No. tR (min) Formula Identification Precursor ions (m /z ) Diff (ppm) Fragment (m /z ) Type Reference standard 1 0.25 C27 H30 O16 Rutin 609.1461[M − H]− −3.414 301.0351, F Yes 2 1.05 C15 H10 O7 Quercetin 301.0353[M − H]− 3.724 273.0405, F 3 1.68 C8 H8 O4 Vanillic acid 167.0349 [M − H]− 0.867 152.0105, PO 4 2.35 C17 H20 O9 Methyl chlorogenic acid 367.1034[M − H]− 5.239 191.0553, P 5 3.57 C11 H14 O5 Genipin 225.0768[M − H]− 2.738 207.0659, I Yes 6 3.82 C6 H6 O3 Pyrogallic acid 125.0244[M − H]− −1.604 107.4741, PO 7 4.09 C16 H22 O10 Geniposidic acid 373.1140[M − H]− −6.227 211.0940, I 8 4.47 C16 H22 O11 Deacetyl asperulosidic acid 389.1089[M − H]− 3.167 227.0550, I 9 4.85 C10 H14 O10 2-Methylsuccinyl-6′-O-glucoside 293.0514[M − H]− 6.047 131.0450 PO 10 4.92 C15 H22 O9 Aucubin 345.1191[M − H]− 2.335 183.0660, I 11 5.37 C17 H26 O11 Harpagide acetate 405.1402[M − H]− −1.364 191.0554, I 12 6.23 C15 H10 O6 Kaempferol 285.0404[M − H]− 4.615 257.0453, F Yes 13 7.41 C23 H34 O15 Genipin gentian diglycoside 549.1824[M − H]− 5.378 387.2035, I 14 7.50 C25 H24 O11 3-Caffeoyl-5-coumaroyl-quinic acid 499.12458[M − H]− 5.81 353.1080, P 15 8.32 C19 H18 O11 Isomangiferin 421.0776[M − H]− −1.966 259.0224 F 16 8.44 C9 H6 O3 Umbelliferone 161.0244[M − H]− −0.249 135.0441, P 17 8.99 C7 H6 O5 Gallic acid 169.0142[M − H]− 0.179 125.0232, PO Yes 18 9.25 C6 H6 O4 2-Hydroxyphenol 141.0193[M − H]− 3.247 123.0175 PO 19 9.76 C15 H14 O6 L-Epicatechin 289.0717[M − H]− 7.333 271.0235, F 20 10.56 C4 H4 O4 Maleic acid 115.0036[M − H]− −0.479 71.0124 PO 21 11.43 C15 H24 O10 Harpagide 363.1296[M − H]− 0.977 183.0652, I 22 12.53 C16 H18 O9 Chlorogenic acid 353.0878[M − H]− 0.854 191.0554, P Yes 23 14.13 C8 H8 O4 Methyl protocatechuic acid 167.0349[M − H]− 0.508 152.0106, PO 24 15.84 C8 H8 O4 Isovanillic acid 167.0349[M − H]− −2.536 123.0439 PO 25 18.23 C13 H16 O9 Protocatechuic acid-4-glucoside 315.0721[M − H]− −1.392 108.0204 PO 26 19.56 C14 H18 O9 4-Glucopyranoxy-3-benzoic acid 329.0878[M − H]− 4.340 167.0340, O 27 20.23 C9 H12 O5 Rehmaglutin C 199.0611[M − H]− 3.316 155.0704, I 28 20.39 C18 H24 O12 Asperulosidic acid 431.1194[M − H]− −3.114 269.0198, I 29 21.77 C16 H18 O9 Neochlorogenic acid 353.0878[M − H]− −0.699 191.0554, P 30 22.36 C16 H18 O9 4-Caffeoylquinic acid 353.0878[M − H]− 3.941 191.0554, P 31 23.28 C20 H24 O7 Cycloolivil 375.1449[M − H]− −2.075 327.1343, L 32 24.28 C9 H8 O4 Caffeic acid 179.0349[M − H]− 0.856 135.0440 P Yes 33 24.36 C9 H10 O4 Dihydrocaffeic acid 181.0506[M − H]− 1.849 163.0390, P 34 26.50 C7 H6 O4 Gentianic acid 153.0193[M − H]− −0.295 109.0282 PO 35 27.23 C7 H6 O4 Protocatechuic acid 153.0193[M − H]− 0.685 109.0283, PO 36 28.03 C42 H70 O12 Ginsenoside F4 789.4759[M + Na]+ −1.837 707.1499, T 37 28.55 C20 H24 O7 Oleoresin 375.1449[M − H]− −1.018 179.0341, L 38 29.40 C16 H18 O9 Cryptochlorogenic acid 353.0878[M − H]− 3.516 191.0554, P 39 30.90 C20 H24 07 Olivil 375.1449[M − H]− −2.635 327.1360, L 40 32.26 C17 H24 O10 Geniposide 387.1296[M − H]− 3.128 207.1025, I 41 33.49 C33 H44 O19 Naringin dihydrochalcone 4-O-β -D-glucoside 743.2404[M − H]− 3.128 373.1295, F 42 34.26 C27 H32 O16 Hydroxysafflor yellow A 611.1617[M − H]− 2.207 491.1200, F Yes 43 37.58 C10 H10 O4 Ferulic acid 193.0506[M − H]− 2.208 178.0264, P Yes 44 38.11 C32 H42 O16 Pinoresinol diglucoside 681.2400[M − H]− 2.039 519.5070, L 45 39.59 C16 H18 O8 3-O-p-Coumaroylquinic acid 337.0928[M − H]− 6.688 191.0553, P 46 40.21 C27 H36 O13 Citrusin B 567.2083[M − H]− −4.289 341.1384, L 47 41.77 C27 H30 O17 Quercetin-3, 4′-O-di-β -glucopyranoside 625.1410[M − H]− 0.831 463.0884, F 48 42.23 C15 H26 O9 Eucommioside 349.1504[M − H]− −1.102 187.1528, I 49 43.69 C10 H10 O3 Coniferyl aldehyde 177.0557[M − H]− −0.101 162.0312 P 50 46.23 C20 H22 O7 Erythroglycerin-β -terpineol aldehyde ether 373.1292[M − H]− 4.259 177.0548, P 51 48.38 C26 H28 O16 Quercetin 3-O-sambubioside 595.1305[M + H]+ −0.638 301.0327 F 52 49.62 C26 H32 O11 Pinoresinol-4′-O-β -D-glucopyranoside 519.1871[M − H]− −3.929 357.1345, L 53 54.63 C26 H32 O11 Pinoresinol-β -D-glucoside 519.1871[M − H]− 3.334 357.1345, L 54 55.16 C21 H20 O12 Isoquercitrin 463.0881[M − H]− 3.623 301.0349, F Yes 55 56.44 C22 H28 O14 5-(3 ′-o-caffeoylglucosyl) quinine 515.1406[M − H]− 8.420 191.0555, P 56 57.45 C22 H28 O14 1-O-(3 ′-o-caffeoylglucosyl) quinine 515.1406[M − H]− 2.499 179.0341, P 57 57.73 C33 H40 O21 Quercetin 3-glucosyl-(1->3)-rhamnosyl-(1->6)-galactoside 771.1989[M − H]− 2.070 609.1469, F 58 58.66 C28 H36 O13 Syringaresionl-O-β -D-g1ucopyranoside 579.2083[M − H]− 3.298 417.1557 P 59 59.50 C35 H60 O6 Daucosterol 575.4317[M − H]− 2.329 397.7564 T 60 62.59 C25 H24 O12 1,5-Dicaffeoylquinic acid 515.1194[M − H]− 2.499 353.0881, P 61 63.34 C25 H24 O12 Isochlorogenic acid A 515.1194[M − H]− 1.288 353.0881, P 62 64.00 C42 H72 O15 6-O-β -D-Glucopyranosyl-20-o-β -D-glucopyranosyl-3β ,6β ,12β ,20 (S)7-25-pentaphydroxydammar-23-enedroginsenoside Rg1 839.4763[M + Na]+ −2.644 659.4114 T 63 65.10 C25 H24 O12 Isochlorogenic acid B 515.1194[M − H]− 1.288 353.0881, P 64 66.70 C9 H16 O4 Eucommitol 187.0975[M − H]− 1.521 169.0861, I Yes 65 66.72 C6 H4 O4 Coumalic acid 139.0036[M − H]− 6.332 119.5097 O 66 67.26 C18 H16 O5 Sideroxylin 311.0924[M − H]− 2.177 267.0663 F 67 67.68 C21 H20 O12 Hyperoside 463.0882[M − H]− 4.206 301.03455, F 68 68.78 C15 H26 O7 2-(5-Hydroxyethyl-2,3-dimethyl-2-cyclopenten-1-yl)-glucopyranoside 317.1605[M − H]− 4.580 243.1238, I 69 69.40 C21 H20 O10 Apigenin-7-O-glucuronide 431.0983[M − H]− 3.147 269.0376 F 70 70.29 C9 H16 O3 1-Deoxyeucommitol 171.1026[M − H]− 0.930 127.1118, I 71 72.63 C21 H20 O11 Astragalin 447.0933[M − H]− 2.532 285.0395, F 72 73.55 C21 H18 O11 Baicalin 445.0776[M − H]− 4.724 269.0456 F 73 74.23 C27 H30 O15 Nicotiflorin 593.1511[M − H]− 3.681 285.0404, F 74 74.88 C27 H30 H15 Safflor yellow (A) 593.1511[M − H]− 3.884 285.0404 F Yes 75 75.61 C18 H14 O6 Milletenin C 325.0717[M − H]− 2.650 310.0848 F 76 76.26 C12 H16 O3 3-Butyl-4-hydroxy-4,5-dihydro-2-benzofuran-1(3H)-one 207.1026[M − H]− 0.368 135.0443 O 77 77.03 C11 H12 O4 Ethyl caffeate 207.0662[M − H]− 3.162 179.0341, P 78 77.96 C48 H82 O19 Notoginsenoside R6 985.5342[M + Na]+ −2.049 365.1045, T 79 78.56 C48 H82 O19 Notoginsenoside R3 985.5342[M + Na]+ 2.402 645.4159, T 80 79.20 C28 H32 O16 6-Methoxykaempferol 3-robinobioside 623.16175[M − H]− 1.524 315.0509, F 81 79.40 C29 H36 O15 3,4,6-Trihydroxy-4,2′-dimethoxychalcone 4′-O-rutinoside 623.19814[M − H]− 6.18 315.0510, F 82 79.58 C48 H82 O19 Notoginsenoside M 985.5342[M + Na]+ −3.227 805.4688, T 83 81.76 C48 H82 O19 Notoginsenoside N 985.5342[M + Na]+ −2.983 805.4689 T 84 82.77 C48 H82 O19 20-O-Glucoginsenoside Rf 985.5342[M + Na]+ −1.684 805.4689, T 85 83.83 C23 H22 O11 Apigenin 7-(2″-acetylglucoside) 473.1089[M − H]− 1.569 413.0891, F 86 84.34 C41 H68 O12 Notoginsenoside T5 775.4602[M + Na]+ −2.385 692.0035, T 87 84.47 C47 H80 O18 Notoginsenoside R1 931.5271[M − H]− 0.633 799.4888, T Yes 88 85.37 C15 H10 O6 Luteolin 285.0404[M − H]− 4.720 257.0453, F 89 85.76 C42 H72 O14 Majoroside F4 823.4814[M + Na]+ −1.603 643.4166 T 90 86.17 C42 H72 O14 3-O-β -D-Glucopyranosyl-6-O-β -D-glucopyranosyl-20-(S)-protopanaxatriol 823.4814[M + Na]+ −3.157 703.0069, T 91 87.18 C42 H72 O14 Gynoside B 823.4814[M + Na]+ −1.603 643.4164 T 92 87.69 C42 H72 O14 Ginsenoside Rg1 823.4814[M + Na]+ −1.603 643.4104 T 93 88.21 C45 H74 O17 Malonyl ginsenoside Rg1 909.4818[M + Na]+ −1.891 865.4895, T 94 89.59 C48 H80 O19 Notoginsenoside G 983.5186[M + Na]+ −2.897 803.4535 T 95 89.94 C30 H28 O12 4,2′,3′,4′-Tetrahydroxychalcone 4′-O-(2″-O-p-coumaroyl) glucoside 579.1507[M − H]− 0.622 271.0614, F 96 90.05 C15 H10 O5 Genistein 269.0455[M − H]− 4.572 225.0554, F Yes 97 90.57 C15 H10 O5 Apigenin 269.0455[M − H]− 4.572 225.0555, F Yes 98 91.24 C41 H70 O13 Pseudoginsenoside RT3 793.4708[M + Na]+ 3.882 613.4072 T 99 91.79 C44 H74 O15 Yesanchinoside D 865.4919[M + Na]+ −4.633 685.4267 T 100 92.47 C30 H26 O12 Apigenin-7-O-(6″-coumaroyl) glucoside 577.1351[M − H]− 1.390 431.0988, F 101 92.96 C20 H22 O6 Epipinoresinol 357.1343[M − H]− 1.216 151.1533, L 102 94.52 C42 H72 O14 Ginsenoside Rf 823.4814[M + Na]+ −2.113 661.5368, T 103 95.39 C41 H70 O13 Notoginsenoside R2 793.4708[M + Na]+ −2.583 661.4249, T 104 95.89 C42 H72 O13 Ginsenoside Rg2 807.4865[M + Na]+ −1.362 661.4281, T 105 96.47 C36 H62 O9 Gypenoside LXXVI 661.4286[M + Na]+ 2.479 601.2890, T 106 97.28 C36 H62 O9 Ginsenoside Rh1 661.4286[M + Na]+ −1.769 481.3650, T 107 98.42 C59 H100 O27 Ginsenoside Ra3 1263.6344[M + Na]+ −2.327 789.4784, T 108 99.42 C59 H100 O27 Notoginsenoside Fa 1263.6344[M + Na]+ −0.688 921.5158 T 109 100.51 C54 H92 O22 Notoginsenoside I 1115.5972[M + Na]+ −1.470 773.4795, T 110 101.91 C54 H92 O23 Ginsenoside Rb1 1107.5956[M − H]− 0.589 945.5432, T Yes 111 102.94 C42 H72 O13 Ginsenoside Rg3 807.4865[M + Na]+ −0.904 365.1046 T 112 103.85 C48 H82 O18 Ginsenoside Re 969.5393[M + Na]+ −1.908 789.4742 T Yes 113 105.07 C54 H92 O23 Yesanchinoside E 1131.5921[M + Na]+ −5.768 789.4737, T 114 106.08 C38 H64 O10 6′-O-Acetylginsenoside F1 703.4391[M + Na]+ 0.071 481.3647 T 115 106.58 C56 H94 O24 Quinquenoside R1 1173.6027[M + Na]+ −2.548 831.4845, T 116 107.65 C56 H94 O24 6‴-O-Acetylginsenoside Rb1 1173.6027[M + Na]+ −2.326 831.4845, T 117 108.75 C53 H90 O22 Ginsenoside Rb2 1101.5815[M + Na]+ −1.479 789.4740, T 118 109.76 C53 H90 O22 Notoginsenoside L 1101.5815[M + Na]+ −1.479 789.4740 T 119 110.33 C57 H94 O26 Malonyl ginsenoside Rb1 1217.5925[M + Na]+ −2.727 1173.5993, T 120 111.31 C48 H82 O17 Vina-ginsenoside R3 953.5444[M + Na]+ −2.349 773.4788 T 121 111.47 C48 H82 O18 Gypenoside XVII 969.5393[M + Na]+ −0.908 365.1048 T 122 112.04 C57 H94 O26 3-(β -D-Glucopyranosyl-β -D-glucopyranosyl)-20-O-(6-O-malonyl-β -D-glucopyranosyl-β -D-glucopyranosyl)-3β ,12β ,20(S)-trihydroxydammar-24-ene 1217.5925[M + Na]+ −1.07 1173.6008, T 123 112.53 C48 H82 O18 Ginsenoside Rd 945.5428[M − H]− 0.857 783.4907, T Yes 124 112.57 C36 H62 O8 Notoginsenoside R7 645.4336[M + Na]+ −3.249 627.3813, T 125 113.48 C36 H60 O8 36 H60 O7 Ginsenoside Rh3 643.4180[M + Na]+ −3.232 583.3644, T 126 113.89 C51 H84 O21 Malonyl ginsenoside Rd 1055.5397[M + Na]+ 3.598 875.4738, T 127 114.07 C48 H82 O18 Gypenoside LXXII 969.5393[M + Na]+ −1.691 789.4739 T 128 114.88 C36 H62 O11 Notoginsenoside T4 693.4184[M + Na]+ −3.763 633.3707 T 129 115.36 C47 H80 O17 3-O-[β -D-Glucopyranosyl(1–2)-β -D-glucopyranosyl]-20-O-β -D-xylopyranosyl-3β ,12β ,20(s)-trihydroxydammar-24-ene 939.5287[M + Na]+ −0.872 789.4735 T 130 116.22 C15 H10 O5 Baicalein 269.0455[M − H]− 4.238 197.1905 F Yes 131 117.02 C47 H80 O18 6-O-[Xylopyranosyl-β -D-glucopyranosyl]-3β ,6β ,12β ,20(s),25-pentahydroxydammar 811.4814[M + Na]+ 1.208 793.3365, T 132 117.70 C20 H22 O6 Pinoresinol 357.1343[M − H]− 1.340 313.1811, L 133 118.87 C42 H72 O13 Ginsenoside F2 807.4865[M + Na]+ 0.458 627.4217 T 134 120.08 C42 H72 O13 Gypenoside LXXV 807.4865[M + Na]+ 7.789 365.1045 T 135 121.53 C29 H42 O5 Ulmoidol 469.2959[M − H]− 3.715 423.2238 T 136 121.65 C28 H34 O4 Unknown 433.2384[M − H]− −0.685 433.2577 O 137 122.04 C36 H60 O9 Ginsenoside Rh7 659.4129[M + Na]+ −0.349 599.3925 T 138 122.50 C32 H42 O17 1-Hydroxypinoresinol-4,4″-di-O-β -D-glucopyranoside 697.2349[M − H]− 0.112 535.1532, L 139 122.99 C20 H24 O8 Threo-dihydroxydehy-drodiconiferyl alcohol 391.1398[M − H]− −3.313 313.1747, L 140 123.91 C16 H32 O2 Palmitic acid 255.2329[M − H]− 1.978 241.3251 O Yes 141 124.01 C20 H24 O8 Erytho-dihydroxydehydrodiconiferyl alcohol 391.1398[M − H]− −2.359 341.1587, L 142 125.83 C18 H36 O2 Palmitic acid ethyl ester 283.2642[M − H]− 3.859 89.0229 O 143 127.10 C9 H12 O4 Eucommidiol 183.0662[M − H]− 0.268 139.1124, I
