No. t R Name Classification Formula Theoretical mass (Da) Measured mass (Da) Error (ppm) Precursor ions Main MS/MS fragment ions Source Ref. 1 0.99 Citric acid☆ Organic acids C6 H8 O7 191.0197 191.0201 2.1 [M − H]− 129.0196, 111.009 ZSS, ASR, ARP [16 ] 2 1.37 Geniposidic acid Iridoid glycoside C16 H22 O10 373.1140 373.1143 0.8 [M − H]− 211.0605, 193.0497, 167.0703, 149.0595, 123.0437 RRP [10 ] 3 1.85 Decaffeoylacteoside☆ Phenylethanoid glycosides C20 H30 O12 461.1664 461.1669 1.1 [M − H]− 375.1314, 315.1314, 297.0980, 135.0452 RRP [17 ] 4 1.95 Mussaenosidic acid☆ Iridoid glycoside C16 H24 O10 375.1297 375.1299 0.5 [M − H]− 213.0778, 169.0873, 151.0766 RRP [18 ] 5 2.05 5-Caffeoylquinic acid☆ Organic acids C16 H18 O9 353.0878 353.0878 0.0 [M − H]− 191.0563, 179.0352, 161.0245, 155.0350, 111.0088 ASR [19 ] 6 2.34 3-Caffeoylquinic amide Organic acids C16 H19 NO8 354.1183 354.1178 −1.5 [M + H]+ 192.0650, 174.0545, 146.0597 [10 ] 7 2.82 Ferulic acid hexoside☆ Organic acids C16 H20 O9 355.1035 355.1042 2.0 [M − H]− 193.0509, 149.0610, 178.0271, 134.0375 ASR [20 ] 8 3.01 3-Caffeoylquinic amide isomer Organic acids C16 H19 NO8 354.1183 354.1177 −1.8 [M + H]+ 192.0650, 174.0545, 146.0597 [10 ] 9 3.03 Hydroxybenzoic acid☆ Organic acids C7 H6 O3 137.0244 137.0244 0.0 [M − H]− 136.0170, 108.0215 ZSS [16 ] 10 3.21 p-Hydroxybenzyl malonic acid☆ Organic acids C10 H10 O5 209.0455 209.0456 0.5 [M − H]− 419.0982, 165.0562, 121.0662 GRP [21 ] 11 3.34 Sanjoinine IB☆ Alkaloids C19 H21 NO4 328.1543 328.1534 −2.7 [M + H]+ 265.0855, 251.0665, 237.0902, 223.0712 ZSS [22 ] 12 3.53 Magnocurarine☆ Alkaloids C19 H24 NO3 + 314.1751 314.1748 −1.0 [M]+ 269.1179, 237.0897, 209.0947, 175.0744, 107.0491 ZSS [22 ] 13 3.69 Chlorogenic acid Organic acids C16 H18 O9 353.0878 353.0885 2.0 [M − H]− 191.0563, 127.0404 ASR [20 ] 14 4.26 Sibiricose A5 Sucrose esters C22 H30 O14 517.1563 517.1568 1.0 [M − H]− 341.1097, 193.0512, 175.0404, 160.0169 PRP [23 ] 15 4.55 4-Caffeoylquinic acid Organic acids C16 H18 O9 353.0878 353.0883 1.4 [M − H]− 191.0562, 179.0350, 173.0457, 161.0243, 111.0453, 93.0346 ASR [10 ] 16 4.74 Vanillic acid Organic acids C8 H8 O4 167.0350 167.0351 0.6 [M − H]− 123.0452 ASR [24 ] 17 5.32 Sibiricose A6☆ Sucrose esters C23 H32 O15 547.1668 547.1678 1.8 [M − H]− 367.1034, 341.1094, 223.0616, 205.0508, 190.0274 PRP [25 , 26 ] 18 5.54 Sanjoinine K Alkaloids C17 H19 NO3 286.1438 286.1431 −2.3 [M + H]+ 269.1154, 237.0905, 175.0751, 107.0492 ZSS [16 ] 19 5.90 Ferulic acid hexoside isomer☆ Organic acids C16 H20 O9 355.1035 355.1041 1.7 [M − H]− 193.0512, 149.0610, 178.0273, 134.0376 ASR [20 ] 20 5.99 Darendoside B☆ Phenylethanoid glycosides C21 H32 O12 475.1821 475.1830 1.9 [M − H]− 329.1228, 311.1144, 161.0459, 113.0247 RRP [27 ] 21 6.18 Liquiritigenin-7,4′-di-O-glucoside Flavonoids C27 H32 O14 579.1719 579.1733 2.4 [M − H]− 417.1212, 255.0669, 135.0086 GRP [28 ] 22 6.38 Caffeic acid Organic acids C9 H8 O4 179.0350 179.0352 1.1 [M − H]− 151.0459, 135.0499 ASR [10 ] 23 7.47 Magnoflorine Alkaloids C20 H23 NO4 + 342.1700 342.1689 −3.2 [M + H]+ 297.1113, 282.0876, 265.0848 ZSS [16 ] 24 9.46 Feruoylquinic acid☆ Organic acids C17 H20 O9 367.1035 367.1043 2.2 [M − H]− 191.0563, 173.0461, 111.0453, 93.035 ASR [20 ] 25 9.82 Lotusine☆ Alkaloids C19 H24 NO3 + 314.1751 314.1752 0.3 [M]+ 269.1162, 237.0912, 209.0949, 107.0485 ZSS [22 ] 26 9.94 Feruoylquinic acid isomer☆ Organic acids C17 H20 O9 367.1035 367.1034 −0.3 [M − H]− 191.0564, 173.0457, 111.0450, 93.0347 ASR [20 ] 27 10.04 Sibiricose A1 Sucrose esters C23 H32 O15 547.1668 547.1676 1.5 [M − H]− 367.1040, 223.016, 190.0275 PRP [10 , 23 ] 28 10.23 Vicenin II Flavonoids C27 H30 O15 593.1512 593.1522 1.7 [M − H]− 503.1200, 473.1098, 383.0780, 353.0674, 325.0931, GRP, ZSS [16 , 22 ] 29 10.43 Ferulic acid isomer☆ Organic acids C10 H10 O4 193.0506 193.0506 0.0 [M − H]− 149.0243, 121.0298 30 10.81 Lancerin Xanthones C19 H18 O10 405.0827 405.0833 1.5 [M − H]− 285.0410, 257.0456 PRP [23 ] 31 11.30 Rehmaionoside A/B Ionones C19 H34 O8 435.2239 435.2246 1.6 [M + COOH]− 389.2223, 179.0591 RRP [10 , 17 ] 32 11.49 Ferulic acid Organic acids C10 H10 O4 193.0506 193.0507 0.5 [M − H]− 178.0272, 149.0609, 134.0369 ASR [20 ] 33 11.97 Lancerin isomer☆ Xanthones C19 H18 O10 405.0827 405.0833 1.5 [M − H]− 285.0413, 315.0518, 257.0458 PRP [10 ] 34 12.14 Caaverine☆ Alkaloids C17 H17 NO2 268.1332 268.1321 −4.1 [M − H]− 251.1014, 219.0829, 209.0933, 191.0862 ZSS [22 ] 35 12.45 Sibiricaxanthone A/B Xanthones C24 H26 O14 537.1250 537.1258 1.5 [M − H]− 405.0832, 387.0730, 327.0524, 315.0514, 297.0412, 285.0410, 267.0303, 243.0302 PRP [29 ] 36 12.45 Echinacoside Phenylethanoid glycosides C35 H46 O20 785.2510 785.2520 1.3 [M − H]− 623.2201, 461.1663, 161.0245 RRP [30 ] 37 12.74 Schaftoside Flavonoids C26 H28 O14 563.1406 563.1408 0.4 [M − H]− 353.0674, 443.0992, 473.1098, 383.0778, 503.1197, 425.0877, 413.0882 GRP [31 ] 38 13.12 Sibiricose A2 Sucrose esters C24 H34 O15 561.1825 561.1832 1.2 [M − H]− 607.1888, 323.0991, 237.0771 PRP [10 ] 39 13.41 Rehmaionoside A/B Ionones C19 H34 O8 435.2239 435.2239 0.0 [M + COOH]− 389.2223, 179.0572 RRP [29 ] 40 13.79 Liquiritin Flavonoids C21 H22 O9 417.1191 417.1194 0.7 [M − H]− 255.0665, 135.0089, 119.0504 GRP [31 ] 41 14.08 Polygalaxanthone III Xanthones C25 H28 O15 567.1355 567.1361 1.1 [M − H]− 447.0945, 435.0932, 417.0839, 357.0621, 345.0620, 327.0518, 315.0515, 297.0408 PRP [10 ] 42 14.27 Jionoside E☆ Phenylethanoid glycosides C35 H46 O19 769.2561 769.2568 0.9 [M − H]− 623.2197, 605.2092, 549.1662, 427.1069, 323.0996, 179.0561 RRP [27 ] 43 14.37 Liquiritin apioside Flavonoids C26 H30 O13 549.1614 549.1616 0.4 [M − H]− 255.06581, 135.00719, 119.04859, 417.11804 GRP [31 ] 45 14.47 Asimilobine☆ Alkaloids C17 H17 NO2 268.1332 268.1324 −3.0 [M − H]− 251.1064, 219.0809, 201.0722, 191.0858, 179.0855 ZSS [22 ] 44 14.47 Polygalaxanthone XI☆ Xanthones C25 H28 O15 567.1355 567.1366 1.9 [M − H]− 345.0619, 315.0511 PRP [32 ] 46 14.56 Jionoside A1/jionoside A2 Phenylethanoid glycosides C36 H48 O20 799.2666 799.2672 0.8 [M − H]− 623.2199, 605.2092, 461.1663, 315.1110, 193.0509, 175.0403 RRP [30 ] 47 14.85 Spinosin Flavonoids C28 H32 O15 607.1668 607.1674 1.0 [M − H]− 487.1252, 445.1144, 427.1039, 367.0823, 337.0722, 307.0614 ZSS [16 ] 48 15.33 Swertisin Flavonoids C22 H22 O10 445.1140 445.1147 1.6 [M − H]− 355.0839, 325.0721, 297.0409 ZSS [16 ] 49 15.33 Isoviolanthin/violanthin☆ Flavonoids C27 H30 O14 577.1563 577.1572 1.6 [M − H]− 383.0777, 353.0670, 413.08783, 457.1145, 487.1248 GRP [31 ] 50 15.43 Tenuifoliside B Sucrose esters C30 H36 O17 667.1880 667.1894 2.1 [M − H]− 461.1312, 205.0510, 190.0274, 137.0247, 281.0674 PRP [23 ] 51 15.52 Sibiricose A4☆ Sucrose esters C34 H42 O19 753.2248 753.2254 0.8 [M − H]− 547.1678, 529.1574, 461.1306, 367.1041, 223.0615, 205.0509, 190.0274 PRP [29 ] 52 15.71 Tenuifoliside 638☆ Sucrose esters C29 H34 O16 637.1774 637.1773 −0.2 [M − H]− 461.1309, 443.1208, 175.0402 PRP [29 ] 53 16.48 Acteoside Phenylethanoid glycosides C29 H36 O15 623.1981 623.1989 1.3 [M − H]− 461.1667, 443.1555, 315.1083, 179.0349, 161.0243 RRP [30 ] 54 17.06 6′′′-Vanilloylspinosin☆ Flavonoids C36 H38 O18 757.1985 757.1993 1.1 [M − H]− 637.1556, 607.1694, 445.1143, 427.1038, 367.0827, 307.0621 ZSS [22 ] 55 17.25 Senkyunolide I Phthalides C12 H16 O4 207.1015 207.1009 −2.9 [M + H–H2 O]+ 189.0822, 161.0906, 147.0752 ASR [33 ] 56 17.44 Jionoside B1/Jionoside B2 Phenylethanoid glycosides C37 H50 O20 813.2823 813.2834 1.4 [M − H]− 637.2359, 619.2254, 491.1780, 193.0507, 175.0402, 160.0167 RRP [16 ] 57 17.63 6′′′-P-Hydroxyl-benzoyspinosin☆ Flavonoids C35 H36 O17 727.1880 727.1879 −0.1 [M − H]− 607.1616, 445.1149, 427.1038, 325.0719, 307.0617 ZSS [16 ] 58 17.73 Isoacteoside Phenylethanoid glycosides C29 H36 O15 623.1981 623.1990 1.4 [M − H]− 461.1670, 477.1405, 315.1096, 179.0351, 161.0245 RRP [30 ] 59 18.69 Tenuifoliside A isomer☆ Sucrose esters C31 H38 O17 681.2036 681.2044 1.2 [M − H]− 443.1208, 281.0672, 237.0774, 223.0616, 205.0510, 137.0246 PRP [23 ] 60 18.78 Senkyunolide H Phthalides C12 H16 O4 207.1015 207.1008 −3.4 [M + H–H2 O]+ 189.0812, 161.0938, 147.0689 ASR [33 ] 61 18.98 3,6′-Disinapoyl sucrose Sucrose esters C34 H42 O19 753.2248 753.2249 0.1 [M − H]− 547.1670, 529.1568, 367.1038, 265.0720, 223.0612, 205.0506, 190.0271 PRP [10 ] 62 19.02 Nornuciferine☆ Alkaloids C18 H19 NO2 282.1489 282.1481 −2.7 [M + H]+ 265.1214, 250.0979, 121.0280 ZSS [22 ] 63 19.05 6′′′-Sinapoyl spinosin Flavonoids C39 H42 O19 815.2393 815.2379 −1.7 [M + H]+ 429.1181, 411.1037, 369.1162, 327.0855, 207.0647, 351.0833, 297.0750, 175.0385 ZSS [16 ] 64 19.21 6′′′-Dihydrophaseoylspinosin☆ Flavonoids C43 H52 O19 873.3176 873.3158 −2.0 [M + H]+ 855.2986, 447.1263, 429.1140, 411.1057, 393.0969, 381.0947, 351.0846, 327.0854, 297.0752, 247.1321 ZSS [22 ] 65 19.56 3,4,5-Trimethoxycinnamic acid☆ Organic acids C12 H14 O5 237.0768 237.0770 0.8 [M − H]− 193.0873, 108.0215 PRP [34 ] 66 19.60 6′′′-p-Coumaroyl spinosin Flavonoids C37 H38 O17 755.2182 755.2166 −2.1 [M + H]+ 429.1170, 411.1080, 351.0850, 327.0854, 147.0438, 635.1770, 381.0957, 297.0750 ZSS [16 ] 67 19.66 Jionoside D Phenylethanoid glycosides C30 H38 O15 637.2138 637.2137 −0.2 [M − H]− 161.0242, 461.1660, 267.0660, 175.0401 RRP [10 ] 68 19.66 Arillanin A☆ Sucrose esters C33 H40 O18 723.2142 723.2149 1.0 [M − H]− 547.1679, 265.0722, 223.0617, 205.0510, 175.0404, 160.0170 PRP [32 ] 69 19.73 6′′′-Feruloyl spinosin Flavonoids C38 H40 O18 785.2287 785.2263 −3.1 [M + H]+ 665.1891, 447.1275, 429.1168, 411.1068, 393.0957, 351.0852, 327.0853, 297.0750, 177.0542 ZSS [10 ] 70 19.95 Tenuifoliside 652☆ Sucrose esters C30 H36 O16 651.1931 651.1942 1.7 [M − H]− 443.1199, 281.0671, 207.0668, 175.0403, 137.0244 PRP [29 ] 71 20.81 Ononin☆ Flavonoids C22 H22 O9 475.1246 475.1249 0.6 [M + COOH]− 475.1249, 267.0664, 252.0429 GRP [31 ] 72 21.00 Tenuifoliside 652 isomer☆ Sucrose esters C30 H36 O16 651.1931 651.1941 1.5 [M − H]− 443.1199, 205.0509, 190.0272, 175.0033, 121.0297 PRP [29 ] 73 21.10 Isoliquiritin apioside Flavonoids C26 H30 O13 549.1614 549.1620 1.1 [M − H]− 255.0667, 135.0090, 119.0505, 417.1200 GRP [10 ] 74 21.48 Isoliquiritin Flavonoids C21 H22 O9 417.1191 417.1197 1.4 [M − H]− 255.0666, 135.0089, 119.0404 GRP [10 ] 75 21.77 Leucosceptoside A Phenylethanoid glycosides C30 H38 O15 637.2138 637.2129 −1.4 [M − H]− 461.1661, 175.0400, 265.0722, 161.0239 RRP [30 ] 76 21.77 Tenuifoliside A Sucrose esters C31 H38 O17 681.2036 681.2038 0.3 [M − H]− 443.1203, 281.0671, 239.0564, 179.0352, 137.0245 PRP [10 ] 77 22.06 Liquiritigenin Flavonoids C15 H12 O4 255.0663 255.0665 0.8 [M − H]− 135.0086, 119.0502 GRP [31 ] 78 22.64 Neoisoliquiritin☆ Flavonoids C21 H22 O9 417.1191 417.1197 1.4 [M − H]− 255.0667, 135.0089, 119.0505 GRP [28 ] 79 22.64 Notoginsenoside R1☆ Saponins C47 H80 O18 977.5327 977.5334 0.7 [M + COOH]− 931.5284, 637.4332, 475.3809 GRR [35 ] 80 22.83 6′′′-(-)-Phaseoylspinosin☆ Flavonoids C43 H50 O19 869.2874 869.2884 1.2 [M − H]− 839.2765, 607.1683, 589.1575, 427.1045 ZSS [22 ] 81 23.70 Tenuifoliose G Oligosaccharide esters C66 H84 O38 1483.4568 1483.4582 0.9 [M − H]− 1337.39795, 1295.38232, 1161.35095, 1119.34119, 997.30548, 851.27283, 753.22705, 631.18640, 452.31161, 307.08231, 175.03891, 163.03868, 145.02803 PRP [10 ] 82 23.80 Senkyunolide D☆ Phthalides C12 H14 O4 221.0819 221.0820 0.5 [M − H]− 177.0921, 147.0450 ASR [36 ] 83 23.80 Tenuifoliose M Oligosaccharide esters C65 H82 O37 1453.4462 1453.4490 1.9 [M − H]− 1307.3873, 1161.3532, 997.3064, 835.2514, 307.0824, 163.0385, 145.0280 PRP [10 ] 84 24.48 Ginsenoside Rg1 Saponins C42 H72 O14 845.4904 845.4912 0.9 [M + COOH]− 799.4877, 637.4342, 475.3809, 161.0458, 179.0565 GRR [31 ] 85 24.67 Licorice glycoside B Flavonoids C35 H36 O15 695.1981 695.1991 1.4 [M − H]− 549.1634, 163.0409, 417.1202, 255.0665, 399.1099, 531.1523, 175.0403 GRP [31 ] 86 24.77 Isomartynoside☆ Phenylethanoid glycosides C31 H40 O15 651.2294 651.2303 1.4 [M − H]− 505.1703, 475.1826, 193.0511, 175.0403, 160.017, 113.0245 RRP [37 ] 87 24.77 Licorice glycoside A Flavonoids C36 H38 O16 725.2087 725.2095 1.1 [M − H]− 549.1639, 255.0668, 193.0508, 135.0086 GRP [38 ] 88 24.86 Ginsenoside Re Saponins C48 H82 O18 991.5483 991.5501 1.8 [M + COOH]− 945.5442, 783.4916, 637.4329, 475.3793, 179.0562, 161.0457 GRR [31 ] 89 26.11 Senkyunolide D isomer☆ Phthalides C12 H14 O4 221.0819 221.0817 −0.9 [M − H]− 177.0920, 147.0453 ASR [36 ] 90 26.31 Tenuifoliside C Sucrose esters C35 H44 O19 767.2404 767.2416 1.6 [M − H]− 529.1567, 367.1038, 237.077, 223.0613, 205.0507, 190.0271 PRP [10 ] 91 26.69 Tenuifoliose T☆ Oligosaccharide esters C56 H70 O32 1253.3777 1253.3792 1.2 [M − H]− 1223.3637, 1077.3279, 955.2908, 647.1988, 451.1232, 307.0810, 287.0549, 257.0444 PRP [23 ] 92 26.88 Martynoside☆ Phenylethanoid glycosides C31 H40 O15 651.2294 651.2299 0.8 [M − H]− 505.172, 475.1829, 193.0508, 175.0403, 160.0169, 113.0244 RRP [17 ] 93 26.90 (hydroxy benzoyl)-(hydroxy cinnamoyl)-trihydroxyphenyl sucrose Sucrose esters C34 H42 O18 783.2353 783.2365 1.5 [M + COOH]− 737.2325, 615.1934, 467.1415, 323.0980, 179.0547, 161.0458, 147.0453, 121.0296 PRP [10 ] 94 27.75 Tenuifoliose L Oligosaccharide esters C67 H84 O38 1495.4569 1495.4569 0.0 [M − H]− 1349.3923, 1307.3988, 163.0410, 145.0294 PRP [10 ] 95 28.14 Tenuifoliose K Oligosaccharide esters C57 H70 O32 1265.3777 1265.3801 1.9 [M − H]− 1119.3395, 1077.3346, 997.3037, 163.0403, 145.0294 PRP [10 ] 96 29.00 Tenuifoliose C Oligosaccharide esters C58 H72 O33 1295.3883 1295.3903 1.5 [M − H]− 1173.3653, 1119.3401, 1077.3265, 997.3061, 145.0296, 175.0404 PRP [10 ] 97 29.78 Amphibine D☆ Alkaloids C36 H49 N5 O5 632.3806 632.3805 −0.2 [M + H]+ 289.1874, 148.1111 ZSS [16 ] 98 30.35 Desacylsenegasaponin B☆ Saponins C57 H70 O32 1265.5808 1265.5831 1.8 [M − H]− 455.3179, 425.3077 PRP [29 ] 99 30.44 Uralsaponin C Saponins C42 H64 O16 823.4122 823.4133 1.3 [M − H]− 647.3829, 351.0580, 193.0357 GRP [28 ] 100 30.44 Tenuifoliose I Oligosaccharide esters C59 H72 O33 1307.3883 1307.3904 1.6 [M − H]− 1161.3529, 1119.3479, 1101.3331, 997.3023, 631.1891, 163.0400, 145.0299 PRP [10 ] 101 30.70 Aeginetic acid☆ Ionones C15 H24 O4 267.1602 267.1610 3.0 [M − H]− 223.1780, 205.1615, 178.9208, 153.0924 RRP [39 ] 102 30.81 Methoxyl benzoyl-trimethoxyl cinnamoyl sucrose Sucrose esters C32 H40 O17 741.2248 741.2255 0.9 [M + COOH]− 237.0773, 151.0402 PRP [10 ] 103 31.12 Tenuifoliose D Oligosaccharide esters C60 H74 O34 1337.3989 1337.4007 1.3 [M − H]− 1161.3546, 1119.3412, 1039.3161, 997.3030, 175.0404 PRP [10 ] 104 31.41 Notoginsenoside R2 Saponins C41 H70 O13 815.4834 815.4834 0.0 [M + COOH]− 769.4745, 637.4342, 475.3791, 161.0462 GRR [40 ] 105 31.41 Tenuifoliose E☆ Oligosaccharide esters C58 H72 O33 1295.3883 1295.3933 3.9 [M − H]− 1173.3506, 1119.3442, 795.2398, 175.0404, 145.0300 PRP [29 ] 106 31.79 Polygalasaponin XXIII☆ Saponins C53 H82 O24 1101.5123 1101.5164 3.7 [M − H]− 423.2925, 453.3029 PRP [29 ] 107 32.08 Polygalasaponin XXVIII Saponins C53 H84 O24 1103.5380 1103.5328 −4.7 [M − H]− 455.3185, 425.3075 PRP [23 ] 108 32.28 24-Hydroxyl-licorice-saponin A3 Saponins C48 H72 O22 999.4442 999.4488 4.6 [M − H]− 837.3942, 351.0584, 193.0359 GRP [10 ] 109 32.57 Tenuifoliose J☆ Oligosaccharide esters C59 H72 O33 1307.3883 1307.3898 1.1 [M − H]− 1161.3549, 1039.3096, 163.0408, 145.0304 PRP [29 , 32 ] 110 32.81 Butylidenephthalide Phthalides C12 H12 O2 189.0910 189.0904 −3.2 [M + H]+ 171.0799, 161.0954, 143.0852, 117.0694 ASR [20 ] 111 32.85 Senkyunolide F☆ Phthalides C12 H14 O3 205.0870 205.0880 4.9 [M − H]− 161.0975 ASR [20 ] 112 32.92 Uralsaponin F Saponins C44 H64 O19 895.3969 895.3995 2.9 [M − H]− 719.3703, 351.0586, 193.0363 GRP [31 ] 113 32.95 Onjisaponin TF Saponins C59 H94 O28 1249.5859 1249.5880 1.7 [M − H]− 1025.5362, 455.3185, 425.3077 PRP [23 ] 114 33.05 Licorice saponin H2/K2☆ Saponins C42 H62 O16 821.3965 821.3981 1.9 [M − H]− 351.0583, 193.0364, 175.0255 GRP [28 , 41 ] 115 33.05 22-Hydroxyl-licorice-saponin G2 Saponins C42 H62 O18 853.3863 853.3882 2.2 [M − H]− 677.3568, 351.0583, 193.0365 GRP [28 ] 116 33.22 Butylphthalide Phthalides C12 H14 O2 191.1067 191.1062 −2.6 [M + H]+ 173.0959, 155.0842, 145.1008, 117.0698 ASR [20 ] 117 33.34 Tenuifoliose B Oligosaccharide esters C60 H74 O34 1337.3989 1337.4027 2.8 [M − H]− 1161.3551, 1119.342, 1101.3324, 1039.3156, 175.0410, 145.0306 PRP [10 ] 118 33.92 Ginsenoside Rf Saponins C42 H72 O14 845.4904 845.4928 2.8 [M + COOH]− 799.4880, 637.4349, 475.3820, 179.0574, 161.0466 GRR [35 ] 119 33.92 Tenuifoliose H Oligosaccharide esters C61 H74 O34 1349.3989 1349.4019 2.2 [M − H]− 1307.3907, 1161.3503, 731.2194, 145.0304 PRP [10 ] 120 34.40 Senkyunolide A Phthalides C12 H16 O2 193.1223 193.1218 −2.6 [M + H]+ 147.1170, 175.1113, 137.0593 ASR [20 ] 121 34.59 Tenuifoliose A Oligosaccharide esters C62 H76 O35 1379.4094 1379.4131 2.7 [M − H]− 1203.3649, 1161.3529, 175.041, 145.0303 PRP [10 ] 122 35.08 Tenuifoliose N☆ Oligosaccharide esters C63 H78 O36 1409.4200 1409.4234 2.4 [M − H]− 1233.3879, 175.0410 PRP [23 ] 123 35.37 Ginsenoside F5☆ Saponins C41 H70 O13 815.4834 815.4821 −1.6 [M + COOH]− 769.4765, 637.4337, 475.3807 GRR [42 ] 124 35.41 Licorice saponin A3 Saponins C48 H72 O21 983.4493 983.4518 2.5 [M − H]− 821.3988, 645.3687, 351.0584, 193.0366 GRP [31 ] 125 35.79 24-Hydroxyl-licorice-saponin E2 Saponins C42 H60 O17 835.3793 835.3785 −1.0 [M − H]− 659.3446, 351.0582, 193.0362 GRP [28 ] 126 35.84 Isoliquiritigenin☆ Flavonoids C15 H12 O4 255.0663 255.0674 4.3 [M − H]− 135.0094, 119.0510 [28 ] 127 36.04 Formononetin☆ Flavonoids C16 H12 O4 267.0663 267.0671 3.0 [M − H]− 252.0458, 195.0458 [31 ] 128 36.32 Senkyunolide F isomer☆ Phthalides C12 H14 O3 205.0870 205.0879 4.4 [M − H]− 161.0993 ASR [20 ] 129 36.42 22β -Acetoxyl-glycyrrhizin Saponins C44 H64 O18 879.4020 879.4034 1.6 [M − H]− 351.0583, 193.0362 GRP [31 ] 130 36.61 Tenuifolin Saponins C36 H56 O12 679.3699 679.3718 2.8 [M − H]− 455.3180, 425.3074 PRP [10 ] 131 36.71 Ginsenoside F3☆ Saponins C41 H70 O13 815.4834 815.4818 −2.0 [M + COOH]− 769.4761, 637.4332, 475.3810, 161.0463 GRR [42 ] 132 36.90 20(S)-Ginsenoside Rh1 Saponins C36 H62 O9 683.4376 683.4390 2.0 [M + COOH]− 637.4335, 475.3806, 161.0462 GRR [10 ] 133 36.90 20(S)-Ginsenoside Rg2 Saponins C42 H72 O13 829.4955 829.4969 1.7 [M + COOH]− 783.4911, 637.4334, 475.3807, 161.0461 GRR [35 ] 134 36.90 22-Hydroxyl-glycyrrhizin Saponins C42 H62 O17 837.3914 837.3929 1.8 [M − H]− 661.3603, 485.3294, 351.0583, 193.0362 GRP [28 ] 135 37.35 Senkyunolide A isomer☆ Phthalides C12 H16 O2 193.1223 193.1217 −3.1 [M + H]+ 147.1163, 175.1113, 137.0594 ASR [20 ] 136 37.39 20(R)-Ginsenoside Rg2 Saponins C42 H72 O13 829.4955 829.4972 2.0 [M + COOH]− 783.4913, 637.4332, 475.3808, 161.0462 GRR [42 ] 137 37.68 20(R)-Ginsenoside Rh1 Saponins C36 H62 O9 683.4376 683.4393 2.5 [M + COOH]− 637.4336, 475.3807, 161.0463 GRR [40 ] 138 37.89 Jujuboside A Saponins C58 H94 O26 1251.6015 1251.6036 1.7 [M + COOH]− 1205.5983, 1073.5549, 749.4461, 455.1431, 179.0564, 161.0463 ZSS [16 ] 139 38.73 Ginsenoside Rb1 Saponins C54 H92 O23 1153.6011 1153.6033 1.9 [M + COOH]− 1107.5962, 945.5427, 783.4889, 621.4396, 459.3908 GRR [31 ] 140 39.41 Licorice saponin E2 Saponins C42 H60 O16 819.3809 819.3819 1.2 [M − H]− 645.3648, 351.0581, 193.0362 GRP [28 ] 141 39.70 Ginsenoside Ro Saponins C48 H76 O19 955.4908 955.4918 1.0 [M − H]− 793.4382, 775.4275, 749.451, 731.4392, 523.3806, 455.3537, 613.3755, 569.3857, 179.0569, 119.0355 GRR [31 ] 142 39.70 Ginsenoside Rc Saponins C53 H90 O22 1123.5906 1123.5918 1.1 [M + COOH]− 1077.5854, 915.5348, 459.3809, 149.0451, 191.0563 GRR [35 ] 143 39.79 Licorice saponin G2 Saponins C42 H62 O17 837.3914 837.3921 0.8 [M − H]− 775.3927, 661.3593, 485.3277, 351.0576, 193.0359 GRP [28 ] 144 40.75 Ginsenoside Rb2 Saponins C53 H90 O22 1123.5906 1123.5908 0.2 [M + COOH]− 1077.5865, 783.4945, 621.4307, 459.3789 GRR [35 ] 145 41.14 Ginsenoside Rb3 Saponins C53 H90 O22 1123.5906 1123.5907 0.1 [M + COOH]− 1077.5871, 783.4955, 621.4311, 459.3792 GRR [43 ] 146 41.33 Rhaoglycyrrhizin Saponins C48 H72 O20 967.4544 967.4567 2.4 [M − H]− 497.1159, 321.0841, 339.0941 GRP [10 ] 147 41.33 Jujuboside B Saponins C52 H84 O21 1045.5578 1045.5582 0.4 [M + H]+ 733.4491, 587.39348, 533.3637, 455.3536, 437.3432, 369.2802 ZSS [16 ] 148 42.59 Chikusetsusaponin IVa Saponins C42 H66 O14 793.4380 793.4389 1.1 [M − H]− 631.3854, 455.3525, 569.3834 GRR [31 ] 149 42.68 Ginsenoside Rd Saponins C48 H82 O18 991.5483 991.5496 1.3 [M + COOH]− 945.5438, 783.4892, 621.438, 459.3857, 179.0563, 161.0457 GRR [35 ] 150 42.78 Glycyrrhizic acid Saponins C42 H62 O16 821.3965 821.3972 0.9 [M − H]− 759.3961, 645.3648, 469.3324, 351.0572, 193.0356 GRP [31 ] 151 43.19 Senkyunolide A isomer☆ Phthalides C12 H16 O2 193.1223 193.1220 −1.6 [M + H]+ 147.1166, 175.1117, 137.0599 ASR [20 ] 152 44.03 6,8-Dihydroxy-1,2,4-trimethoxyxanthone☆ Xanthones C16 H14 O7 317.0667 317.0675 2.5 [M − H]− 302.0444, 287.0203, 259.0254, 231.0297 [23 ] 153 44.61 Licorice saponin B2☆ Saponins C42 H64 O15 807.4172 807.4178 0.7 [M − H]− 631.3870, 351.0572, 193.0356 GRP [31 ] 154 44.62 Atractylenolide I Terpene lactones C15 H18 O2 231.1379 231.1373 −2.6 [M + H]+ 213.1266, 203.1427, 189.0913, 185.1314, 157.1007 ARP [10 ] 155 44.70 Atractylenolide III Terpene lactones C15 H20 O3 249.1485 249.1485 −0.1 [M + H]+ 231.1405, 213.1207, 185.1277, 175.0688 ARP [10 ] 156 45.19 Uralsaponin B Saponins C42 H62 O16 821.3965 821.3972 0.9 [M − H]− 759.3961, 645.3648, 469.3324, 351.0572, 193.0356 GRP [44 ] 157 46.15 Licorice saponin J2 Saponins C42 H64 O16 823.4122 823.4131 1.1 [M − H]− 351.0573, 193.0357 GRP [41 ] 158 46.25 Ginsenoside Rg6 Saponins C42 H70 O12 811.4849 811.4852 0.4 [M + COOH]− 765.4808, 619.4225, 205.0721, 161.0459 GRR [31 ] 159 46.25 Senegasaponin B☆ Saponins C69 H102 O31 1425.6332 1425.6381 3.4 [M − H]− 1395.6243, 1201.5864, 455.3163, 425.3061 PRP [29 ] 160 46.25 Onjisaponin Z☆ Saponins C71 H106 O32 1469.6594 1469.6600 0.4 [M − H]− 1245.6054, 1439.6517, 425.3061, 405.1400, 455.3165 PRP [29 ] 161 46.34 Onjisaponin E Saponins C71 H106 O33 1485.6544 1485.6545 0.1 [M − H]− 455.3187, 425.3029 PRP [23 ] 162 46.53 Onjisaponin Y☆ Saponins C69 H102 O30 1409.6383 1409.6376 −0.5 [M − H]− 1379.6184, 1185.5881, 425.3062, 455.3166 PRP [29 ] 163 46.53 Onjisaponin G☆ Saponins C70 H104 O32 1455.6438 1455.6447 0.6 [M − H]− 1425.6341, 993.5078, 425.3062, 455.3166 PRP [23 ] 164 46.63 Ginsenoside Rg4☆ Saponins C42 H70 O12 811.4849 811.4854 0.6 [M + COOH]− 765.4798, 619.4212, 161.0456 GRR [42 ] 165 46.82 Ginsenoside Rk3 Saponins C36 H60 O8 665.4270 665.4271 0.2 [M + COOH]− 619.4211, 457.3698, 161.0458 GRR [31 ] 166 46.82 Licorice saponin C2☆ Saponins C42 H62 O15 805.4016 805.4020 0.5 [M − H]− 645.3637, 351.0575, 193.0356 GRP [41 ] 167 46.92 Onjisaponin TH Saponins C65 H96 O28 1323.6015 1323.5991 −1.8 [M − H]− 455.3171, 425.3048 PRP [23 ] 168 47.11 Ginsenoside Rh4 Saponins C36 H60 O8 665.4270 665.4277 1.1 [M + COOH]− 619.4218, 457.3679, 161.0459 GRR [31 ] 169 47.40 Zingibroside R1 Saponins C42 H66 O14 793.4380 793.4386 0.8 [M − H]− 731.4390, 631.3853, 613.3751, 569.3853, 455.3538 GRR [42 ] 170 47.88 Ginsenoside Rg3 Saponins C42 H72 O13 829.4955 829.4953 −0.2 [M + COOH]− 783.4894, 621.4369, 459.3844, 161.0456 GRR [31 ] 171 48.10 E-Ligustilide Phthalides C12 H14 O2 191.1067 191.1060 −3.7 [M + H]+ 173.0959, 163.1111, 155.0845, 145.1010 ASR [20 , 33 ] 172 48.17 Licochalcone A☆ Flavonoids C21 H22 O4 337.1445 337.1445 0.0 [M − H]− 307.0978, 281.082, 243.104 [31 ] 173 48.56 Isoglycyrol☆ Flavonoids C21 H18 O6 365.1031 365.1029 −0.5 [M − H]− 335.0561, 307.0248, 295.0251 [31 ] 174 49.13 20(S)-Ginsenoside Rs3 Saponins C44 H74 O14 871.5061 871.5056 −0.6 [M + COOH]− 825.5012, 783.4903, 621.4387, 459.3845, 765.4792 [35 ] 175 49.26 Atractylenolide II Terpene lactones C15 H20 O2 233.1536 233.1532 −1.7 [M + H]+ 215.1431, 187.1473, 169.1047, 151.0747, 145.1009 ARP [10 ] 176 49.33 20(R)-Ginsenoside Rs3☆ Saponins C44 H74 O14 871.5061 871.5074 1.5 [M + COOH]− 825.5021, 783.4910, 621.4384, 459.3875, 765.4807 [35 ] 177 49.39 Z-Ligustilide Phthalides C12 H14 O2 191.1067 191.1062 −2.6 [M + H]+ 173.0956, 163.1112, 155.0847, 145.1010 ASR [20 , 33 ] 178 50.00 Ginsenoside Rk1 Saponins C42 H70 O12 811.4849 811.4850 0.1 [M + COOH]− 765.4802, 603.4275, 161.0458 [31 ] 179 50.19 Ginsenoside Rg5 Saponins C42 H70 O12 811.4849 811.4856 0.9 [M + COOH]− 765.4800, 603.4263, 161.0458 [40 ] 180 52.21 Glycyrrhetinic acid☆ Saponins C30 H46 O4 469.3323 469.3327 0.9 [M − H]− 425.3406 [31 ]
