東方粉枝藻及波氏粉枝藻雙半乳糖基二醯基甘油及圈扇藻醯基間苯三酚類化合物的分離與其結構鑑定

Abstract

第一部份 東方粉枝藻(Liagora orientalis)及波氏粉枝藻(Liagora boergesnii)雙半乳糖基二醯基甘油的分離與結構鑑定 實驗室大量培養的東方粉枝藻(Liagora orientalis)和波氏粉枝藻(Liagora boergesnii)絲狀體，其丙酮萃出物經過速分管柱層析得到一系列雙糖基二醯基甘油，經由核磁共振譜、紅外光吸收光譜、電子撞擊質譜分析及快速原子撞擊質譜及利用化學反應後進行甲基酯及糖衍生物的氣相層析質譜，推測此一系列化合物結構如下： 該一系列化合物的結構圖（略） 1：R,R′= C16:0, C16:0 2: C18:1, C16:0 3: C20:5, C16:0 4: C20:4, C16:0 其中雙糖基反應成糖的TMS衍生物及alditol acetate衍生物和部份甲基化的alditol acetate進行氣相層析質譜分離分析，證實為1,6鍵結之雙半乳糖；而醯基甘油上的脂肪酸在東方粉枝藻為 C16:0 (58.57%), C18:1 (16.48%), C20:5 (11.44%), C20:4 (3.71%)；而波氏粉枝藻則為 C16:0 (45.48%), C18:l (12.34%), C20:5 (32.21%), C20:4 (1.51%）的組成存在。 雙糖基二醯基甘油的溶血活性及抗血小板凝集活性並不存在。 第二部份 圈扇藻（Zonaria diesingiana）醯基間苯三酚類化合物的分離與光譜分析 本省北海岸採集的圈扇藻（Zonaria diesingiana）分離出兩個醯基間苯三酚類化合物，其中之一為 2-（17’-hydroxy-l’-oxoeicosa-5',8',11',14'(all Z)-tetraenyl）-l,3,5-trihydroxybenzene，首次以二維核磁共振譜對各碳13原子核化學位移重新鑑別，並提出舊有文獻（Gerwick & Fenical, 1982）對 C-3', C-4', C-16', C-18’數據上的修正；另一為 2-（ 1’-oxoeicosa-5',8',11',14',17' (all Z)－pentaenyl)-1,3,5-trihydroxybenzene，同樣亦對舊有文獻（Amicoet.al.,1981）上 C-3',C-4’之化學位移提出修正。並提出分子內氫鍵形成之有無在核磁共振譜上的表現情形。

Part Ⅰ: Isolation and characterization of digalactosyldiacylglycerols from Liagora orientalis and L. boergesnii. A series of digalactosyldiacylglycerols has been isolated from cultured filamentous phase of L. orientalis and L. boergesnii (Rhodophyta). These were extracted with acetone and seperated through Si-flash column chromotography, and their structures were characterized by EIMS, FABMS and NMR, IR spectroscopic methods. The galactose residues of digalactosyldiacylglycerols have been determined as 1,6-linked digalactose through GCMS analysis of their TMS-sugar derivatives, alditol acetates and partially methylated alditol acetates. The fatty acid residues of digalactosyldiacylglycerols from L. orientalis have been determined as C16:0 (58.57%), C18:l (16.48%), C20:5 (11.44%), C20:4 (3.71%), and the fatty acid residues of digalactosyldiacylglycerols from L. boergesnii have been determined as C16:0 (58.57%), C18:l (16.48%), C20:5 (11.44%), C20:4 (3.71%). The structure is sbbreviated. 1: R, R′= C16:0, C16:0 2: C18:1, C16:0 3: C20:5, C16:0 4: C20:4, C16:0 These compounds were then subjected to hemolysis and antiplatelet acativty assay, there is no significant difference compared with the control. Part Ⅱ: Isolation and characterization of acylphlorglucinols from Zonaria diesingiana. Two acyiphiorglucinols have been isolated from Zonaria diesingiana collected from the north coast in Taiwan. Based on 1H, 13C, 1H-1H COSY and 13C-1H COSY NMR, one is assigned as 2-(17’-hydroxy-l’-oxoeicosa-5’, 8’, 11’, 14’ (all Z)-tetraenyl)-1,3,5-trihydroxybenzene, and its 13C-NMR data at C-3’, C-4’, C-16’, C-18’ are different from the published report (Gerwick & Fenical,1982).The other is 2-(1’-oxoeicosa-5’,8’,11’,14’,17’(all Z)-pentaenyl)-l ,3,5-trihydroxybenzene, and its 13C-NMR data at C-3’and C-4’are also different from the published report (Gerwick & Fenical,1982).This is the first time determing these two structures by two dimention NMR, and make some corrections on the published data.