V o l. 26 N o. 4 2 0 0 5 4 CH EM ICAL JOU RNAL O F CH IN ESE UN IV ERS IT IES 638 641,,, (, 130022) (, 021400)., 4,.,,. ; ; O 657 A 025120790 (2005) 0420638204 (A con itum kusnez of f ii R eichb. ),, [1 4 ]. (ES I),.,.,,,.,,, [5 ]., (deoxyacon itine) (hypacon itine) (acon itine) (m esacon itine) 102 (acon ifine) (beiw u tine) ;, [6 ] ; [7 ] 3. C 8,. [8 ],.,,. 1 1. 1 ; ; (A con itum kusnez of f ii R eichb. ),. F inn ign L CQ, : 180, 418 kv, 15 V, 25% 43%, 60 un it, 38 V, 2 ul gm in. 1. 2 1100, 1102 0191 m g, 50 ml : 2004206210. : ( : 2003CCA 03100) (KGCX22SW 2213206) ( : 39930210, 30271600). : (1943 ),,,,,. E2m ail: m slab@ciac. jl. cn
N o. 4 : 639 ; 10 g 40 ml 1 h, 100,. 2 2. 1 1.,,,. [ 7, 9 ], m gz 646, 632, 616, 630, 648 662 102 ; m gz 590, 574, 604 588 (benzoylm esacon ine ) ( benzoylhypacon ine ) F ig. 1 Full- scan ESImass spectrum of the ethanolic extract ( benzoyl2acon ine ) of A con itum kusnezof f ii (benzoyldeoxyacon ine), C 8 [6 ] ;, m gz 674, 688, 690 704 m gz 800 950, [ 7, 8 ],,,,. Schem e 1. A lkalo ids R 1 R 2 R 3 R 4 [M + H ] + A conitine Et OH A cetyl H 646 M esaconitine M e OH A cetyl H 632 H ypaconitine M e H A cetyl H 616 D eoxyaconitine Et H A cetyl H 630 Benzoylaconine E t OH H H 604 Benzoylm esaconine M e OH H H 590 Benzoylhypaconine M e H H H 574 Benzo ldeoxyaconitine Et H H H 588 Beiw utine M e OH A cetyl OH 648 A conifine Et OH A cetyl OH 662 32A cetylm esaconitine M e O acetyl A cetyl H 674 32A cetylaconitine Et O acetyl A cetyl H 688 32A cetylbeiw utine M e O acetyl A cetyl OH 690 32A cetylaconifine Et O acetyl A cetyl OH 704 Scheme 1 The structures of acon itum alkalo ids in A con itum kusnezof f ii 2. 2,, 1. C 8 ( 60), [8 ]., CH 3OH, CO C 6H 5COOH., H 2O, H 2O. Schem e 1, C 3, C 3, C 3 C 13 C 15, C 3, C 15 CO., C 14, C 14. 1 m gz 616, 632
6 40 V o l. 26 646 ( ),. ( ) ( 60), m gz 570,, ( ). 102 ( ), C 10. Table 1 M S 2 and M S 3 spectra of [M + H ] + ion s for HA, M A and AC A conitine HA M A A C A conitine HA M A A C M S 2 M H + 616 (18) 632 (24) 646 (42) M H + - 60 556 (100) 572 (100) 586 (100) M S 3 M H + - 60 556 (8) 572 (10) 586 (30) M H + - 60-18 554 (5) 568 (4) M H + - 60-32 524 (100) 540 (66) 554 (50) M H + - 60-32- 18 522 (28) 536 (16) M S 3 M H + - 60-32- 28 496 (80) 512 (100) 526 (100) M H + - 60-323 2 492 (8) 508 (8) 522 (3) M H + - 60-323 2-18 490 (6) 504 (2) M H + - 60-323 2-28 464 (6) 480 (6) 494 (5) M H + - 60-323 3-122 338 (18) 354 (16) 368 (18) 1, m gz 604 590 [6 ] ; m gz 574 588,,, C 8,.,. m gz 590 ( ) (Schem e 1), m gz 590 ( 60), ( 18) m gz 572, ( 1)., m gz 590 m gz 572 m gz 572, m gz 590. 3, Schem e 1. 1, m gz 674, 688, 690 704 4. 2 m gz 704, 32 2102 2 [8 ],,,, 32 2102 2., 3 ( ) 32 32 32 2102 2. [M H - CH 3COOH ] +, [M H - 92 ] +, [M H - 120 ] + [M H - 152 ] +, CH 3COOH + CH 3OH, 2CH 3COOH CH 3COOH + CO + CH 3OH, 2CH 3COOH + CH 3OH CH 3COOH + CO + 2CH 3OH ;, m gz 60 CH 3COOH CH 3OH + CO, m gz 278 [8 ]. F ig. 2 ESI-M S 2 (A) and ESI-M S 3 (B) spectra of the ion at m gz 704 from the ESI-M S spectrum of A con itum kusnezof f ii, C 8, C 8
N o. 4 : 641 C 8,.,,, [9 ]., m gz 938 ( ) m gz 294, 310, 352 366 m gz 644, 628, 586 572,, ( ) 32 2102, 32,, 4 4, m gz 938 4, 32 2102 282 2, 32 282 2, 82 2 82 2. )., C 8 ( [ 1 ] D esai H. K., H art B. P., Caldw ell R. W. et a l.. J. N aṫ P rod. [J ], 1998, 61: 743 748 [ 2 ] Suzuk i Y., O yam a T., Ish ige A. et a l.. P lanta M ed. [J ], 1994, 60: 391 394 [ 3 ] Am eri A.. J. Pharm aco l. [J ], 1998, 342: 183 191 [ 4 ] HUAN G Yuan ( ), HOU Sh i2x iang ( ), X IE Rui2X i( ). Ch ina Journal of Ch inesem ateriam edica ( ) [J ], 1997, 22 (11) : 667 671 [ 5 ] WAN G Yong ( ), SON G Feng2Rui( ), J IN Dong2M ing ( ) et al.. Chem. J. Ch inese U niversities( ) [J ], 2004, 25 (1) : 85 89 [ 6 ] L I Zheng2Bang ( ), LU β Guang2H ua ( ), CH EN Dong2L in ( ) et al.. N atural P roduct Research and D evelopm ent ( ) [J ], 1997, 9 (1) : 9 14 [ 7 ] REN Yu2L in ( ), HUAN G Zhao2Hong ( ), J IA Sh i2shan ( ). A cta Pharm aceuitca Sinica ( ) [J ], 1999, 34 (11) : 873 876 [ 8 ] W ang Y., Song F. R., Xu Q. X.. J. M ass Spectrom. [J ], 2003, 38: 962 970 [ 9 ] Xu Q. X., W ang Y., L iu C. M. et a l.. A nal. Sci. [J ], 2003, 19: 1599 1603 Analysis of Nord iterpeno id A lkalo ids in Roots of A con itum kusnezof f ii by Electrospray Ion ization Tandem M ass Spectrom etry XU Q ing2xuan, W AN G Yong, L IU Zh i2q iang, L IU Shu2Y ing 3 (L aboratory of N ew D rug R esearch, Chang chun Institu te of A pp lied Chem istry, Ch inese A cad em y of S cience, Chang chun 130022, Ch ina) T IAN Cheng (M anz hou li Insp ection A nd Q uarantine T echnical Centre, M anz hou li 021400, Ch ina) Abstract E lectro sp ray ion ization tandem m ass spectrom etry (ES I2M S n ) w as app lied fo r sim u ltaneou s determ ination of no rditerpeno id alkalo ids in the roo ts of A con itum kusnez off ii w ithou t any chem ical iso lation. T he structu re info rm ation of the alkalo ids w as go tten by electro sp ray ion ization tandem m ass spectrom etry ( ES I2M S n ). A cco rdingly, fou r k inds of no rditerpeno id alkalo ids, such as monoester alkalo ids, dierster alkalo ids, triester alkalo ids and lipo2alkalo ids, w ere sim u ltaneou sly determ ined in the roo ts of A con itum kusnez off ii. A lso, triester alkalo ids and lipo2alkalo ids are firstly found in the roo ts of A con itum kusnez off ii. Keywords A con itum kusnez off ii; N o rditerpeno id alkalo id; E lectro sp ray ion ization tandem m ass spectrom etry (Ed. : K, G)
g 619 Syn thesis of M os2gcarbon Com posite Nanotubes SON G Xu2Chun 3, ZH EN G Y i2fan, HAN Gu i, Y IN H ao2yong, CAO Guang2Sheng Chem. J. Ch inese U niv., 2005, 26 (4), 617_ 619 622 Optica l Properties and Syn thesis of Copper Sulf ide Nanorods by Solid- sta te Reaction a t L ow Hea ting Tem pera ture ZHOU J ie, J IA D ian2zeng 3, L IU L ang Chem. J. Ch inese U niv., 2005, 26 (4), 620_ 622 627 Prepara tion of Nano- iron N itr ide by Tem pera ture-programm ed Reaction from Nano- iron Ox ides ZH EN G M ing2yuan, CH EN G R u i2h ua, CH EN X iao2w ei, L I N ing, CON G Yu, W AN G X iao2dong, ZHAN G T ao 3 Chem. J. Ch inese U niv., 2005, 26 (4), 623_ 627 637 Starch Nanoparticle a s Tran sgen ic Veh icle M ed ia ted by Ultra sound L IU Jun, L IU Xuan2M ing 3, X IAO Su2Yao, TON G Chun2Y i, TAN G Dong2Y ing, ZHAO L i2j ian Chem. J. Ch inese U niv., 2005, 26 (4), 634_ 637 641 Ana lysis of Nord iterpeno id A lka lo ids in Roots of A con itum kusnezof f ii by Electrospray Ion iza tion Tandem M a ss Spectrom etry XU Q ing2xuan, W AN G Yong, L IU Zh i2q iang, L IU Shu2Y ing 3, T IAN Cheng Chem. J. Ch inese U niv., 2005, 26 (4), 638_ 641 646 M olecular Im pr in ting-chem ilum inescence D eterm ina tion of Ana lg in H E Yun2H ua, L g U J iu2r u 3, ZHAN G Hong2Ge, DU J ian2x iu Chem. J. Ch inese U niv., 2005, 26 (4), 642_ 646