.0583 Yinyanghuo D Flavonoids YYH 69 25.84 C25 H26 O6 421.1666 2.2 [M−H]− 351.1189 Yinyanghuo B Flavonoids YYH C25 H26 O6 423.1829 6.5 [M+H]+ 349.1055 Yinyanghuo B Flavonoids YYH 70 26.15 C18 H32 O3 297.2423 −0.3 [M+H]+ 119.0855 13-Hydroxy-9,11-octadecadienoic acid Organic acids HQ 71 26.23 C41 H62 O15 793.4010 −0.8 [M−H]− 631.3795, 673.3972 Achyranthoside C_qt Triterpenoids NX 72 26.71 C45 H56 O23 1003.2895 5.1 [M+K]+ 313.0709 Korepimedoside B Flavonoids YYH 73 26.94 C27 H44 O7 481.3162 0.4 [M+H]+ 251.1605 Inokosterone Steroids NX 74 28.62 C16 H30 O2 277.2149 4.1 [M+Na]+ 223.1695 2,15-Hexadecanedione Others YYH 75 29.06 C25 H24 O6 421.1631 −3.6 [M+H]+ 367.1135 Yinyanghuo A Flavonoids YYH 76 29.63 C21 H20 O5 351.1228 −2.9 [M−H]− 293.0440 Artonin U Flavonoids YYH C21 H20 O5 353.1355 −8.2 [M+H]+ 297.0770 Artonin U Flavonoids YYH 77 29.76 C37 H60 O10 699.3821 −8.5 [M+Cl]− 277.2148, 353.2030 AstragalosideII_qt Triterpenoids HQ 78 30.20 C25 H26 O5 405.1700 −1.8 [M−H]− 295.0594 8,3′-diprenylapigenin Flavonoids YYH C25 H26 O5 407.1848 −1.2 [M+H]+ 149.0233, 295.0598, 351.1224 8,3′-diprenylapigenin Flavonoids YYH 79 32.96 C16 H22 O4 301.1402 −2.7 [M+Na]+ , [M+H]+ , [M+K]+ 149.0231 DBP Others NX 80 37.98 C30 H48 O3 455.3506 −5.3 [M−H]− , [M+HCOO]− 277.2164 Oleanolic acid Triterpenoids YYH NX 81 38.19 C18 H30 O2 279.2309 −3.4 [M+H]+ 95.0854 Linolenic acid Organic acids HQ 82 38.31 C22 H22 O11 507.1170 5.2 [M+HCOO]− , [M+Cl]− 223.0281 Rhamnocitrin-3-O-glucoside Flavonoids HQ C22 H22 O11 501.0842 9.7 [M+K]+ 191.0004, 207.0315, 281.0502 Rhamnocitrin-3-O-glucoside Flavonoids HQ 83 41.16 C18 H32 O2 281.2470 −1.9 [M+H]+ 95.0852 EIC Organic acids HQ 84 44.22 C21 H18 O11 447.0959 8.4 [M+H]+ 191.0001 Baicalin Flavonoids NX 85 46.85 C47 H78 O18 931.5353 9.8 [M+H]+ 115.0034, 147.0651, 553.3685 Asernestioside A Triterpenoids HQ 86 46.86 C27 H30 O16 655.1574 8.8 [M+HCOO]− 91.0223, 223.0270 Rutin Flavonoids YYH NX HQ C27 H30 O16 633.1487 9.6 [M+Na]+ , [M+H]+ , [M+K]+ 115.0034, 147.0651, 190.9999, 207.0309, 355.068 Rutin Flavonoids YYH NX HQ 87 48.41 C49 H80 O19 1011.4944 1.8 [M+K]+ 147.0656, 184.0726, 621.3171 Asernestioside B Triterpenoids HQ 88 49.83 C17 H14 O6 315.0886 7.2 [M+H]+ 207.0301, 281.0486 Jaranol Flavonoids HQ 89 50.62 C35 H60 O6 621.4377 0.8 [M+HCOO]− , [M+Cl]− 277.2198 Daucosterol Steroids YYH NX 90 52.31 C33 H42 O15 717.2087 −9.5 [M+K]+ 221.0835, 429.0876 Wanepimedoside A Flavonoids YYH 91 57.66 C20 H36 O2 309.2763 −8.2 [M+H]+ 89.0612 Linoelaidyl acetate Others YYH 92 57.75 C29 H38 O16 665.2115 9.5 [M+Na]+ 133.0854 5′-Hydroxyiso-muronulatol-2′,5′-di-O-glucoside Saccharide HQ 93 57.90 C29 H48 O 413.3796 4.3 [M+H]+ 95.0869 Stigmasterol Steroids NX
