Table 1.
Chromatographic and mass data of the components detected in Arnebiae Radix though UHPLC-Q-Exactive Orbitrap MS.
| No. | Batch | tR | Theoretical Mass m/z | Experimental Mass m/z | Error (ppm) | Formula | MS/MS Fragment (-) |
Identification |
|---|---|---|---|---|---|---|---|---|
| 1 | A, B, C | 0.83 # | 131.0462 | 131.0450 | −9.05 | C4H8N2O3 | MS2[131]: 114.0183(100), 113.0343(65), 70.0284(37), 95.0237(25), 131.0449(22) | Asparagine |
| 2 | A, B, C | 0.86 # | 145.0619 | 145.0606 | −8.80 | C5H10N2O3 | MS2[145]: 127.0500(100), 128.0340(73), 145.0606(97), 102.0546(48), 109.0394(40) | Glutamine |
| 3 | A, B, C | 0.88 | 387.1144 | 387.1139 | −1.44 | C13H24O13 | MS2[387]: 89.0229(100), 119.0336(45), 179.0550(42), 341.1084(33), 161.0444(16), 221.0658(5) | 2,3,4,5,6-pentahydroxy-7-[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyheptanoic acid |
| 4 | A, B, C | 0.88 # | 341.1089 | 341.1084 | −1.66 | C12H22O11 | MS2[341]: 89.0230(100), 59.0124(48), 71.0124(40), 101.0230(33), 119.0336(29), 113.0231(25) | α,α-Trehalose |
| 5 | A, B, C | 0.88 # | 179.0561 | 179.0550 | −6.27 | C6H12O6 | MS2[341]: 59.0124(100), 89.0230(68), 71.0124(63), 75.0073(48), 101.0230(33), 119.0336(29) | Mannose |
| 6 | A, B, C | 0.88 # | 503.1618 | 503.1612 | −1.19 | C18H32O16 | MS2[503]: 89.0230(100), 101.0230(50), 113.0230(38), 179.0551(26) | Raffinose |
| 7 | A, B, C | 0.89 # | 135.0299 | 135.0286 | −9.68 | C4H8O5 | MS2[135]: 75.0073(100), 135.0287(51), 72.9917(13), 89.0230(11), 59.0124(10) | Threonic acid |
| 8 | A, B, C | 0.90 # | 195.0510 | 195.0500 | −5.26 | C6H12O7 | MS2[195]: 195.0501(100), 75.0073(82), 129.0180(76), 99.0074(22), 87.0073(21), 59.0124(12) | Gluconic acid |
| 9 | A, B, C | 0.90 # | 191.0561 | 191.0551 | −5.25 | C7H12O6 | MS2[191]: 111.0074(100), 87.0073(35), 85.0280(28), 191.0551(12) | Quinic acid |
| 10 | A, B, C | 0.91 # | 149.0455 | 149.0443 | −8.17 | C5H10O5 | MS2[149]: 149.0443(100), 89.0230(76), 59.0124(32), 75.0073(32) | Arabinose |
| 11 | A, B, C | 0.92 # | 193.0354 | 193.0344 | −5.16 | C6H10O7 | MS2[193]: 103.0023(100), 59.0124(29), 85.0280(16), 193.0708(10) | β-D-Glucopyranuronic acid |
| 12 | A, B, C | 0.93 # | 133.0142 | 133.0130 | −9.60 | C4H6O5 | MS2[133]: 115.0023(100), 71.0124(44), 133.0130(32) | Malic acid |
| 13 | A, B, C | 0.93 # | 177.0405 | 177.0395 | −5.60 | C6H10O6 | MS2[177]: 59.0124(100), 129.0181(42), 99.0074(34), 89.0230(32), 177.0397(31) | δ-Gluconic acidδ-lactone |
| 14 | A, B, C | 0.94 # | 191.0197 | 191.0188 | −5.01 | C6H8O7 | MS2[191]: 111.0074(100), 87.0073(35), 85.0280(28), 191.0188(11) | Citric acid isomer |
| 15 | A, B, C | 1.17 # | 191.0197 | 191.0188 | −5.01 | C6H8O7 | MS2[191]: 111.0074(100), 87.0073(34), 85.0281(23), 191.0188(10) | Citric acid |
| 16 | A, B, C | 1.17 # | 147.0299 | 147.0287 | −8.35 | C5H8O5 | MS2[147]: 129.0180(100), 85.0280(28), 103.0386(20), 147.0287(18), 101.0230(17) | α-Hydroxyglutaric acid |
| 17 | A, B, C | 1.17 # | 243.0623 | 243.0617 | −2.35 | C9H12N2O6 | MS2[243]: 110.0234(100), 128.0340(24), 200.0556(21), 152.0342(16), 140.0341(11) | Uridine |
| 18 | A, B, C | 1.17 | 167.0211 | 167.0199 | −6.79 | C5H4N4O3 | MS2[167]: 167.0200(100), 124.0140(38) | Uric acid |
| 19 | A, B, C | 1.31 # | 161.0455 | 161.0444 | −7.37 | C6H10O5 | MS2[161]: 99.0437(100), 57.0332(63), 101.0230(33), 161.0444(29), 59.0124(22) | 3-Hydroxy-3-methylglutaric acid |
| 20 | A, B, C | 1.42 # | 145.0506 | 145.0495 | −8.02 | C6H10O4 | MS2[145]: 145.0494(100), 101.0594(50) | 3-Methylglutaric acid |
| 21 | A, B, C | 1.66 # | 169.0142 | 169.0133 | −5.49 | C7H6O5 | MS2[169]: 125.0231(100) | Gallic acid |
| 22 | A, B, C | 1.92 | 164.0717 | 164.0707 | −6.23 | C9H11NO2 | MS2[164]: 147.0440(100), 164.0706(59), 72.0077(28), 96.9587(13) | Phenylalanine |
| 23 | A, B, C | 1.96 # | 137.0244 | 137.0232 | −8.74 | C7H6O3 | MS2[137]: 93.0331(100), 137.0231(37) | Salicylic acid |
| 24 | A, B, C | 2.14 # | 218.1034 | 218.1028 | −2.60 | C9H17NO5 | MS2[218]: 88.0389(100), 146.0810(50), 218.1027(13), 71.0124(9) | Pantothenic acid |
| 25 | A, B, C | 2.28 # | 197.0455 | 197.0447 | −4.40 | C9H10O5 | MS2[167]: 72.9917(100), 135.0439(67), 179.0340(58), 123.0439(50), 197.0445(11) | Danshensu |
| 26 | A, B, C | 2.28 # | 417.0827 | 417.0800 | −6.62 | C20H18O10 | MS2[417]: 219.0268(100), 197.0445(21), 179.0339(5) | Salvianolic acid D |
| 27 | A, B, C | 2.35 # | 167.0350 | 167.0339 | −6.36 | C8H8O4 | MS2[167]: 167.0339(100), 123.0439(87) | Vanillic acid |
| 28 | A, B, C | 2.81 # | 153.0193 | 153.0183 | −3.10 | C7H6O4 | MS2[153]: 109.0281(100), 153.0182(30), 126.0911(19) | Protocatechuic acid |
| 29 | B, C | 2.96 # | 158.0823 | 158.0811 | −7.38 | C7H13NO3 | MS2[158]: 116.0704(100), 158.0811(21) | N-Acetylvaline |
| 30 | A, B, C | 3.33 # | 181.0506 | 181.0497 | −5.43 | C9H10O4 | MS2[181]: 163.0389(100), 181.0496(68), 135.0439(54), 137.0231(42), 119.0489(34) | Ethyl 3,4-dihydroxybenzoate |
| 31 | A, B, C | 3.35 # | 167.0350 | 167.0339 | −6.24 | C8H8O4 | MS2[167]: 123.0438(100), 167.0339(10) | Isovanillic acid |
| 32 | A, B, C | 3.46 # | 203.0826 | 203.0818 | −3.85 | C11H12N2O2 | MS2[203]: 116.0492(100), 203.0816(70), 74.0233(36), 72.0077(32), 159.0916(31), 142.0650(29) | Tryptophan |
| 33 | A, B, C | 3.66 # | 175.0612 | 175.0601 | −6.16 | C7H12O5 | MS2[175]: 146.9600(100), 115.0387(80), 175.0601(69), 113.0594(32), 85.0644(31) | 2-Isopropylmalic acid |
| 34 | A, B, C | 3.77 # | 161.0244 | 161.0231 | −8.25 | C9H6O3 | MS2[161]: 161.0233(100), 133.0282(66) | 7-Hydroxycoumarin |
| 35 | A, B, C | 3.80 # | 153.0193 | 153.0182 | −3.82 | C7H6O4 | MS2[153]: 109.0282(100), 153.0181(57) | Gentisic acid |
| 36 | A, B, C | 4.16 # | 188.0353 | 188.0345 | −4.51 | C10H7NO3 | MS2[188]: 144.0443(100), 188.0343(4) | Kynurenic acid |
| 37 | C | 4.51 # | 465.1038 | 465.1038 | −0.20 | C21H22O12 | MS2[465]: 285.0403(100), 125.0232(85), 275.0563(53), 177.0189(26), 151.0033(21), 303.0518(19) | Taxifolin-glucoside |
| 38 | B, C | 4.62 *# | 289.0718 | 289.0721 | 1.00 | C15H14O6 | MS2[289]: 245.0816(100), 289.0721(94), 125.0233(62), 109.0283(58), 179.0340(48), 151.0390(30), 161.0594(20) | Catechin/Catechin hydrate |
| 39 | A, B, C | 4.78 # | 163.0401 | 163.0390 | −6.61 | C9H8O3 | MS2[163]: 163.0389(100), 120.0522(32) | 3-Coumaric acid |
| 40 | A, B, C | 5.02 # | 163.0401 | 163.0390 | −6.74 | C9H8O3 | MS2[163]: 119.0489(100), 163.0390(16) | p-Coumaric acid |
| 41 | A, C | 5.08 # | 465.1038 | 465.1037 | −0.26 | C21H22O12 | MS2[465]: 285.0403(100), 125.0232(39), 275.0558(12), 177.0183(14), 151.0033(21), 303.0507(8) | Taxifolin-glucoside isomer |
| 42 | B, C | 5.17 # | 172.0979 | 172.0969 | −5.85 | C8H15NO3 | MS2[172]: 130.0861(100), 172.0969(16), 128.1068(2) | N-Acetyl-L-leucine |
| 43 | A, B, C | 5.22 | 179.0350 | 179.0340 | −5.49 | C9H8O4 | MS2[179]: 135.0439(100), 179.0340(29) | Caffeic acid |
| 44 | B, C | 5.33 # | 151.0401 | 151.0390 | −7.14 | C8H8O3 | MS2[151]: 107.0489(100), 151.0387(5) | 2-Hydroxyphenylacetic acid |
| 45 | A, B, C | 5.41 # | 193.0506 | 193.0497 | −4.68 | C10H10O4 | MS2[193]: 134.0361(100), 149.0596(34), 193.0499(13) | Ferulic acid |
| 46 | A, B, C | 5.94 # | 375.1310 | 375.1307 | −0.96 | C17H20N4O6 | MS2[375]: 255.0884(100), 212.0821(18), 151.0388(18), 161.0234(14) | Riboflavin |
| 47 | C | 6.01 # | 449.1089 | 449.1090 | 0.17 | C21H22O11 | MS2[449]: 259.0608(100), 59.0124(94), 269.0455(78), 125.0233(37), 287.0564(32), 178.9974(18) | Eriodictyol-glucoside |
| 48 | A, B, C | 6.01 # | 206.0823 | 206.0817 | −3.00 | C11H13NO3 | MS2[206]: 164.0706(100), 147.0440(28), 58.0285(24), 206.0814(21), 70.0285(14) | N-Acetyl-L-phenylalanine |
| 49 | A, B, C | 6.16 # | 167.0350 | 167.0340 | −5.88 | C8H8O4 | MS2[167]: 167.0339(100), 152.0103(19) | 4-Methoxysalicylic acid |
| 50 | A, B, C | 6.49 # | 173.0819 | 173.0809 | −5.79 | C8H14O4 | MS2[173]: 111.0802(100), 173.0809(55), 129.0908(6), 112.0835(5) | Suberic acid |
| 51 | A, B, C | 6.54 # | 537.1038 | 537.1036 | 0.52 | C27H22O12 | MS2[537]: 339.0504(100), 229.0137(64), 295.0609(56), 197.0446(31), 135.0439(25), 179.0338(14) | Salvianolic acid U |
| 52 | A, B, C | 6.54 # | 163.0401 | 163.0390 | −6.61 | C9H8O3 | MS2[163]: 119.0490(100), 163.0389(14), 120.0522(6) | 4-Coumaric acid isomer |
| 53 | A, B, C | 6.61 # | 313.0718 | 313.0715 | −0.74 | C17H14O6 | MS2[313]: 109.0281(100), 147.0439(38), 159.0440(27), 269.0816(14) | Salvianolic acid F |
| 54 | A, B, C | 6.67 # | 174.0561 | 174.0550 | −5.82 | C10H9NO2 | MS2[174]: 146.9600(100), 174.0550(67), 130.0650(35) | Indole-3-acetic acid |
| 55 | A, B, C | 6.71 # | 537.1038 | 537.1036 | 0.52 | C27H22O12 | MS2[537]: 197.0446(100), 135.0439(80), 339.0505(68), 229.0137(64), 295.0609(63), 179.0340(42) | Salvianolic acid T |
| 56 | A, B, C | 6.91 # | 537.1038 | 537.1033 | −0.97 | C27H22O12 | MS2[537]: 197.0447(100), 135.0439(71), 339.0506(64), 295.0609(58), 229.0137(47), 179.0340(41) | Salvianolic acid J |
| 57 | B, C | 6.91 # | 313.0718 | 313.0711 | −2.09 | C17H14O6 | MS2[313]: 269.0818(100), 313.0716(46), 203.0341(44), 159.0443(31), 109.0281(22) | Salvianolic acid F isomer |
| 58 | A, B, C | 6.91 # | 493.1140 | 493.1135 | −1.08 | C26H22O10 | MS2[493]: 197.0446(100), 135.0439(63), 295.0609(34), 179.0339(33), 72.9917(24), 269.0818(21) | Salvianolic acid A isomer |
| 59 | C | 7.03 # | 433.1140 | 433.1140 | −0.17 | C21H22O10 | MS2[433]: 271.0609(100), 151.0030(30), 98.9477(74), 119.0489(11) | Naringenin-glucoside |
| 60 | A, B, C | 7.13 # | 193.0506 | 193.0497 | −4.83 | C10H10O4 | MS2[193]: 134.0361(100), 193.0496(13), 149.0596(7) | Isoferulic acid |
| 61 | C | 7.22 # | 449.1089 | 449.1087 | −0.53 | C21H22O11 | MS2[449]: 151.0025(100), 287.0558(65), 135.0439(46), 98.9477(41), 96.9587(12) | Eriodictyol hexoside 1 |
| 62 | C | 7.30 # | 433.1140 | 433.1134 | −1.44 | C21H22O10 | MS2[433]: 271.0610(100), 151.0025(33), 98.9476(10), 119.0492(6) | Naringenin-glucoside isomer |
| 63 | A, B, C | 7.50 *# | 609.1461 | 609.1456 | −0.79 | C27H30O16 | MS2[609]: 300.0273(100), 301.0345(57) | Rutin |
| 64 | A, B, C | 7.57 # | 137.0244 | 137.0231 | −9.40 | C7H6O3 | MS2[137]: 93.0332(100), 137.0232(52) | Salicylic acid isomer |
| 65 | B, C | 7.60 # | 715.1305 | 715.1303 | −0.30 | C36H28O16 | MS2[715]: 197.0446(100), 151.0390(54), 135.0437(40), 177.0182(39), 179.0339(35) | DidehydioSalvianolic acid B |
| 66 | C | 7.77 *# | 463.0882 | 463.0881 | −0.28 | C21H20O12 | MS2[463]: 300.0272(100), 301.0346(56), 151.0025(4), 178.9980(2) | Isoquercitrin |
| 67 | A, B, C | 7.81 # | 163.0401 | 163.0390 | −6.74 | C9H8O3 | MS2[163]: 163.0389(100), 137.0596(91), 119.0489(46), 162.8380(17) | 4-Coumaric acid |
| 68 | A, B, C | 7.88 # | 551.1195 | 551.1198 | 0.46 | C28H24O12 | MS2[551]: 197.0447(100), 135.0440(74), 59.0124(62), 353.0659(50), 179.0341(45), 309.0770(41) | Monomethyl lithospermate isomer |
| 69 | A, B, C | 7.92 # | 717.1461 | 717.1456 | −0.75 | C36H30O16 | MS2[717]: 339.0505(100), 321.0760(40), 295.0611(20), 197.0449(26), 135.0440(16), 179.03469(6) | Salvianolic acid B isomer |
| 70 | A, B, C | 8.02 # | 537.1038 | 537.1034 | −0.86 | C27H22O12 | MS2[537]: 295.0609(100), 339.0504(44), 109.0282(41), 185.0233(31), 277.0504(13) | Salvianolic acid isomer |
| 71 | A, B, C | 8.19 # | 357.0616 | 357.0611 | −1.46 | C18H14O8 | MS2[357]: 135.0439(100), 229.0135(31), 197.0448(29), 179.0341(23), 109.0280(17) | Salvianolic acid H |
| 72 | B, C | 8.31 # | 277.1445 | 277.1443 | −0.99 | C16H22O4 | MS2[277]: 259.1336(100), 247.1335(88), 174.0675(82), 121.0282(76), 241.1230(47) | De-O-Methyllasiodiplodin |
| 73 | A, B, C | 8.37 *# | 593.1512 | 593.1509 | −0.43 | C27H30O15 | MS2[593]: 285.0401(100), 284.0324(49) | Nicotiflorin |
| 74 | A, B, C | 8.40 # | 187.0976 | 187.0966 | −5.25 | C9H16O4 | MS2[187]: 125.0959(100), 187.0966(50), 97.0645(4), 169.0859(3) | Azelaic acid |
| 75 | A, B, C | 8.50 # | 551.1195 | 551.1201 | 1.13 | C28H24O12 | MS2[551]: 327.0827(100), 135.0439(37), 197.0446(33), 217.0499(24), 229.0137(22), 353.0664(22) | Monomethyl lithospermate |
| 76 | A, B | 8.65 *# | 609.1825 | 609.1829 | 1.61 | C28H34O15 | MS2[609]: 301.0714(100), 302.0744(8) | Hesperidin |
| 77 | A, B, C | 8.84 * | 359.0772 | 359.0769 | −0.95 | C18H16O8 | MS2[359]: 161.0233(100), 197.0446(37), 179.0339(16), 72.9917(11), 135.0440(6) | Rosmarinic acid |
| 78 | A, B, C | 8.88 # | 731.1618 | 731.1613 | −0.60 | C37H32O16 | MS2[731]: 109.0282(100), 335.0921(89), 353.0670(70), 197.0446(61), 489.1185(45) | 9″-Methyl salvianolate B isomer |
| 79 | A, B, C | 9.00 # | 731.1618 | 731.1620 | 0.32 | C37H32O16 | MS2[731]: 367.0821(100), 353.0667(97), 109.0282(74), 197.0446(58), 335.0924(53), 489.1198(35) | 9″-Methyl salvianolate B |
| 80 | A, B, C | 9.22 * | 537.1038 | 537.1036 | −0.51 | C27H22O12 | MS2[537]: 339.0511(100), 197.0447(82), 135.0440(74), 295.0613(66), 179.0338(25) | Lithospermic acid |
| 81 | A, B, C | 9.22 # | 493.1140 | 493.1138 | −0.45 | C26H22O10 | MS2[493]: 185.0235(100), 109.0281(94), 295.0608(77), 203.0343(21), 159.0440(20), 135.0439(19), 197.0448(17), 179.0343(12) | Salvianolic acid A |
| 82 | C | 9.68 # | 493.1140 | 493.1140 | −0.09 | C26H22O10 | MS2[493]: 197.0446(100), 135.0439(82), 295.0608(55), 179.0338(38), 185.0234(33), 109.0281(33), 269.0817(30) | Salvianolic acid A isomer |
| 83 | C | 10.19 * | 717.1461 | 717.1460 | −0.15 | C36H30O16 | MS2[717]: 321.0401(100), 339.0507(29), 295.0609(16), 185.0237(10), 197.0444(3), 135.0438(2), 179.0339(2) | Salvianolic acid B |
| 84 | A, B, C | 10.33 # | 357.0616 | 357.0616 | −0.12 | C18H14O8 | MS2[357]: 135.0439(100), 337.0353(56), 72.9917(27), 179.0339(26), 197.0446(25), 321.0403(18) | Salvianolic acid I |
| 85 | A, B, C | 10.66 # | 731.1618 | 731.1625 | 1.07 | C37H32O16 | MS2[731]: 229.0136(100), 339.0506(76), 313.0716(59), 203.0340(47), 267.0659(32) | 9″-Methyl salvianolate B isomer |
| 86 | A, B, C | 11.04 # | 277.1445 | 277.1441 | −1.56 | C16H22O4 | MS2[277]: 277.1443(100), 233.1541(74), 203.1433(11) | Dibutylphthalate |
| 87 | B, C | 11.16 # | 373.0929 | 373.0926 | −0.73 | C19H18O8 | MS2[373]: 135.0439(100), 175.0391(65), 197.0447(57), 179.0340(27), 72.9917(23), 161.0235(15) | Methyl rosmarinate |
| 88 | A, B, C | 11.20 # | 201.1132 | 201.1125 | −3.79 | C10H18O4 | MS2[201]: 139.1116(100), 201.1123(92), 183.1017(47) | 3-tert-Butyladipic acid |
| 89 | A, B, C | 11.65 * | 491.0984 | 491.0980 | −0.84 | C26H20O10 | MS2[491]: 311.0559(100), 135.0439(35), 197.0447(4), 179.0341(2) | Salvianolic acid C |
| 90 | C | 11.87 # | 551.1195 | 551.1193 | −0.44 | C28H24O12 | MS2[551]: 321.0400(100), 231.0292(22), 109.0281(21), 293.0455(17), 135.0440(11), 197.0447(8), 179.0337(4) | Monomethyl lithospermate isomer |
| 91 | B, C | 11.92 # | 731.1618 | 731.1627 | 1.32 | C37H32O16 | MS2[731]: 335.0560(100), 353.0666(60), 309.0762(38), 135.0439(33), 197.0446(20) | 9″-Methyl salvianolate B isomer |
| 92 | A | 12.49 *# | 301.0354 | 301.0353 | −0.22 | C15H10O7 | MS2[301]: 151.0026(100), 301.0359(89), 178.9977(53), 121.0283(19) | Quercetin |
| 93 | C | 13.01 # | 731.1618 | 731.1630 | 1.73 | C37H32O16 | MS2[731]: 339.0507(100), 229.0137(42), 295.0607(30), 359.0772(19) | 9″-Methyl salvianolate B isomer |
| 94 | A, B, C | 13.13 # | 363.1085 | 363.1086 | 0.03 | C18H20O8 | MS2[363]: 218.0214(100), 190.0262(79), 303.0872(74), 227.0343(70), 219.0251(5) | Shikonin derivative |
| 95 | C | 13.25 *# | 271.0612 | 271.0613 | 0.31 | C15H12O5 | MS2[271]: 151.0025(100), 271.0612(62), 119.0490(42), 227.1071(23), 107.0125(14), 93.0332(14), 177.0185(11) | Naringenin |
| 96 | A, B, C | 14.54 # | 285.0405 | 285.0408 | 1.30 | C15H10O6 | MS2[285]: 285.0406(100), 227.0711(16), 241.0508(11), 215.0701(11) | Kaempferol |
| 97 | A, B, C | 14.56 | 253.0870 | 253.0869 | −0.67 | C16H14O3 | MS2[253]: 237.0551(100), 238.0615(31), 270.0533(20), 253.0505(14) | Rhizonone |
| 98 | A, B, C | 14.57 | 315.1238 | 315.1239 | 0.43 | C18H20O5 | MS2[315]: 241.0865(100), 256.1102(65), 300.1002(27), 271.0973(22), 285.0762(11) | Ethylshikonin |
| 99 | A, B, C | 14.61 # | 299.0561 | 299.0561 | 0.03 | C16H12O6 | MS2[301]: 284.0323(100), 255.0293(16), 299.0560(12), 285.0359(10) | Hispidulin |
| 100 | C | 15.35 # | 583.2562 | 583.2564 | 0.24 | C33H36N4O6 | MS2[583]: 285.1242(100), 297.1239(15), 241.1341(9), 213.1030(3) | Bilirubin |
| 101 | A, B, C | 15.35 # | 187.1340 | 187.1331 | −4.53 | C10H20O3 | MS2[187]: 59.0124(100), 125.0960(21), 141.8672(14), 187.1324(14) | 3-Hydroxydecanoic acid |
| 102 | A, B, C | 15.74 # | 371.1500 | 371.1497 | −0.87 | C21H24O6 | MS2[371]: 271.0970(100), 253.0863(52), 99.0439(49), 241.0868(40), 225.0916(38) | Valerylshikonin isomer |
| 103 | A, B, C | 15.85 # | 403.1398 | 403.1398 | −0.03 | C21H24O8 | MS2[403]: 303.0875(100), 218.0215(96), 227.0345(65), 190.0258(75), 99.0435(83) | Shikonin derivative |
| 104 | B, C | 15.96 | 391.1762 | 391.1762 | −0.20 | C21H28O7 | MS2[391]: 255.1024(100), 273.1133(92), 190.0262(18), 117.0544(17), 227.0340(14) | Hydroxyshikonofuran J |
| 105 | A, B, C | 15.99 # | 391.1398 | 391.1399 | 0.21 | C20H24O8 | MS2[363]: 218.0215(100), 303.0872(98), 227.0343(87), 190.0262(82), 87.0437(71) | Shikonin derivative |
| 106 | A, B, C | 16.05 | 269.0819 | 269.0819 | −0.09 | C16H14O4 | MS2[269]: 136.0153(100), 251.0712(58), 223.0753(44), 269.0817(41), 241.0870(31) | Dehydratedshikonin |
| 107 | A, B, C | 16.13 | 333.1344 | 333.1341 | −0.82 | C18H22O6 | MS2[333]: 255.1023(100), 273.1129(66), 219.0292(15), 254.0937(2), 237.0917(1) | Hydroxyshikonofuran A |
| 108 | B, C | 16.31 | 391.1762 | 391.1763 | 0.27 | C21H28O7 | MS2[391]: 255.1023(100), 273.1133(91), 117.0545(25) | Hydroxyshikonofuran K |
| 109 | C | 16.36 # | 283.0612 | 283.0611 | −0.45 | C16H12O5 | MS2[283]: 283.0608(100), 240.0423(27), 257.0451(19), 239.0373(3) | Glycitein |
| 110 | A, B, C | 16.46 # | 333.1344 | 333.1343 | −0.07 | C18H22O6 | MS2[333]: 255.1023(100), 273.1130(65), 315.1576(30), 254.0945(2), 237.0918(2) | Hydroxyshikonofuran A isomer |
| 111 | A, B, C | 16.76 | 315.1238 | 315.1238 | −0.06 | C18H20O5 | MS2[315]: 255.1023(100), 59.0125(29), 227.1077(13), 237.0922(11), 121.0281(7), 187.0390(4) | Shikonofuran A |
| 112 | A, B, C | 16.76 | 347.1136 | 347.1134 | −0.57 | C18H20O7 | MS2[347]: 241.0867(100), 287.0922(73), 269.0824(69), 59.0124(68), 227.1079(23) | Shikonin acetate |
| 113 | A, B, C | 16.79 # | 305.1758 | 305.1758 | 1.63 | C18H26O4 | MS2[305]: 135.0803(100), 249.1492(62), 174.9551(46), 235.0195(26), 146.9600(26) | Octyl ferulate |
| 114 | C | 16.87 *# | 283.0612 | 283.0612 | −0.03 | C16H12O5 | MS2[283]: 283.0608(100), 268.0377(67), 265.1805(10) | Baicalein |
| 115 | A, B, C | 17.67 # | 349.1293 | 349.1292 | −0.37 | C18H22O7 | MS2[349]: 255.1023(100), 227.1071(43), 237.0921(13) | Shikonofurans derivative |
| 116 | A, B, C | 17.00 | 405.1555 | 405.1558 | 0.74 | C21H26O8 | MS2[405]: 303.0870(100), 218.0214(59), 190.0262(58), 227.0343(56), 245.0451(54), 101.0594(53) | Dihydrohydroxyshikonin tiglate |
| 117 | A, B, C | 17.11 * | 299.0561 | 299.0560 | −0.38 | C16H12O6 | MS2[299]: 299.0558(100), 254.0581(27), 237.0556(25), 281.0452(22), 284.0333(13) | Kaempferide |
| 118 | A, B, C | 17.14 # | 313.0718 | 313.0716 | −0.46 | C17H14O6 | MS2[313]: 298.0482(100), 202.1159(82), 283.0243(53), 312.2260(47), 255.0294(24) | Pectolinarigenin |
| 119 | B, C | 17.19 | 345.0980 | 345.0975 | −1.47 | C18H18O7 | MS2[345]: 285.0766(100), 267.0674(32), 257.0807(25), 59.0123(20) | Lithospermidin C |
| 120 | A, B, C | 18.04 * | 287.0925 | 287.0923 | −0.62 | C16H16O5 | MS2[287]: 218.0214(100), 219.0255(9), 190.0261(2) | Shikonin |
| 121 | B, C | 18.15 | 433.1868 | 433.1871 | 0.65 | C23H30O8 | MS2[433]: 255.1023(100), 273.1131(84), 273.9557(16), 59.0126(5) | Hydroxyshikonofuran F |
| 122 | A, B, C | 18.17 | 361.1657 | 361.1655 | −0.54 | C20H26O6 | MS2[361]: 255.1022(100), 273.1129(73), 259.0607(15), 87.0439(4) | Hydroxyshikonofuran G |
| 123 | B, C | 18.45 | 433.1868 | 433.1866 | −0.56 | C23H30O8 | MS2[433]: 255.1023(100), 273.1131(81), 59.0123(6), 237.0913(3) | Hydroxyshikonofuran H |
| 124 | A, B, C | 18.47 | 361.1657 | 361.1658 | 0.39 | C20H26O6 | MS2[361]: 255.1022(100), 273.1128(72), 218.0214(10), 87.0438(3) | Hydroxyshikonofuran D |
| 125 | A, B, C | 18.57 # | 269.0455 | 269.0454 | 3.57 | C15H10O5 | MS2[301]: 269.0454(100), 149.0229(1) | Apigenin |
| 126 | A, B, C | 18.65 # | 345.0980 | 345.0975 | −1.47 | C18H18O7 | MS2[345]: 285.0766(100), 267.0659(14), 257.0817(8), 59.0124(4), 239.0709(1) | Lithospermidin C isomer |
| 127 | A, B, C | 18.83 | 343.1551 | 343.1551 | −0.03 | C20H24O5 | MS2[343]: 283.0974(100), 266.0824(14), 255.1023(35), 87.0438(16), 227.1078(3) | Shikonofuran D |
| 128 | A, B, C | 18.89 | 343.1187 | 343.1184 | −0.80 | C19H20O6 | MS2[343]: 283.0974(100), 255.1023(35), 87.0438(16), 266.0824(14) | 1-Methoxyacetylshikonin |
| 129 | A, B, C | 18.92 | 373.1657 | 373.1658 | 0.37 | C21H26O6 | MS2[373]: 255.1022(100), 273.1131(61), 174.9551(35) | Hydroxyshikonofuran I |
| 130 | C | 18.99 # | 357.2071 | 357.2071 | −0.04 | C22H30O4 | MS2[357]: 357.2070(100), 339.1964(69), 295.2061(31), 327.1965(30), 269.0819(13) | Cannabidiolic acid |
| 131 | A, B, C | 19.04 # | 269.0819 | 269.0812 | −0.20 | C16H14O4 | MS2[269]: 269.0816(100), 254.0582(80), 149.0231(42), 133.0646(37), 210.0677(35) | Medicarpin |
| 132 | A, B, C | 19.16 | 373.1657 | 373.1655 | −0.36 | C21H26O6 | MS2[373]: 255.1025(100), 273.1130(67), 174.9550(24) | Hydroxyshikonofuran E |
| 133 | B, C | 19.33 | 375.1813 | 375.1812 | 1.03 | C21H28O6 | MS2[375]: 255.1025(100), 273.1132(71) | Hydroxyshikonofuran B |
| 134 | A, B, C | 19.33 | 343.1187 | 343.1185 | −0.53 | C19H20O6 | MS2[343]: 283.0973(100), 255.1021(13) | 1-methoxyacetylshikonin isomer |
| 135 | A, B, C | 19.49 | 375.1813 | 375.1810 | 0.72 | C21H28O6 | MS2[375]: 255.1023(100), 273.1132(74) | Hydroxyshikonofuran L |
| 136 | A, B, C | 19.52 | 355.1551 | 355.1546 | −1.49 | C21H24O5 | MS2[355]: 255.1025(100), 355.3217(70), 99.0438(58), 218.0218(30), 227.1070(15), 237.0919(4) | Shikonofuran E |
| 137 | B, C | 19.67 | 375.1813 | 375.1784 | −7.74 | C21H28O6 | MS2[375]: 255.1024(100), 273.1131(69), 101.0594(3) | Hydroxyshikonofuran C |
| 138 | A, B, C | 19.74 | 359.1136 | 359.1139 | 0.82 | C19H20O7 | MS2[359]: 299.0921(100), 284.0687(57), 359.1137(11), 161.0234(9), 271.0973(7) | 1/4-methoxylithospermidin C |
| 139 | A, B, C | 19.80 | 425.1242 | 425.1245 | 1.90 | C23H22O8 | MS2[425]: 321.1494(100), 178.9977(59), 227.1074(58), 271.0969(27), 363.1226(21), 245.1178(16), 345.1130(12) | Unknown |
| 140 | A, B, C | 19.80 | 375.1813 | 375.1811 | −0.52 | C21H28O6 | MS2[375]: 255.1023(100), 273.1131(72), 101.0594(3) | Hydroxyshikonofuran M |
| 141 | A, B | 20.06 | 357.1707 | 357.1705 | −0.61 | C21H26O5 | MS2[357]: 255.1023(100), 101.0594(47), 297.1130(18), 227.1069(9), 121.0281(7), 237.0916(6) | Shikonofuran B |
| 142 | A, B, C | 20.15 | 357.1707 | 357.1704 | −0.95 | C21H26O5 | MS2[357]: 255.1023(100), 101.0594(45), 227.1068(10), 237.0921(8), 121.0283(8), 172.0517(2), 143.0497(2) | Shikonofuran C |
| 143 | A, B, C | 20.16 | 371.1500 | 371.1497 | −0.79 | C21H24O6 | MS2[371]: 269.0817(100), 241.0866(16), 251.0706(7) | α,α-dimethylpropionylshikonin |
| 144 | A, B, C | 20.50 | 387.1449 | 387.1448 | −0.30 | C21H24O7 | MS2[387]: 117.0544(100), 269.0813(31), 251.0711(31), 59.0123(21), 241.0867(13) | β-hydroxyisovalerylshikonin |
| 145 | A, B, C | 20.94 | 401.1606 | 401.1605 | 1.16 | C22H26O7 | MS2[401]: 299.0923(100), 255.1027(57), 121.0284(15), 313.0705(10), 237.0908(10) | 1-Methoxy-β-hydroxyisovalerylshikonin |
| 146 | A, B, C | 21.33 | 387.1449 | 387.1448 | −0.23 | C21H24O7 | MS2[387]: 101.0594(100), 189.0184(76), 285.0765(60), 217.0135(49), 257.0814(28), 267.0659(19) | Lithospermidin A |
| 147 | B, C | 21.69 | 459.1661 | 459.1664 | 0.71 | C24H28O9 | MS2[459]: 299.0916(100), 59.0124(58), 271.0966(36), 281.0820(21) | 1/4-methoxylithospermidin H |
| 148 | B, C | 21.70 | 445.1504 | 445.1503 | −0.18 | C23H26O9 | MS2[445]: 285.0766(100), 257.0819(9), 59.0124(8), 267.0657(7) | Lithospermidin D |
| 149 | A, B | 21.76 # | 271.0976 | 271.0974 | −0.53 | C16H16O4 | MS2[271]: 253.0867(100), 271.0968(73), 203.0342(58), 256.0739(44), 238.0630(39) | Deoxyshikonin isomer |
| 150 | A, B, C | 21.89 * | 329.1031 | 329.1030 | −0.19 | C18H18O6 | MS2[329]: 269.0818(100), 251.0710(81), 241.0868(48), 59.0124(47) | Acetylshikonin |
| 151 | A, B, C | 22.80 | 387.1449 | 387.1449 | 0.01 | C21H24O7 | MS2[387]: 299.0923(100), 270.0893(94), 285.0756(68), 271.0954(66), 87.0438(63), 253.0864(24) | 1/4-methoxylithospermidin I |
| 152 | A, B, C | 22.84 | 373.1293 | 373.1293 | 0.15 | C20H22O7 | MS2[373]: 285.0768(100), 267.0663(10), 257.0817(9), 174.9552(8), 87.0438(6) | Lithospermidin E |
| 153 | B, C | 23.03 # | 445.1504 | 445.1497 | −1.61 | C23H26O9 | MS2[445]: 285.0768(100), 257.0817(49), 59.0123(18), 267.0655(7) | Lithospermidin D isomer |
| 154 | A, B, C | 23.13 | 387.1449 | 387.1447 | −0.56 | C21H24O7 | MS2[387]: 299.0903(100), 285.0767(78), 270.0897(74), 87.0438(58), 271.0974(50) | 1/4-methoxylithospermidin E |
| 155 | A, B, C | 24.03 | 285.0768 | 285.0767 | −0.66 | C16H14O5 | MS2[285]: 285.0766(100), 267.0659(55), 227.0344(50), 73.0281(8), 257.0817(6), 239.0708(2) | Sakuranetin |
| 156 | B, C | 24.23 # | 445.1504 | 445.1504 | −0.11 | C23H26O9 | MS2[445]: 285.0771(100), 257.0809(93), 59.0124(35) | Lithospermidin D isomer |
| 157 | A, B, C | 24.57 | 399.1449 | 399.1445 | −1.07 | C22H24O7 | MS2[399]: 270.0891(100), 299.0921(98), 271.0978(68), 99.0437(56), 281.0811(21) | 1/4-methoxylithospermidin J |
| 158 | A, B, C | 24.63 | 385.1293 | 385.1292 | −0.33 | C21H22O7 | MS2[385]: 285.0767(100), 257.0817(11), 99.0438(9), 267.0651(8) | Lithospermidin F |
| 159 | A, B, C | 24.81 | 399.1449 | 399.1445 | −1.07 | C22H24O7 | MS2[399]: 299.0921(100), 271.0957(63), 99.0438(53), 281.0811(25) | 1/4-methoxylithospermidin F |
| 160 | A, B, C | 24.99 | 343.1187 | 343.1193 | 1.69 | C19H20O6 | MS2[343]: 57.0332(100), 343.2271(79), 269.0806(55), 251.0713(51), 285.1859(50), 73.0281(43), 241.0872(33) | Propionylshikonin |
| 161 | A, B, C | 25.48 | 401.1606 | 401.1603 | −0.67 | C22H26O7 | MS2[401]: 299.0919(100), 270.0900(92), 101.0594(61), 271.0976(53), 281.0826(21), 253.0871(17) | 1/4-methoxylithospermidin A |
| 162 | A, B, C | 25.60 | 387.1449 | 387.1448 | −0.30 | C21H24O7 | MS2[387]: 285.0766(100), 257.0816(9), 101.0594(9), 267.0658(8) | Lithospermidin B |
| 163 | B, C | 26.29 | 459.1661 | 459.1654 | −1.41 | C24H28O9 | MS2[459]: 299.0922(100), 271.0971(10), 59.0124(9) | 1/4-methoxylithospermidin D |
| 164 | B | 26.38 # | 445.1504 | 445.1500 | −0.94 | C23H26O9 | MS2[445]: 285.0768(100), 257.0815(54), 59.0125(21), 267.0662(6) | Lithospermidin D isomer |
| 165 | B | 26.38 # | 271.0976 | 271.0974 | −0.86 | C16H16O4 | MS2[271]: 253.0867(100), 271.0966(71), 203.0341(57), 256.0736(48), 238.0629(39) | Deoxyshikonin isomer |
| 166 | A, B, C | 26.60 | 429.1555 | 429.1552 | −0.59 | C23H26O8 | MS2[429]: 269.0822(100), 251.0710(65), 59.0125(65), 241.0866(35) | 5-acetoxy-valerylshikonin |
| 167 | A, B | 28.04 # | 271.0976 | 271.0974 | −0.53 | C16H16O4 | MS2[271]: 253.0866(100), 271.0967(66), 203.0341(54), 256.0738(45), 238.0629(42) | Deoxyshikonin isomer |
| 168 | B, C | 28.07 | 429.1555 | 429.1551 | −0.87 | C23H26O8 | MS2[429]: 269.0822(100), 251.0706(63), 59.0124(61), 241.0871(37) | β-acetoxyisovalerylshikonin |
| 169 | A, B, C | 28.08 # | 425.1242 | 425.1227 | −2.13 | C23H22O8 | MS2[425]: 269.0818(100), 251.0710(27), 87.0437(17), 241.0966(10) | Shikonin derivative |
| 170 | A, B, C | 28.16 | 357.1344 | 357.1342 | −0.40 | C20H22O6 | MS2[357]: 269.0819(100), 251.0713(70), 87.0438(63), 241.0863(50), 223.0820(4) | Butyrylshikonin |
| 171 | A, B, C | 29.19 | 357.1344 | 357.1342 | −0.40 | C20H22O6 | MS2[357]: 269.0819(100), 251.0707(66), 87.0437(72), 241.0866(43) | Isobutyrylshikonin |
| 172 | A, B, C | 29.53 | 399.1449 | 339.1999 | 9.71 | C22H24O7 | MS2[399]: 299.0923(100), 99.0439(11), 281.0812(10), 271.0970(9) | 1/4-Methoxylithospermidin L |
| 173 | A, B, C | 30.11 # | 271.0976 | 271.0974 | −0.64 | C16H16O4 | MS2[271]: 253.0867(100), 271.0967(74), 203.0341(54), 256.0736(45), 238.0631(41) | Deoxyshikonin isomer |
| 174 | A, B, C | 30.19 * | 369.1344 | 369.1342 | −0.39 | C21H22O6 | MS2[369]: 269.0818(100), 251.0710(71), 99.0438(68), 270.0888(57), 241.0867(49) | β,β-dimethylacrylshikonin |
| 175 | A, B, C | 30.44 | 401.1606 | 401.1603 | −0.59 | C22H26O7 | MS2[401]: 299.0924(100), 121.0283(15), 271.0959(12), 101.0592(11), 281.0879(10) | 1/4-methoxylithospermidin B |
| 176 | A, B, C | 30.64 | 599.1923 | 599.1926 | 1.52 | C34H32O10 | MS2[599]: 426.1099(100), 412.0935(42), 102.9554(26), 132.4304(21), 116.5537(21), 59.0124(21) | 7-(11′-Deoxyalkannin)-Acetylshikonin |
| 177 | A | 30.72 | 369.1344 | 369.1340 | −1.07 | C21H22O6 | MS2[369]: 269.0817(100), 251.0709(68), 99.0438(61), 241.0864(52) | α-methylene-butenoylshikonin |
| 178 | A, B, C | 30.89 # | 271.0976 | 271.0974 | −0.53 | C16H16O4 | MS2[271]: 253.0868(100), 271.0968(77), 203.0343(64), 256.0738(47), 238.0630(40) | Deoxyshikonin isomer |
| 179 | A, B, C | 30.98 | 371.1500 | 371.1497 | −0.95 | C21H24O6 | MS2[371]: 269.0818(100), 251.0710(66), 101.0594(65), 241.0865(43) | α-methylbutyrylshikonin |
| 180 | A, B, C | 31.62 | 555.1661 | 555.1657 | −0.63 | C32H28O9 | MS2[555]: 486.0952(100), 555.1646(11) | Shikometabolin B |
| 181 | A, B, C | 31.78 | 599.1923 | 599.1936 | 3.14 | C34H32O10 | MS2[599]: 412.0944(100), 426.1105(77) | 7-(11′-Deoxyalkannin)-Acetylalkannin |
| 182 | A | 32.05 | 369.1344 | 369.1343 | −0.14 | C21H22O6 | MS2[369]: 269.0816(100), 251.0705(48), 99.0439(43), 241.0871(37) | Tigloylshikonin |
| 183 | A, B, C | 33.05 | 371.1500 | 371.1497 | −0.95 | C21H24O6 | MS2[371]: 269.0819(100), 101.0594(71), 251.0710(64), 241.0866(47) | Isovalerylshikonin |
| 184 | A, B, C | 34.64 # | 271.0976 | 271.0973 | −1.08 | C16H16O4 | MS2[271]: 253.0866(100), 271.0974(66), 203.0341(58), 256.0735(45), 238.0630(37) | Deoxyshikonin isomer |
| 185 | A | 35.15 | 369.1344 | 369.1342 | −0.47 | C21H22O6 | MS2[369]: 269.0829(100), 251.0721(46), 99.0443(54), 241.0867(40) | Angeloylshikonin |
| 186 | A, B, C | 35.84 | 627.2236 | 627.2235 | 0.69 | C36H36O10 | MS2[627]: 426.1100(100), 412.0944(80), 87.0437(45), 495.1801(24), 349.1006(12), 290.5349(12) | 7-(11′-Deoxyalkannin)-Isobutyrylshikonin |
| 187 | A, B, C | 38.59 | 639.2236 | 639.2231 | 0.19 | C37H36O10 | MS2[639]: 537.1556(100), 639.2231(5), 509.1626(4), 519.1473(2), 101.0590(2) | 7-(11′-Deoxyalkannin)-β,β-dimethylacrylshikonin |
| 188 | A, B, C | 38.89 | 639.2236 | 639.2232 | 0.30 | C37H36O10 | MS2[639]: 537.1553(100), 639.2230(4), 519.1443(2), 101.0589(1) | 7-(11′-Deoxyalkannin)-β,β-dimethylacrylalkannin |
* Identified by comparison with standards. # First reported in Arnebiae Radix.