海洋来源邻苯二甲酸酯类化学成分和构效关系研究

The Chemical Constituents and Structure-antifouling-activity Relationships of PAEs from Marine Organisms

采用多种色谱分离技术,从柳珊瑚Anthogorgia caerulea、枯草芽孢杆菌和真菌Cladosporium sp.发酵液中分离了8个邻苯二甲酸酯类化合物,运用MS、1H NMR和13C NMR等波谱方法并结合文献对照分别鉴定为邻苯二甲酸二（2-乙基）己酯（1）、2-O-butyl-1-O-（2’-ethylhexyl） benzene-1,8-dicarboxylate（2）、邻苯二甲酸二（2-丙基）戊酯（3）、邻苯二甲酸二丁酯（4）、邻苯二甲酸二异酯（5）、邻苯二甲酸二（2-乙基）丁酯（6）、邻苯二甲酸二（2-乙基）壬酯（7）、邻苯二甲酸二（2-乙基）癸酯（8）.除化合物6以外,其他化合物均首次从以上三种海洋生物中分离得到,其中化合物2首次从海洋生物中分离获得.化合物1～8显示出抗海洋污损生物藤壶幼虫附着能力,最强活性EC50为1.93±0.93 μg/mL（化合物8）.构效关系研究表明脂类结构单元、脂肪侧链、脂肪支链与邻苯二甲酸酯类化合物抗海洋污损生物附着能力密切相关.

The PAEs from the gorgouian Anthogorgia caerulea,and the ethyl acetate extract of the culture broth of Bacillus subtilis and Cladosporium sp.were isolated and purified by chromatography on sihca gel,sephadex LH-20 columns,and HPLC and structurally identified by spectral analysis.Eight compounds were identified as di-（2-ethylhexyl）phthalate （1）,2-O-butyl-1-O-（2＇-ethylhexyl） benzene-1,8-dicarboxylate （2）,di-（2-propylpentyl） phthalate （3）,dibutyl phthalate （4）,diisobutyl phthalate （5）,bis （2-ethylbutyl） phthalate （6）,bis （2-ethylnonyl） phthalate （7）,bis（2-ethyldecyl） phthalate （8）.Compound 2 previously isolated from terrestrial organism but first obtained as marine natural product,and the other compounds were isolated from Anthogorgia caerulea,Bacillus subtilis,and Cladosporium sp.for the first time except 6.The antilarval activity of compound 1-8 was evaluated in setdement inhibition assay with laboratoryreared Balanus amphitrite （Cirripedia） larvae.The most potent metabolites produced by Cladosporium sp.were bis （2-ethyldecyl） phthalate （EC50 =1.93 ± 0.93 μg/mL）.The lipophilicgroup,side-chain fatty,and branched-chain fatty were very inhibitive to the larval settlement in the tube-building B.amphitrite larvae.