Table 1.
Summary of chemical constituents identified in Tinospora sinensis by HPLC-LTQ-Orbitrap.
| NO. | tR/min | Identification | Empirical Formula | Proposed Ions | Experimental Mass m/z | Theoretical Mass m/z | Mass Error (×10−6) | MS2 Data (Measured) |
|---|---|---|---|---|---|---|---|---|
| 1 | 16.13 | (2,3,4,6)-2-(Acetoxymethyl)-6-(((2,4,6,6,10,10)-2-(furan-3-yl)-9,10-dimethoxy-7-(methoxycarbonyl)-6,10-dimethyl-4-oxododecahydro-1H-benzo[f]isochromen-6-yl)oxy)-tetrahydro-2H-pyran-3,4,5-triyl triacetate * | C37H49O17 | [M − H]− | 765.29578 | 765.29642 | 0.836 | 747(10), 737(48), 721(38), 720(43), 719(100), 697(5), 672(11), 555(18) |
| 2 | 17.69 | Cordioside | C26H33O12 | [M − H]− | 537.19592 | 537.19665 | 1.359 | 519(4), 491(8), 490(13), 375(100), 357(43), 327(88), 297(4) |
| 3 | 18.55 | (4,6,6,7,9,10,10,10)-2-(Furan-3-yl)-7-hydroxy-10b-methyl-4-oxo-6-(((3,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)-tetrahydro-2H-pyran-2-yl)-oxy)dodecahydro-1H-benzo-[f]isochromene-9,10-diyl diacetate * | C28H37O14 | [M − H]− | 597.21661 | 597.21778 | 1.959 | 579(3), 551(60), 476(7), 435(10), 389(96), 359(100) |
| 4 | 20.51 | (2,5,6,8,9,10,12)-15,16-Epoxy-2-hydroxy-6-O-{β-d-xylopyranosyl(1→6)-d-glucopyranosyl}-cleroda-3,13(16),14-trien-17,12-olid-18-oic acid methyl ester * | C32H43O16 | [M − H]− | 683.25372 | 683.25456 | 1.229 | 665(68), 639(12), 637(16), 615(95), 520(100), 519(79), 370(15), 309(37) |
| 5 | 21.89 | 1-Deacetyltinosposide A | C24H33O12 | [M − H]− | 513.19678 | 513.19665 | −0.253 | 495(3), 351(12), 333(100), 307(11), 305(5), 271(5) |
| 6 | 25.01 | Cordifoliside D | C26H33O12 | [M − H]− | 537.19623 | 537.19665 | 0.782 | 519(38), 492(22), 491(100), 490(71), 469(71), 297(38) |
| 7 | 26.40 | Tinospinoside D | C27H35O13 | [M − H]− | 567.20660 | 567.20721 | 1.075 | 552(1), 521(9), 404(0.5), 359(100), 341(2), 329(2) |
| 8 | 26.55 | (6,6,10,10,10)-Methyl 10-acetoxy-2-(furan-3-yl)-9-hydroxy-10b-methyl-4-oxo-6-(((3,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)-dodecahydro-1H-benzo[f]-isochromene-7-carboxylate * | C28H37O14 | [M − H]− | 597.21741 | 597.21778 | 0.619 | 565(4), 551(21), 550(25), 535(10), 463(12), 435(12), 389(100), 388(12) |
| 9 | 26.98 | Borapetoside B | C27H35O12 | [M − H]− | 551.21204 | 551.21230 | 0.471 | 536(5), 533(2), 507(3), 389(100), 388(15), 371(2), 370(7), 329(2) |
| 10 | 27.65 | Amritoside C | C27H35O13 | [M − H]− | 567.20612 | 567.20721 | 1.921 | 552(6), 529(20), 521(100), 404(10), 341(4) |
| 11 | 29.43 | Tinospinoside B | C27H35O12 | [M − H]− | 551.21298 | 551.21230 | −1.233 | 533(9), 532(31), 515(12), 505(100), 389(8), 344(8) |
| 12 | 29.52 | (2,4,6,6,7,7,8,9,9,9)-2-(furan-3-yl)-6a,9b-dimethyl-6-(((2,3,4,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)-tetrahydro-2H-pyran-2-yl)oxy)decahydro-1H-9,7-(epoxymethano)-oxireno[2′,3′:4,5]benzo[1,2-f]isochromene-4,11(2H)-dione * | C26H31O12 | [M − H]− | 535.18036 | 535.18100 | 1.196 | 517(0.5), 489(2), 467(2), 373(100), 345(1), 343(2), 313(2) |
| 13 | 30.82 | Tinosposinenside A | C27H35O12 | [M − H]− | 551.21173 | 551.21230 | 1.034 | 536(5), 533(3), 507(3), 389(100), 374(11), 371(16), 359(2), 341(7) |
| 14 | 31.03 | (6,6,7,9,10,10,10)-2-(Furan-3-yl)-7-hydroxy-10b-methyl-4-oxo-6-(((3,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)-tetrahydro-2H-pyran-2-yl)oxy)dodecahydro-1H-benzo-[f]isochromene-9,10-diyl diacetate * | C28H37O14 | [M − H]− | 597.21692 | 597.21778 | 1.440 | 579(4), 561(11), 551(13), 529(19), 515(5), 477(6), 435(12), 389(82), 359(100) |
| 15 | 31.41 | Rumphioside A | C27H35O13 | [M − H]− | 567.20685 | 567.20721 | 0.635 | 549(14), 548(25), 535(25), 521(34), 405(46), 404(100), 359(56) |
| 16 | 31.97 | Furanoid diterpene glycoside | C26H33O11 | [M − H]− | 521.20099 | 521.20173 | 1.420 | 506(1), 359(100), 345(3), 344(4), 341(3) |
| 17 | 32.03 | Rumphioside F | C27H35O13 | [M − H]− | 567.20642 | 567.20721 | 1.393 | 549(22), 521(47), 491(100), 405(11), 404(18), 387(19) |
| 18 | 33.06 | (2,6,6,7,9,10,10,10)-2-(Furan-3-yl)-6,9,10-trihydroxy-10b-methyl-7-(((2,3,4,5,6)-3,4,5-trihydroxy-6-(hydroxyl-methyl)tetrahydro-2H-pyran-2-yl)oxy)decahydro-1H-benzo[f]isochromen-4(2H)-one * | C24H33O12 | [M − H]− | 513.19635 | 513.19665 | 0.585 | 495(3), 467(1), 351(100), 305(60), 287(7), 161(3) |
| 19 | 34.12 | (2R,5R,6R,8R,9S,10S,12S)-15,16-Epoxy-2-hydroxy-6-O-(β-d-glucopyranosyl)-cleroda-3,13(16),14-trien-17,12-olid-18-oic acid methyl ester | C27H35O12 | [M − H]− | 551.21185 | 551.21230 | 0.816 | 533(2), 519(3), 505(4), 482(4), 389(100), 327(67) |
| 20 | 35.07 | Tinosineside B | C28H37O14 | [M − H]− | 597.21716 | 597.21778 | 1.038 | 578(20), 551(100), 529(10), 517(12), 461(25), 179(49) |
| 21 | 35.26 | Palmatoside F | C26H31O12 | [M − H]− | 535.17987 | 535.18100 | 2.111 | 520(4), 517(2), 488(3), 373(93), 329(100) |
| 22 | 35.35 | (2,6,7,9,10,10,10)-2-(Furan-3-yl)-7,10-dihydroxy-9-methoxy-10b-methyl-6-(((2,3,4,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)deca-hydro-1H-benzo[f]isochromen-4(2H)-one * | C25H35O12 | [M − H]− | 527.21241 | 527.21230 | −0.209 | 511(14), 509(3), 494(14), 481(100), 347(6), 300(7) |
| 23 | 35.80 | Amritoside A | C26H35O13 | [M − H]− | 555.20624 | 555.20721 | 1.747 | 537(5), 513(34), 495(53), 467(19), 393(100), 375(5), 305(74), 287(7) |
| 24 | 36.87 | Rumphioside D | C37H49O17 | [M − H]− | 765.29431 | 765.29642 | 2.757 | 747(19), 734(20), 721(37), 719(41), 718(100), 697(18), 600(26), 418(4), 393(11) |
| 25 | 38.12 | (4,6,6,9,10,10)-Methyl 9-acetoxy-2-(furan-3-yl)-4a- hydroxy-10b-methyl-4-oxo-6-(((3,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)-dodecahydro-1H-benzo[f]isochromene-7-carboxylate * | C28H37O14 | [M − H]− | 597.21619 | 597.21778 | 2.662 | 582(73), 579(9), 556(41), 551(28), 550(72), 434(31), 416(33), 389(75), 329(100) |
| 26 | 38.15 | Sagittatayunnanoside D | C26H35O11 | [M − H]− | 523.21667 | 523.21738 | 1.357 | 508(1), 505(1), 361(100), 347(8), 343(4), 329(4) |
| 27 | 38.26 | Borapetoside H | C33H45O17 | [M − H]− | 713.26588 | 713.26512 | −1.066 | 694(12), 668(18), 667(29), 666(100), 645(23), 551(21), 533(6), 389(6) |
| 28 | 38.38 | (5R,6R,8S,9R,10R,12S)-15,16-Epoxy-2-oxo-6-O-(β-d-glucopyranosyl)–cleroda-3,13(16) 14-trien-17,12-olid-18-oic acid methyl ester | C27H33O12 | [M − H]− | 549.19592 | 549.19665 | 1.329 | 531(0.4), 503(5), 481(3), 387(100), 249(1) |
| 29 | 38.80 | Isocolumbin a | C20H21O6 | [M − H]− | 357.13321 | 357.13326 | 0.140 | 342(9), 339(2), 313(1), 311(13), 151(100), 135(37) |
| 30 | 38.84 | Tinoside | C26H31O11 | [M − H]− | 519.18542 | 519.18608 | 1.271 | 501(0.1), 473(0.3), 358(0.4), 357(100) |
| 31 | 39.44 | Tinosineside A | C26H35O13 | [M − H]− | 555.20581 | 555.20721 | 2.522 | 513(100), 495(69), 393(2), 375(8), 333(28), 315(10), 307(13), 305(1) |
| 32 | 40.03 | Tinocapilactone B | C22H25O8 | [M − H]− | 417.15411 | 417.15439 | 0.671 | 402(42), 371(9), 356(2), 181(100), 166(34), 151(16) |
| 33 | 40.61 | Tinoscorside C | C27H33O12 | [M − H]− | 549.19586 | 549.19665 | 1.438 | 531(7), 513(2), 503(13), 481(10), 417(5), 387(100) |
| 34 | 40.79 | (1,3,10,10)-9-(2-Methoxy-2,5-dihydrofuran-3-yl)-10a-methyl-4,7-dioxo-3-(((2,3,4,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)tetra-decahydroisobenzofuro[7,1-fg]isochromen-1-yl acetate * | C28H37O14 | [M − H]− | 597.21655 | 597.21778 | 2.060 | 579(51), 551(100), 528(39), 471(12) |
| 35 | 41.60 | Rumphioside I | C27H35O12 | [M − H]− | 551.21210 | 551.21230 | 0.363 | 533(9), 519(11), 505(2), 482(3), 339(100), 324(5) |
| 36 | 42.17 | Borapetoside C | C27H35O11 | [M − H]− | 535.21637 | 535.21738 | 1.887 | 520(1), 517(4), 488(1), 373(100), 359(5), 358(7), 355(2), 341(5) |
| 37 | 43.22 | (1,2,7,8)-1-(2-Ffuran-3-yl)-2-hydroxyethyl)-2-hydroxy-5-(methoxycarbonyl)-1-methyl-7-(((3,4,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)-1,2,3,4,6,7,8,8-octahydronaphthalene-2-carboxylic acid * | C26H35O13 | [M − H]− | 555.20630 | 555.20721 | 1.639 | 537(0.2), 513(1), 495(100), 393(0.2), 333(1), 297(2), 178(0.2) |
| 38 | 43.99 | Tinosposinenside B | C28H37O13 | [M − H]− | 581.22162 | 581.22286 | 2.133 | 563(8), 535(37), 419(2), 373(33), 343(100), 297(6) |
| 39 | 44.59 | Borapetoside A | C26H33O12 | [M − H]− | 537.19604 | 537.19665 | 1.136 | 519(4), 493(2), 491(62), 375(3), 371(5), 357(1), 341(2), 329(100), 297(1) |
| 40 | 45.22 | 8-Hydroxycolumbin | C20H21O7 | [M − H]− | 373.12759 | 373.12817 | 1.554 | 358(2), 343(45), 325(6), 313(100) |
| 41 | 45.78 | 6-Hydroxycolumbin | C20H21O7 | [M − H]− | 373.12759 | 373.12817 | 1.554 | 358(9), 355(7), 343(79), 329(3), 325(15), 313(100), 305(3), 261(2) |
| 42 | 46.04 | Boropetoside G | C27H37O11 | [M − H]− | 537.23218 | 537.23303 | 1.582 | 518(1), 375(100), 361(9), 360(2), 357(2), 343(2) |
| 43 | 46.82 | (4,6,6,9,10,10)-Methyl 9-acetoxy-2-(furan-3-yl)-4a-hydroxy-10b-methyl-4-oxo-6-(((3,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)dodec-ahydro-1H-benzo[f]isochromene-7-carboxylate * | C28H37O14 | [M − H]− | 597.2168 | 597.21778 | 1.641 | 579(23), 565(52), 564(45), 551(27), 529(31), 389(10), 329(100) |
| 44 | 46.89 | Tinocrisposide | C27H35O11 | [M − H]− | 535.21600 | 535.21738 | 2.578 | 520(2), 516(5), 488(7), 373(100), 359(8), 358(6), 355(3), 341(2) |
| 45 | 49.44 | Cordifolide A | C28H37O12S | [M − H]− | 597.19922 | 597.20002 | 1.340 | 579(13), 553(33), 550(53), 533(100), 528(25), 467(43), 466(25), 434(18), 372(32), 359(11) |
| 46 | 49.89 | (2R,5R,6R,8S,9S,10S,12S)-15,16-Epoxy-2-hydroxy-6-O-{β-d-glucopyranosyl-(1→6)-α-d-xylopyranosyl}-cleroda-3,13(16),14-trien-17,12-olid-18-oic acid methyl ester | C32H43O16 | [M − H]− | 683.25416 | 683.25456 | 0.585 | 665(2), 664(11), 637(2), 615(3), 534(3), 520(100), 502(93), 490(12) |
| 47 | 50.40 | 3-((6,6,7,10,10,10)-7-Hydroxy-6a,10b-dimethyl-4,12-dioxo-6-(((3,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)-tetrahydro-2H-pyran-2-yl)oxy)-2,4,4,5,6,6,7,10,10,10-decahydro-1H-10,7-(epoxymethano)benzo[f]isochromen-2-yl)tetrahydrofuran-2-yl acetate * | C28H37O14 | [M − H]− | 597.21680 | 597.21778 | 1.641 | 579(1), 561(15), 551(9), 495(6), 487(7), 486(66), 435(4), 433(100), 297(44) |
| 48 | 51.12 | Tinosposinenside C | C26H35O12 | [M − H]− | 539.21155 | 539.21230 | 1.391 | 521(3), 497(100), 479(86), 478(8), 377(2) |
| 49 | 52.20 | (1,3,10,10)-9-(2-Methoxy-2,5-dihydrofuran-3-yl)-10a-methyl-4,7-dioxo-3a-(((2,3,4,5,6)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl)oxy)tetra-decahydroisobenzofuro[7,1-fg]isochromen-1-yl acetate * | C28H37O14 | [M − H]− | 597.21655 | 597.21778 | 2.060 | 579(0.4), 551(98), 509(7), 491(100), 481(6), 435(2) |
| 50 | 59.05 | 6′-O-Lactoylborapetoside B | C30H39O14 | [M − H]− | 623.23434 | 623.23343 | −1.460 | 513(3), 460(100), 458(7), 446(7), 444(4), 297(1), 283(12) |
| 51 | 59.98 | Columbin a | C20H21O6 | [M − H]− | 357.13297 | 357.13326 | 0.812 | |
| 52 | 60.37 | Tinospinoside E | C26H29O11 | [M − H]− | 517.16986 | 517.17043 | 1.102 | 499(26), 473(10), 471(20), 381(13), 355(6), 341(11), 162(100), 151(6) |
| 53 | 61.73 | Tinosporaside | C25H31O10 | [M − H]− | 491.19087 | 491.19117 | 0.611 | 473(28), 472(100), 460(8), 444(0.3), 327(0.4), 312(2) |
| C26H33O12 | [M − H + HCOOH]− | 537.19697 | 537.19665 | −0.596 | 519(4), 518(11), 491(25), 490(100), 357(3), 343(4), 327(8) | |||
| 54 | 62.14 | Sagittatayunnanoside B | C33H47O17 | [M − H]− | 715.28030 | 715.28077 | 0.657 | 670(2), 628(1), 652(1), 552(100), 551(16) |
| 55 | 63.08 | Tinospinoside C | C27H35O12 | [M − H]− | 551.21155 | 551.21230 | 1.361 | 533(73), 507(90), 505(100), 483(85), 415(84), 389(22), 343(81) |
| 56 | 63.14 | Sagittatayunnanoside C | C32H47O15 | [M − H]− | 671.28912 | 671.29094 | 2.711 | 653(1), 627(2), 509(50), 347(27), 329(100), 301(70), 241(25) |
| 57 | 63.83 | Tinosponone | C19H21O5 | [M − H]− | 329.13791 | 329.13835 | 1.337 | 314(100), 311(24), 285(70), 191(18) |
| 58 | 65.99 | Sagittatayunnanoside A | C26H37O10 | [M − H]− | 509.23792 | 509.23812 | 0.393 | 491(5), 465(5), 347(33), 329(100), 301(89), 257(9), 241(11) |
| 59 | 69.79 | 2-O-Lactoylborapetoside B | C30H39O14 | [M − H]− | 623.23334 | 623.23343 | 0.144 | 608(1), 591(23), 551(7), 486(16), 460(100), 297(34) |
| 60 | 78.98 | Tinotufolin D | C20H25O4 | [M − H]− | 329.17441 | 329.17473 | 0.972 | 311(36), 285(100), 293(7), 267(10), 249(16) |
| 61 | 82.48 | (2aβ,3α,5aβ,6β,7α,8aα)-6-2-(3-Furanyl)ethyl-2a,3,4,5,5a,6,7,8,8a,8b-decahydro-2a,3-dihydroxy-6,7,8b-trimethyl-2H-naphtho1,8-bcfuran-2-one | C20H27O5 | [M − H]− | 347.18491 | 347.18530 | 1.123 | 329(63), 303(3), 301(100), 285(3), 187(1) |
| 62 | 88.91 | (3,4,5,8)-Methyl-5-(2-(furan-3-yl)ethyl)-3-hydroxy-5,8a-dimethyl-3,4,4,5,6,7,8,8a-octahydronaphthalene-1-carboxylate * | C20H27O4 | [M − H]− | 331.19016 | 331.19038 | 0.664 | 313(9), 287(15), 285(100), 283(30), 271(2), 257(5), 243(2), 237(0.4) |
| 63 | 95.27 | Tinotufolin C | C21H31O5 | [M − H]− | 363.21662 | 363.21660 | −0.055 | 345(0.1), 334(0.2), 317(69), 295(100) |
a Comparison with standards. * Tentatively identified as new compounds.