苯菲啶类生物碱的波谱学特征
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摘要
目的对苯菲啶类生物碱的结构、分布、类型及不同类型苯菲啶类生物碱的质谱裂解规律及波谱学特征进行综述,为进一步研究苯菲啶类生物碱提供帮助。方法通过查阅近年来有关苯菲啶类生物碱的国内外相关文献并进行总结。结果苯菲啶类生物碱可分成3种类型,不同类型的苯菲啶类生物碱的质谱裂解规律不同且在波谱学上存在差异。结论苯菲啶类生物碱按照结构差异可分为Ⅰ型(hexahydrobenzophenanthridine)、Ⅱ型(dihydrobenzophenanthridine)及Ⅲ型(quaternary benzophenathridine) 3种类型。质谱分析发现,Ⅰ型生物碱的质谱裂解途径主要是M-H_2O,M-H_2O-CH_3和M-H_2O-NH_2CH_3,而Ⅲ型生物碱由于具有稳定的母核,很难进行质谱裂解。Ⅱ型生物碱优先失去C-8位取代基形成稳定的苯菲啶类生物碱。在核磁共振波谱中,Ⅰ型生物碱的立体构型及取代基的不同对H-6,Me-13及H-14产生较大影响。Ⅱ型生物碱随C-8取代基的不同,N-Me的化学位移值变化较大。Ⅲ型生物碱N-Me的化学位移值大于其他2种类型。在CD谱中,Ⅰ型与具有8取代的Ⅱ型生物碱均在~1L_a带(200～240 nm)和~1L_b带(260～280 nm)具有特征性的Cotton效应,因此可以通过测定CD光谱来确定它们的立体构型。
Objective To review the structures and types of benzophenanthridine alkaloids,as well as the mass spectral fragmentation behavior and spectral characteristics of three types of benzophenanthridine alkaloids,which can provide the help to further study the benzophenanthridine alkaloids in future.Methods The pertinent literatures about benzophenanthridine alkaloids of recent years were reviewed and summarized.Results Benzophenanthridine alkaloids can be classified into three categories and there were differences between these three types of alkaloids in fragmentation patterns and wave-spectroscopic data.Conclusion Benzophenanthridine alkaloids can be classified into three types,type I(hexahydrobenzophenanthridine),type II(dihydrobenzophenanthridine),and type III(quaternarybenzophenathridine) according to their structural characteristics.In the course of analyzing mass spectrum of these alkaloids,we find that type III alkaloids are difficult to form fragment ions due to their stable nucleus,and type II alkaloids preferentially loses the C-8 substituent to form a stable benzophenanthridine alkaloids.In addition,the fragmentation pathway of type Ⅰ is M-H_2O,M-H_2O-CH_3 and M-H_2O-NH_2CH_3.In the 1 H NMR and ~(13)C NMR spectrum,the chemical shift value of N-Me in type III shows a larger chemical shift than the other two types.However,the chemical shift value of N-Me in the type II alkaloids was changed with the C-8 substituent.The absolute configuration and the difference substituent groups of type I alkaloids have a large effect on the chemical shift values of H-6,Me-13 and H-14.In the CD spectrum,type I and type II with C-8 substitutions have characteristic Cotton effects in the ~1L_a band(200-240 nm) and ~1L_b band(260-280 nm),and their absolute configuration can be determined by CD spectra.
Objective To review the structures and types of benzophenanthridine alkaloids,as well as the mass spectral fragmentation behavior and spectral characteristics of three types of benzophenanthridine alkaloids,which can provide the help to further study the benzophenanthridine alkaloids in future.Methods The pertinent literatures about benzophenanthridine alkaloids of recent years were reviewed and summarized.Results Benzophenanthridine alkaloids can be classified into three categories and there were differences between these three types of alkaloids in fragmentation patterns and wave-spectroscopic data.Conclusion Benzophenanthridine alkaloids can be classified into three types,type I(hexahydrobenzophenanthridine),type II(dihydrobenzophenanthridine),and type III(quaternarybenzophenathridine) according to their structural characteristics.In the course of analyzing mass spectrum of these alkaloids,we find that type III alkaloids are difficult to form fragment ions due to their stable nucleus,and type II alkaloids preferentially loses the C-8 substituent to form a stable benzophenanthridine alkaloids.In addition,the fragmentation pathway of type Ⅰ is M-H_2O,M-H_2O-CH_3 and M-H_2O-NH_2CH_3.In the 1 H NMR and ~(13)C NMR spectrum,the chemical shift value of N-Me in type III shows a larger chemical shift than the other two types.However,the chemical shift value of N-Me in the type II alkaloids was changed with the C-8 substituent.The absolute configuration and the difference substituent groups of type I alkaloids have a large effect on the chemical shift values of H-6,Me-13 and H-14.In the CD spectrum,type I and type II with C-8 substitutions have characteristic Cotton effects in the ~1L_a band(200-240 nm) and ~1L_b band(260-280 nm),and their absolute configuration can be determined by CD spectra.
引文
[1]KRANE B D,FAGBULE M O,SHAMMA M,et al.The benzophenanthridine alkaloids[J].Journal of Natural Products,1984,47(1):1-43.
[2]周天达.苯骈菲啶类生物碱在中国罂粟科和芸香科一些属中的分布初探[J].植物学报,1986,4(12):38-41.
[3]HAN N,YANG Z Y,LIU Z H,et al.Research progress on natural benzophenanthridine alkaloids and their pharmacological functions:A review[J].Natural Product Communications,2016,11:1181-1188.
[4]KIM D K,EUN J S,SHIN T Y,et al.Benzo[C]phenanthridine alkaloids from Corydalis incisa[J].Archives of Pharmacal Research,2000,23(6):589-591.
[5]NE CˇAS M,DOSTL J,KEJNOVSKI,et al.M olecular and crystal structures of(+)-homochelidonine,(+)-chelamine,and(-)-norchelidonine[J].Journal of M olecular Structure,2005,734(1):1-6.
[6]TAKAO N,IWASA K,KAMIGAUCHI M,et al.Studies on the alkaloids of papaveraceous plants:XXX.Conformational analysis of some hydro-benzo[C]phenanthridine-type alkaloids[J].Chemical&Pharmaceutical Bulletin,1978,26(6):1880-1889.
[7]LIU Z H,CHANG S,GUAN X Y,et al.The metabolites of ambinine,a benzo[C]phenanthridine alkaloid,in rats identified by ultra-performance liquid chromatography-quadrupoletime-of-flight mass spectrometry(UPLC/Q-TOF-MS/MS)[J].Journal of Chromatography.2016,1033-1034.
[8]丛浦珠,李笋玉.天然有机质谱学[M].北京:中国医药科技出版社,2003:362-367.
[9]ZHU W,TU Z,DING M.Alkaloids from the Root of Zanthoxylum nitidum var.fastuosum[J].Journal of Wuhan Botanical Research,1986,4(3):253-256.
[10]KHALID S A,WATERMAN P G.6-Hydroxymethyldihydronitidine from Fagaropsis angolensis[J].Journal of Natural Products,1985,48(1):118-119.
[11]CUI Z,ZHU P,ONDA M,et al.Absolute stereochemistry of(-)-ambinine[J].Journal of Natural Products,1990,53(5):1182-1186.
[12]YANG Z Y,JIANG B H,TENG F K,et al.Ambiguanine A-G,hexahydrobenzophenanthridine alkaloids from Corydalis ambigua var.amurensis[J].Phytochemistry,2014,105(5):158-163.
[13]LIU Z H,LI Q,CHANG S,et al.Protective effect of hexahydrobenzo[C]phenanthridine alkaloids isolated from Corydalis ambigua var.amurensis on myocardial ischemia-hypoxia cells[J].Phytochemistry Letters,2016,17:258-262.
[14]YANG C H,CHENG M J,CHIANG M Y,et al.Dihydrobenzo[C]phenanthridine alkaloids from stem bark of Zanthoxylum nitidum[J].Journal of Natural Products,2008,71(4):669-673.
[15]HU J,ZHANG W D,LIU R H,et al.Benzophenanthridine alkaloids from Zanthoxylum nitidum(Roxb.)DC,and their analgesic and anti-inflammatory activities[J].Chemistry&Biodiversity,2006,3(9):990-995.
[16]CHEN J J,FANG H Y,DUH C Y,et al.New indolopyridoquinazoline,benzo[C]phenanthridines and cytotoxic constituents from Zanthoxylum integrifoliolum[J].Planta Medica,2005,71(5):470-475.
[17]DENG A J,QIN H L.Cytotoxic dihydrobenzophenanthridine alkaloids from the roots of Macleaya microcarpa[J].Phytochemistry,2010,71(7):816-822.
[18]TIN-WA M,FONG H S,ABRAHAM D J,et al.Structure of sanguidimerine,a new major alkaloid from Sanguinaria canadensis(papaveraceae)[J].Journal of Pharmaceutical Sciences,1972,61(11):1846-1847.
[19]卿志星,程辟,曾建国.博落回中生物碱质谱裂解规律研究进展[J].中草药,2013,44(20):29-39.
[20]HAO H,QI C F.Chemical study on alkaloids from Corydalis bulleyana[J].Planta M edica,1986,52(03):193-198.
[21]JULLIAN V,BOURDY G,GEORGES S,et al.Validation of use of a traditional antimalarial remedy from French Guiana,Zanthoxylum rhoifolium Lam[J].Journal of Ethnopharmacology,2006,106(3):348-352.
[22]YANG Z Y,LIU Z H,JIANG B H,et al.Ambidalmines A-E and ambidimerine F:bioactive dihydrobenzophenanthridine alkaloids from Corydalis ambigua var.amurensis[J].European Journal of M edicinal Chemistry,2014,84(6):417-424.
[23]IS C,YL W S,IW T,et al.Alkaloids from root bark of Zanthoxylum simulans[J].Phytochemistry,1996,42(1):217-219.
[24]TOUSˇEK J R,DOM M ISSE R,DOSTL J,et al.Structural studies of benzophenanthridine alkaloid free bases by NM R spectroscopy[J].M agnetic Resonance in Chemistry,2010,40(2):147-152.
[25]TOUSˇEK J R,DOM M ISSE R,DOSTL J,et al.Configurations and conformations of sanguinarine and chelerythrine free bases stereoisomers[J].Journal of M olecular Structure,2002,613(1):103-113.
[26]GATHUNGU R M,OLDHAM J T,BIRD S S,et al.Application of an integrated LC-UV-M S-NM R platform to the identification of secondary metabolites from cell cultures:benzophenanthridine alkaloids from elicited Eschscholzia californica(california poppy)cell cultures[J].Anal M ethods,2012,4(5):1315-1325.
[27]BERTUZZI T,AGOSTI B,GUALLA A,et al.LC-M S-M S determination of sanguinarine and chelerythrine using a HILIC column[J].Chromatographia,2010,72(9/10):969-973.
[28]CHANG Z,LIU F,WANG S,et al.Studies on the chemical constitiuents of Zanthoxylum simulans Hance[J].Acta Pharmaceutica Sinica,1981,16(5):394-396.
[29]YANG C H,CHENG M J,CHIANG M Y,et al.Dihydrobenzophenanthridine alkaloids from Stem Bark of Zanthoxylum nitidum[J].Journal of Natural Products,2008,71(4):669.
[2]周天达.苯骈菲啶类生物碱在中国罂粟科和芸香科一些属中的分布初探[J].植物学报,1986,4(12):38-41.
[3]HAN N,YANG Z Y,LIU Z H,et al.Research progress on natural benzophenanthridine alkaloids and their pharmacological functions:A review[J].Natural Product Communications,2016,11:1181-1188.
[4]KIM D K,EUN J S,SHIN T Y,et al.Benzo[C]phenanthridine alkaloids from Corydalis incisa[J].Archives of Pharmacal Research,2000,23(6):589-591.
[5]NE CˇAS M,DOSTL J,KEJNOVSKI,et al.M olecular and crystal structures of(+)-homochelidonine,(+)-chelamine,and(-)-norchelidonine[J].Journal of M olecular Structure,2005,734(1):1-6.
[6]TAKAO N,IWASA K,KAMIGAUCHI M,et al.Studies on the alkaloids of papaveraceous plants:XXX.Conformational analysis of some hydro-benzo[C]phenanthridine-type alkaloids[J].Chemical&Pharmaceutical Bulletin,1978,26(6):1880-1889.
[7]LIU Z H,CHANG S,GUAN X Y,et al.The metabolites of ambinine,a benzo[C]phenanthridine alkaloid,in rats identified by ultra-performance liquid chromatography-quadrupoletime-of-flight mass spectrometry(UPLC/Q-TOF-MS/MS)[J].Journal of Chromatography.2016,1033-1034.
[8]丛浦珠,李笋玉.天然有机质谱学[M].北京:中国医药科技出版社,2003:362-367.
[9]ZHU W,TU Z,DING M.Alkaloids from the Root of Zanthoxylum nitidum var.fastuosum[J].Journal of Wuhan Botanical Research,1986,4(3):253-256.
[10]KHALID S A,WATERMAN P G.6-Hydroxymethyldihydronitidine from Fagaropsis angolensis[J].Journal of Natural Products,1985,48(1):118-119.
[11]CUI Z,ZHU P,ONDA M,et al.Absolute stereochemistry of(-)-ambinine[J].Journal of Natural Products,1990,53(5):1182-1186.
[12]YANG Z Y,JIANG B H,TENG F K,et al.Ambiguanine A-G,hexahydrobenzophenanthridine alkaloids from Corydalis ambigua var.amurensis[J].Phytochemistry,2014,105(5):158-163.
[13]LIU Z H,LI Q,CHANG S,et al.Protective effect of hexahydrobenzo[C]phenanthridine alkaloids isolated from Corydalis ambigua var.amurensis on myocardial ischemia-hypoxia cells[J].Phytochemistry Letters,2016,17:258-262.
[14]YANG C H,CHENG M J,CHIANG M Y,et al.Dihydrobenzo[C]phenanthridine alkaloids from stem bark of Zanthoxylum nitidum[J].Journal of Natural Products,2008,71(4):669-673.
[15]HU J,ZHANG W D,LIU R H,et al.Benzophenanthridine alkaloids from Zanthoxylum nitidum(Roxb.)DC,and their analgesic and anti-inflammatory activities[J].Chemistry&Biodiversity,2006,3(9):990-995.
[16]CHEN J J,FANG H Y,DUH C Y,et al.New indolopyridoquinazoline,benzo[C]phenanthridines and cytotoxic constituents from Zanthoxylum integrifoliolum[J].Planta Medica,2005,71(5):470-475.
[17]DENG A J,QIN H L.Cytotoxic dihydrobenzophenanthridine alkaloids from the roots of Macleaya microcarpa[J].Phytochemistry,2010,71(7):816-822.
[18]TIN-WA M,FONG H S,ABRAHAM D J,et al.Structure of sanguidimerine,a new major alkaloid from Sanguinaria canadensis(papaveraceae)[J].Journal of Pharmaceutical Sciences,1972,61(11):1846-1847.
[19]卿志星,程辟,曾建国.博落回中生物碱质谱裂解规律研究进展[J].中草药,2013,44(20):29-39.
[20]HAO H,QI C F.Chemical study on alkaloids from Corydalis bulleyana[J].Planta M edica,1986,52(03):193-198.
[21]JULLIAN V,BOURDY G,GEORGES S,et al.Validation of use of a traditional antimalarial remedy from French Guiana,Zanthoxylum rhoifolium Lam[J].Journal of Ethnopharmacology,2006,106(3):348-352.
[22]YANG Z Y,LIU Z H,JIANG B H,et al.Ambidalmines A-E and ambidimerine F:bioactive dihydrobenzophenanthridine alkaloids from Corydalis ambigua var.amurensis[J].European Journal of M edicinal Chemistry,2014,84(6):417-424.
[23]IS C,YL W S,IW T,et al.Alkaloids from root bark of Zanthoxylum simulans[J].Phytochemistry,1996,42(1):217-219.
[24]TOUSˇEK J R,DOM M ISSE R,DOSTL J,et al.Structural studies of benzophenanthridine alkaloid free bases by NM R spectroscopy[J].M agnetic Resonance in Chemistry,2010,40(2):147-152.
[25]TOUSˇEK J R,DOM M ISSE R,DOSTL J,et al.Configurations and conformations of sanguinarine and chelerythrine free bases stereoisomers[J].Journal of M olecular Structure,2002,613(1):103-113.
[26]GATHUNGU R M,OLDHAM J T,BIRD S S,et al.Application of an integrated LC-UV-M S-NM R platform to the identification of secondary metabolites from cell cultures:benzophenanthridine alkaloids from elicited Eschscholzia californica(california poppy)cell cultures[J].Anal M ethods,2012,4(5):1315-1325.
[27]BERTUZZI T,AGOSTI B,GUALLA A,et al.LC-M S-M S determination of sanguinarine and chelerythrine using a HILIC column[J].Chromatographia,2010,72(9/10):969-973.
[28]CHANG Z,LIU F,WANG S,et al.Studies on the chemical constitiuents of Zanthoxylum simulans Hance[J].Acta Pharmaceutica Sinica,1981,16(5):394-396.
[29]YANG C H,CHENG M J,CHIANG M Y,et al.Dihydrobenzophenanthridine alkaloids from Stem Bark of Zanthoxylum nitidum[J].Journal of Natural Products,2008,71(4):669.