Delay C, Gavin J A, Aumelas A, Bonnet P A, Roumestand C
Centre de Biochimie Structurale, CNRS-UMR 9955, Université de Montpellier I, Faculté de Pharmacie, France.
Carbohydr Res. 1997 Jul 11;302(1-2):67-78. doi: 10.1016/s0008-6215(97)00101-8.
Saponins SAPO50 and SAPO30, of which SAPO50 is highly haemolytic, have been isolated from the commercial Merck Saponin. Their structures have been determined exclusively by high-field gradient-enhanced NMR methods. The 1H and 13C NMR spectra of these saponins in pyridine-deuterium oxide have been assigned by homonuclear and heteronuclear correlation experiments. Anomeric configurations were obtained by combined use of 1JCH, 3JH-1.H-2, and 1D-NOESY data. Sugar residues were identified by use of 3JHH values obtained from their subspectra recorded using an optimized 1D-zeta-TOCSY sequence. Linkage assignments were made using the ge-HMBC and 1D-NOESY spectra. This study shows that SAPO50 represents a hitherto undescribed saponin with the following structure: 3-O-beta-D-xylopyranosyl-(1-->3)-[beta-D-galactopyranosyl- (1-->2)]-beta-D-glucuronopyranosyl gypsogenin 28-O-(6-deoxy-beta-D-glucopyranosyl)-(1-->4)-[beta-D-xylopyranosyl-(1--> 3)- beta-D-xylopyranosyl-(1-->4)]-alpha-L-rhamnopyranosyl-(1-->2)-beta-D- fucopyranoside. SAPO30, however, corresponds to a saponin previously described [D. Frechet, B. Christ, B. Monegier du Sorbier, H. Fischer, and M. Vuilhorgne, Phytochemistry, 30 (1991) 927-931].
已从市售默克皂苷中分离出皂苷SAPO50和SAPO30，其中SAPO50具有高度溶血活性。它们的结构完全通过高场梯度增强核磁共振方法确定。通过同核和异核相关实验对这些皂苷在吡啶 - 重水中的1H和13C核磁共振谱进行了归属。通过联合使用1JCH、3JH-1.H-2和1D-NOESY数据获得了端基构型。通过使用从使用优化的1D-zeta-TOCSY序列记录的子谱中获得的3JHH值来鉴定糖残基。使用ge-HMBC和1D-NOESY谱进行连接归属。这项研究表明，SAPO50代表一种迄今未描述的具有以下结构的皂苷：3-O-β-D-吡喃木糖基-(1→3)-[β-D-吡喃半乳糖基-(1→2)]-β-D-吡喃葡糖醛酸基绞股蓝皂苷元28-O-(6-脱氧-β-D-吡喃葡萄糖基)-(1→4)-[β-D-吡喃木糖基-(1→3)-β-D-吡喃木糖基-(1→4)]-α-L-鼠李吡喃糖基-(1→2)-β-D-岩藻糖苷。然而，SAPO30对应于先前已描述的一种皂苷[D. Frechet，B. Christ，B. Monegier du Sorbier，H. Fischer和M. Vuilhorgne，植物化学，30 (1991) 927 - 931]。
