Copper R A, Bowers R J, Beckham C J, uxtable R J
Department of Pharmacology, College of Medicine, University of Arizona, Tucson 85724, USA.
J Chromatogr A. 1996 Apr 26;732(1):43-50. doi: 10.1016/0021-9673(95)01241-9.
We have applied a high-speed counter-current chromatography (CCC) technique to the separation and purification of pyrrolizidine alkaloids from Amsinckia tessellata, Symphytum spp., Trichodesma incanum (Boraginaceae), and Senecio douglasii var. longilobus (Asteraceae). Alkaloidal fractions were separated in a solvent system composed of a chloroform mobile phase and 0.2 M potassium phosphate buffer, of an optimum pH, as the stationary phase. Up to 800 mg of sample could be successfully separated in a single run, with excellent resolution of alkaloids. Lycopsamine and several of its acetylated derivatives were resolved from alkaloidal fractions of Amsinckia and Symphytum. However, diastereomeric pairs such as 7-acetyl-lycopsamine and 7-acetyl-intermedine, could not be separated. The presence of diastereoisomers was determined by gas chromatography-mass spectrometry. Trichodesma contained predominantly trichodesmine, which was resolved from a small quantity of incanine. we report the electron impact mass spectrum of incanine for the first time. Resolving power of CCC was sufficient to separate the closely related alkaloids senecionine and seneciphylline from Senecio, in addition to florosenine and retrorsine, Pyrrolizidine alkaloid compositions of the four species, determined by mass spectral techniques, were consistent with literature, except for the lack of riddelliine and the presence of the otonecine-based florosenine in Senecio douglasii var. longilobus.
我们已应用高速逆流色谱（CCC）技术从花菱草、聚合草属植物、苞叶鹤虱（紫草科）和长叶千里光（菊科）中分离纯化吡咯里西啶生物碱。生物碱组分在由氯仿流动相和最佳pH值的0.2M磷酸钾缓冲液组成的溶剂体系中进行分离，其中缓冲液作为固定相。单次运行可成功分离高达800mg的样品，生物碱具有出色的分离度。从花菱草和聚合草的生物碱组分中分离出了石蒜碱及其几种乙酰化衍生物。然而，非对映体对，如7-乙酰基石蒜碱和7-乙酰基中节明碱，无法分离。通过气相色谱-质谱法测定了非对映异构体的存在。苞叶鹤虱主要含有苞叶鹤虱碱，从少量犬齿千里光碱中分离得到。我们首次报道了犬齿千里光碱的电子轰击质谱。CCC的分离能力足以从千里光属植物中分离出密切相关的生物碱千里光宁碱和千里光菲灵碱，此外还能分离出弗洛罗辛碱和反式千里光碱。通过质谱技术测定的这四个物种的吡咯里西啶生物碱组成与文献一致，只是长叶千里光中缺乏瑞德利碱且存在基于耳草次碱的弗洛罗辛碱。
