Table 2.
The summary results of the standards and marker compounds analyzed by HPLC-ESI-TOF-MS technique
| No. | RT (min) | Marker ion Exact Mass (ppm) | Selected fragmental ions Exact mass [Adduct molecular ions – neutral molecules or redicals]+ (molecular formula, ppm) | UV (λmax nm) | Identification | Type of Marker compoundsa |
|---|---|---|---|---|---|---|
| 1 | 13.44 | 469.1703 (−1.5) [M + H]+ (C22H29O11) | 451.1602 [M + H – H2O]+ (C22H27O10, −0.4); 421.1099 [M + H – H2O – 2CH3·]+ (C20H21O10, −8.5); 397.1128 [M + H – 2,2-dimethylepoxyethane]+ (C18H21O10, −1.8); 307.1161 [M + H – glucosyl group]+ (C16H19O6, −6.8); 290.1126 [M + H – glucosyl group – HO·]+ (C16H18O5, −9.6); 289.1060 [M + H – glucosyl group – H2O]+ (C16H17O5, −5.5); 261.1102 [M + H – glucosyl group – H2O – CO]+ (C14H11O5, −9.6); 259.0580 [M + H – glucosyl group – H2O – 2CH3·]+ (C14H11O5, −10.0); 235.0572 [M + H – glucosyl group – 2,2-dimethylepoxyethane]+ (C12H11O5, −14.5). | 300.0, 254.2sh, 215.0 | prim-O-glucosylcimifugin | A |
| 2 | 16.57 | 307.1160 (−7.2) [M + H]+ (C16H19O6) | 289.1068 [M + H – H2O]+ (C16H17O5, −2.8); 259.0573 [M + H – H2O – 2CH3·]+ (C14H11O5, −12.7); 235.0569 [M + H - 2,2-dimethylepoxyethane]+ (C12H11O5, −15.7); 217.0465 [M + H – 2,2-dimethylepoxyethane – H2O]+ (C12H9O4, −16.7); 207.0612 [M + H – 2,2-dimethylepoxyethane – CO]+ (C11H11O4, −21.7) | 298.0, 254.3sh, 217.0 | cimifugin | A |
| 3 | 12.41 | 321.0953 (−6.5) [M + H]+ (C16H17O7) | 303.0852 [M + H – H2O]+ (C16H15O6, −5.6); 273.0367 [M + H – H2O – 2CH3·]+ (C14H9O6, −11.7); 249.0362 [M + H - 2,2-dimethylepoxyethane]+ (C12H9O6, −14.9); 231.0222 [M + H – 2,2-dimethylepoxyethane – H2O]+ (C12H7O5, −17.7); 221.0414 [M + H – 2,2-dimethylepoxyethane – CO]+ (C11H9O5, −16.3) | 310.0, 255.0sh, 217.0 | divaricatacid | A |
| 4 | 38.39 | 639.3508 (−0.2) [M + Na]+ (C35H52O9Na) | 617.3694 [M + H]+ (C35H53O9, 0.6); 599.3591 [M + H – H2O]+ (C35H51O8, 1.2); 577.3390 [M + H – propa-1,2-diene]+ (C32H49O9, 2.3); 467.3165 [M + H – xylose]+ (C30H43O4, 0.9); 449.3050 [M + H – xylose – H2O]+ (C30H41O3, −1.3); 427.2861 [M + H – xylose – propa-1,2-diene]+ (C27H39O4, 3.0); 395.2580 [M + H – xylose – 2,2-dimethylepoxyethane]+ (C26H35O3, − 1.5); 377.2475 [M + H – xylose – H2O – 2,2-dimethylepoxyethane]+ (C26H33O2, −1.6); | cimicifugoside H-1 | Not marker compound | |
| 5 | 28.56 | 655.3448 (−1.5) [M + Na]+ (C35H52O10Na) | 633.3636 [M + H]+ (C35H53O10, −0.5); 615.3523 [M + H – H2O]+ (C35H51O9, −1.6); 575.3218 [M + H – H2O – propa-1,2-diene]+ (C32H47O9, −0.3); 561.3074 [M + H – 2,2-dimethylepoxyethane]+ (C31H45O9, 1.8); 483.3104 [M + H – xylose]+ (C30H43O5, −1.2); 465.3004 [M + H – xylose – H2O]+ (C30H41O4, −0.2); 447.2879 [M + H – xylose – 2H2O]+ (C30H39O3, −4.5) 443.2796 [M + H – xylose – propa-1,2-diene]+ (C27H39O5, −0.2); 425.2690 [M + H – xylose – H2O – propa-1,2-diene]+ (C27H37O4, −0.5); 411.2523 [M + H – xylose – 2,2-dimethylepoxyethane]+ (C26H35O4, −2.9); 393.2419 [M + H – xylose – H2O – 2,2-dimethylepoxyethane]+ (C26H33O3, −2.8); 375.2308 [M + H – xylose – 2H2O – 2,2-dimethylepoxyethane]+ (C26H31O2, − 4.3); | cimicifugoside H-5 | A | |
| 6 | 35.90 | 771.3942 (1.3) [M + Na]+ (C40H60O13Na) | 749.4130 [M + H]+ (C40H61O13, 2.4); 731.3984 [M + H – H2O]+ (C40H59O12, −3.1); 599.3588 [M + H – xylose]+ (C35H51O8, 0.7); 559.3263 [M + H – xylose – propa-1,2-diene]+ (C32H47O8, −1.4); 467.3158 [M + H – 2xylose]+ (C30H43O4, −0.6); 449.3054 [M + H – 2xylose – H2O]+ (C30H41O3, −0.4); 427.2846 [M + H – 2xylose – propa-1,2-diene]+ (C27H39O4, −0.5); 409.2753 [M + H – 2xylose – H2O – propa-1,2-diene]+ (C27H37O3, 2.4); 395.2620 [M + H – 2xylose – 2,2-dimethylepoxyethane]+ (C26H35O3, 8.6); 377.2483 [M + H – 2xylose – H2O – 2,2-dimethylepoxyethane]+ (C26H33O2, 0.5). | shengmacichun dixyloside | D | |
| 7 | 48.12 | 685.3895 (−4.8) [M + Na]+ (C37H58O10Na) | 663.4145 [M + H]+ (C37H59O10, 5.6); 645.3975 [M + H – H2O]+ (C37H57O9, −4.3); 603.3932 [M + H – acetic acid]+ (C35H55O8, 5.8); 585.3770 [M + H – acetic acid – H2O]+ (C35H53O7, −3.6); 545.3511 [M + H – acetic acid – H2O – propa-1,2-diene]+ (C32H49O7, 6.1); 531.3333 [M + H – acetic acid – 2,2-dimethylepoxyethane]+ (C31H47O7, 2.1); 513.3542 [M + H – xylose]+ (C32H49O5, −7.4); 495.3451 [M + H – xylose – H2O]+ (C32H47O4, 4.6); 453.3370 [M + H – xylose – acetic acid]+ (C30H45O3, 0.2); 435.3266 [M + H – xylose – acetic acid – H2O]+ (C30H43O2, 0.7); 413.3070 [M + H – xylose – acetic acid – propa-1,2-diene]+ (C27H41O3, 3.4); 395.2958 [M + H – xylose – acetic acid – H2O – propa-1,2-diene]+ (C27H39O2, 2.0); 381.2799 [M + H – xylose – acetic acid – 2,2-dimethylepoxyethane]+ (C26H37O2, 1.3); 363.2690 [M + H – xylose – acetic acid – H2O – 2,2-dimethylepoxyethane]+ (C26H35O, 0.6). | 23-O-acetylshengmanol 3-O-β-D-xylopyranoside | Not marker compound | |
| 8 | 41.59 | 847.4446 (−1.2) [M + Na]+ (C43H68O15Na) | 825.4619 [M + H]+ (C43H69O15, −2.1); 807.4501 [M + H – H2O]+ (C43H67O14, −3.7); 663.4095 [M + H – glucosyl group]+ (C37H59O10, −2.0); 645.4001 [M + H – glucosyl group – H2O]+ (C37H57O9, −0.3); 513.3581 [M + H – glucosyl group – xylose or arabinose]+ (C32H49O5, 0.2); 495.3475 [M + H – glucosyl group – xylose or arabinose – H2O]+ (C32H47O4, 0.2); 471.3484 [M + H – glucosyl group – xylose or arabinose – Ac]+ (C30H47O4, 2.1); 453.3388 [M + H – glucosyl group – xylose or arabinose – actetic acid]+ (C30H45O3, 4.2); 435.3284 [M + H – glucosyl group – xylose or arabinose – actetic acid – H2O]+ (C30H43O2, 4.8); 431.3179 [M + H – glucosyl group – xylose or arabinose – Ac – propa-1,2-diene]+ (C27H43O4, 4.2); 413.3058 [M + H – glucosyl group – xylose or arabinose – actetic acid – propa-1,2-diene]+ (C27H41O3, 0.5); 381.2804 [M + H – glucosyl group – xylose or arabinose – actetic acid – 2,2-dimethylepoxyethane]+ (C26H37O2, 2.6); 363.2682 [M + H – glucosyl group – xylose or arabinose – actetic acid – H2O – 2,2-dimethylepoxyethane]+ (C26H35O, −1.7) | 23-O-acetylshengmanol-3-O-β-D-glucopyranoside-(1–3)-β-D-xylopyranoside or arabinoside | D | |
| 9 | 32.92 | 703.4042 (1.3) [M + Na]+ (C37H60O11Na) | 663.4106 [M + H – H2O]+ (C37H59O10, −0.5); 645.4000 (C37H57O9, −0.8); 621.4014 [M + H – acetic acid]+ (C35H57O9, 2.9); 603.3905 [M + H – acetic acid – H2O]+ (C35H55O8, 2.2); 585.3795 [M + H – acetic acid – 2H2O]+ (C35H53O7, 1.2); 563.3603 [M + H – acetic acid – H2O – propa-1,2-diene]+ (C32H51O8, 6.0); 531.3677 [M + H – xylose or arabinose]+ (C32H51O6, −3.2); 513.3572 [M + H – xylose or arabinose – H2O]+ (C32H49O5, −3.1); 471.3472 [M + H – xylose or arabinose – acetic acid]+ (C30H47O4, −0.8); 453.3365 [M + H – xylose or arabinose – H2O – acetic acid]+ (C30H45O3, −2.0); 435.3264 [M + H – xylose or arabinose – 2H2O – acetic acid]+ (C30H43O2, 0.4); 399.2909 [M + H – xylose or arabinose – acetic acid – 2,2-dimethylepoxyethane]+ (C26H39O3, 6.2); 395.2963 [M + H – xylose or arabinose – 2H2O – acetic acid – propa-1,2-diene]+ (C27H39O2, 8.3); 381.2785 [M + H – xylose or arabinose – H2O – acetic acid – 2,2-dimethylepoxyethane]+ (C26H37O2, −6.3); 363.2677 [M + H – xylose or arabinose – 2H2O – acetic acid – 2,2-dimethylepoxyethane]+ (C26H35O, −8.3) | 24-O-acetylhydroshengmano l-3-O-β-D-xylopyranoside or arabinoside | C | |
| 10 | 60.93 | 643.3813 (1.4) [M + Na]+ (C35H56O9Na) | 621.4022 [M + H]+ (C35H57O9, 3.1); 603.3898 [M + H – H2O]+ (C35H55O8, −0.2); 585.3795 [M + H – 2H2O]+ (C35H53O7, 0.7); 531.3356 [M + H – H2O – 2,2-dimethylepoxyethane]+ (C31H47O7, 6.4); 471.3481 [M + H – arabinose]+ (C30H47O4, 1.5); 453.3388 [M + H – arabinose – H2O]+ (C30H45O3, 4.2); 435.3286 [M + H – arabinose – 2H2O]+ (C30H43O2, 5.3); 417.3160 [M + H – arabinose – 3H2O]+ (C30H41O, −1.7); 381.2786 [M + H – arabinose – H2O – 2,2-dimethylepoxyethane]+ (C26H37O2, −2.1); 363.2683 [M + H – arabinose – 2H2O – 2,2-dimethylepoxyethane]+ (C26H35O, −1.4) | cimiracemoside C | C | |
| 11 | 78.81 | 685.3916 (−1.8) [M + Na]+ (C37H58O10Na) | 663.4117 [M + H]+ (C37H59O10, 1.4); 645.4024 [M + H – H2O]+ (C37H57O9, 3.3); 603.3891 [M + H – acetic acid]+ (C35H55O8, − 1.0); 585.3789 [M + H – acetic acid – H2O]+ (C35H53O7, −0.3); 513.3586 [M + H – xylose]+ (C32H49O5, 1.2); 495.3496 [M + H – xylose – H2O]+ (C32H47O4, 4.4); 453.3366 [M + H – xylose – acetic acid]+ (C30H45O3, −0.7); 435.3258 [M + H – xylose – acetic acid – H2O]+ (C30H43O2, −1.1); 381.2778 [M + H – xylose – acetic acid – 2,2-dimethylepoxyethane]+ (C26H37O2, −4.2); 363.2677 [M + H – xylose – acetic acid – H2O – 2,2-dimethylepoxyethane]+ (C26H35O, −3.0). | 25-O-acetylcimigenol 3-O-β-D-xylopyranoside | Not marker compound | |
| 12 | 22.41 | 675.3727 (1.0) [M + Na]+ (C35H56O11Na) | 635.3799 [M + H – H2O]+ (C35H55O10, 0.6); 617.3694 [M + H – 2H2O]+ (C35H53O9, 0.6); 599.3583 [M + H – 3H2O]+ (C35H51O8, −0.2); 581.3478 [M + H – 4H2O]+ (C35H49O7, 0.0); 545.3130 [M + H – 2H2O – 2,2-dimethylepoxyethane]+ (C31H45O8, 2.9); 503.3369 [M + H – arabinose]+ (C30H47O6, −0.8); 485.3271 [M + H – arabinose – H2O]+ (C30H45O5, 0.8); 467.3165 [M + H – arabinose – 2H2O]+ (C30H43O4, 0.9); 449.3062 [M + H – arabinose – 3H2O]+ (C30H41O3, 1.3); 413.2722 [M + H – arabinose – H2O – 2,2-dimethylepoxyethane]+ (C26H37O4, 7.3); 395.2588 [M + H – arabinose – 2H2O – 2,2-dimethylepoxyethane]+ (C26H35O3, 0.5); 377.2475 [M + H – arabinose – 3H2O – 2,2-dimethylepoxyethane]+ (C26H33O2, −1.6) | 12β,21-dihydroxycimigenol-3-O-L-arabinoside | C | |
| 13 | 36.65 | 677.3904 (0.4) [M + H]+ (C37H57O11) | 659.3799 [M + H – H2O]+ (C37H55O10, 0.6); 617.3688 [M + H – acetic acid]+ (C35H53O9, −0.4); 599.3578 [M + H – H2O – acetic acid]+ (C35H51O8, −1.0); 581.3455 [M + H – 2H2O – acetic acid]+ (C35H49O7, −4.0); 527.3363 [M + H – xylose]+ (C32H47O6, − 1.9); 467.3164 [M + H – xylose – acetic acid]+ (C30H43O4, 0.6); 449.3047 [M + H – xylose – acetic acid – H2O]+ (C30H41O3, − 2.0); 431.2951 [M + H – xylose – acetic acid – 2H2O]+ (C30H39O2, 0.2); 395.2586 [M + H – xylose – acetic acid – 2,2-dimethylepoxyethane]+ (C26H35O3, 0.0); 377.2465 [M + H – xylose – acetic acid – H2O – 2,2-dimethylepoxyethane]+ (C26H33O2, −4.2); 359.2328 [M + H – xylose – acetic acid – 2H2O – 2,2-dimethylepoxyethane]+ (C26H31O, −13.1) | cimiracemoside A | Not marker compound | |
| 14 | 47.29 | 677.3923 (3.2) [M + H]+ (C37H57O11) | 659.3782 [M + H – H2O]+ (C37H55O10, −2.0); 617.3701 [M + H – acetic acid]+ (C35H53O9, 1.8); 599.3586 [M + H – H2O – acetic acid]+ (C35H51O8, 0.3); 581.3487 [M + H – 2H2O – acetic acid]+ (C35H49O7, 1.5); 527.3391 [M + H – xylose]+ (C32H47O6, 3.4); 467.3171 [M + H – xylose – acetic acid]+ (C30H43O4, 2.1); 449.3063 [M + H – xylose – acetic acid – H2O]+ (C30H41O3, 1.6); 431.2971 [M + H – xylose – acetic acid – 2H2O]+ (C30H39O2, 4.9) | actein | Not marker compound | |
| 15 | 44.42 | 661.3952 (0.0) [M + H]+ (C37H57O10) | 643.3864 [M + H – H2O]+ (C37H55O9, 2.8); 601.3751 [M + H – acetic acid]+ (C35H53O8, 1.8); 583.3648 [M + H – H2O – acetic acid]+ (C35H51O7, 2.2); 565.3551 [M + H – 2H2O – acetic acid]+ (C35H49O6, 3.9); 511.3448 [M + H – xylose]+ (C32H47O5, 4.9); 451.3210 [M + H – xylose – acetic acid]+ (C30H43O3, −0.4); 433.3120 [M + H – xylose – acetic acid – H2O]+ (C30H41O2, 3.0); 415.3036 [M + H – xylose – acetic acid – 2H2O]+ (C30H39O, 8.4) | 26-deoxyactein | Not marker compound | |
| 16 | 52.84 | 625.3726 (1.6) [M + Na]+ (C35H54O8Na) | 603.3911 [M + H]+ (C35H55O8, 2.3); 585.3788 [M + H – H2O]+ (C35H53O7, −0.5); 561.3434 [M + H – H2O – propene]+ (C32H49O8, 1.2); 453.3376 [M + H – arabinose]+ (C30H45O3, 1.5); 435.3236 [M + H – arabinose – H2O]+ (C30H43O2, −6.2); 411.2885 [M + H – arabinose – propene]+ (C27H39O3, −3.4); 397.2731 [M + H – arabinose – 2-methylpropene]+ (C26H37O3, −3.0); 393.2791 [M + H – arabinose – H2O – propene]+ (C27H37O2, −0.8); 379.2625 [M + H – arabinose – H2O – 2-methylpropene]+ (C26H35O2, −3.2) | (23R,24S)-25-anhydrocimigenol-3-O-α-L-arabinose; | D | |
| 17 | 42.16 | 683.3776 (0.7) [M + Na]+ (C37H56O10Na) | 661.3954 [M + H]+ (C37H57O10, 0.3); 601.3738 [M + H – acetic acid]+ (C35H51O7, 2.5); 583.3615 [M + H – acetic acid – H2O]+ (C35H53O8, −0.3); 559.3281 [M + H – acetic acid – propene]+ (C32H47O8, 1.8); 511.3444 [M + H – xylose]+ (C32H47O5, 3.9); 469.3323 [M + H – xylose – Ac]+ (C30H45O4, 1.1); 451.3189 [M + H – xylose – acetic acid]+ (C30H43O3, −5.1); 433.3082 3189 [M + H – xylose – acetic acid – H2O]+ (C30H41O2, −5.8); 427.2848 [M + H – xylose – Ac – propene]+ (C27H39O4, 0.0); 409.2731 [M + H – xylose – acetic acid – propene]+ (C27H37O3, −2.9); 395.2586 [M + H – xylose – acetic acid – 2-methylpropene]+ (C26H35O3, 0.0); 377.2473 [M + H – xylose – acetic acid – H2O – 2-methylpropene]+ (C26H33O2, −2.1) | cimiracemoside K | D | |
| 18 | 57.91 | 623.3569 (1.4) [M + Na]+ (C35H52O8Na) | 601.3752 [M + H]+ (C35H53O8, 2.0); 583.3650 [M + H – H2O]+ (C35H51O7, 2.6); 559.3271 [M + H – propene]+ (C32H47O8, 0.0); 545.3136 [M + H – 2-methylpropene]+ (C31H45O8, 4.0); 527.2999 [M + H – H2O – 2-methylpropene]+ (C31H43O7, −1.9); 469.3320 [M + H – xylosyl group]+ (C30H45O4, 0.4); 451.3220 [M + H – xylose]+ (C30H43O3, 1.8); 433.3062 [M + H – xylose – H2O]+ (C30H41O2, −10.4); 427.2848 [M + H – xylosyl group – propene]+ (C27H39O4, 0.5); 409.2722 [M + H – xylose – propene]+ (C27H37O3, −5.1); 395.2585 [M + H – xylose – 2-methylpropene]+ (C26H35O3, −0.5); 377.2474 [M + H – xylose – H2O – 2-methylpropene]+ (C26H33O2, −1.9); | (23R,24R)-7-en-25-anhydrocimigenol-3-O-β-D-xylopyranoside | D | |
| 19 | 53.99 | 623.3569 (1.4) [M + Na]+ (C35H52O8Na) | 601.3745 [M + H]+ (C35H53O8, 0.8); 583.3651 [M + H – H2O]+ (C35H51O7, 2.7); 559.3276 [M + H – propene]+ (C32H47O8, 0.9); 527.3028 [M + H – H2O – 2-methylpropene]+ (C31H43O7, 3.6); 469.3314 [M + H – arabinosyl group]+ (C30H45O4, −0.9); 451.3222 [M + H – arabinose]+ (C30H43O3, 2.2); 433.3093 [M + H – arabinose – H2O]+ (C30H41O2, −3.2); 427.2842 [M + H – arabinosyl group – propene]+ (C27H39O4, −0.9); 409.2733 [M + H – arabinose – H2O – propene]+ (C27H37O3, −2.4); 395.2586 [M + H – arabinose – H2O – 2-methylpropene]+ (C26H35O3, −0.3); 377.2469 [M + H – arabinose – 2H2O – 2-methylpropene]+ (C26H33O2, −3.2); | (23R,24R)-7-en-25-anhydro cimigenol-3-O-α-L-arabinoside | D | |
| 20 | 36.75 | 643.3842 (3.1) [M + Na]+ (C35H56O9Na) | 621.4006 [M + H]+ (C35H57O9, 0.5); 603.3908 [M + H – H2O]+ (C35H55O8, 1.5); 585.3798 [M + H – 2H2O]+ (C35H53O7, 1.2); 579.3531 [M + H – propene]+ (C32H51O9, −0.3); 561.3434 [M + H – H2O – propene]+ (C32H49O8, 1.2); 471.3478 [M + H – xylose]+ (C30H47O4, 0.8); 453.3381 [M + H – xylose – H2O]+ (C30H45O3, 2.6); 435.3264 [M + H – xylose – 2H2O]+ (C30H43O2, 0.2); 429.2993 [M + H – xylose – propene]+ (C27H41O4, −0.7); 411.2888 [M + H – xylose – H2O – propene]+ (C27H39O3, −2.7); 397.2745 [M + H – xylose – H2O – 2-methylpropene]+ (C26H37O3, 0.5); 379.2635 [M + H – xylose – 2H2O – 2-methylpropene]+ (C26H35O2, 0.5) | Cimidahuside G | D | |
| 21 | 17.55 | 614.3679 (−2.3) [M + H]+ (C35H52NO8) | 596.3611 [M + H – H2O]+ (C35H50NO7, 4.0); 578.3476 [M + H – 2H2O]+ (C35H48NO6, −1.0); 560.3345 [M + H – 3H2O]+ (C35H46NO5, −5.5); 556.3260 [M + H – H2O – propa-1,2-diene]+ (C32H46NO7, −2.5); 464.3148 [M + H – xylose]+ (C30H42NO3, −3.7); 446.3062 [M + H – xylose – H2O]+ (C30H40NO2, 0.7); 428.2952 [M + H – xylose – 2H2O]+ (C30H38NO, −0.2) | Cimicifine A (syn. Cimicifugadine) | B |
a
A: Marker compounds for species other than Actaea racemosa; B: Marker compounds for Asian species; C: Marker compounds for Actaea racemosa; D: Marker compounds for North American species other than Actaea racemosa.