灵芝液态深层发酵产物中10种不饱和脂肪酸类化合物的鉴定

Identification of 10 unsaturated fatty acid compounds in the submerged fermentation products of Ganoderma lingzhi

通过规模化液态深层发酵获得灵芝发酵产物,采用多种硅胶色谱柱层析及重结晶的方式,从中分离得到10个化合物。通过核磁、质谱等波谱分析,鉴定出这些化合物均属于含羟基或酮基的不饱和脂肪酸类化合物,分别为(9S,10R,11E,13R)-9,10,13-trihydroxyoctadec-11-enoicacid(1)和(9S,10R,11E,13S)-9,10,13-trihydroxyoctadec-11-enoicacid(2)的混合物、12S^(*),13S^(*)-dihydroxy-9-oxo-10(E)-octadecenoicacid(3)、9R^(*),10R^(*)-dihydroxy-13-oxo-11(E)-octadecenoicacid(4)、12S^(*),13R^(*)-dihydroxy-9-oxo-10(E)-octadecenoicacid(5)、9S^(*),10R^(*)-dihydroxy-13-oxo-11(E)-octadecenoicacid(6)、10(S)-hydroxy-8(Z)-octadecenoic acid(7)、12-oxooctadeca-8,10-dienoic acid(8)、9,12-dihydroxy-10-eicosenoic acid(9)和9-oxooctadeca-10,12-dienoicacid(10)。这些化合物均为首次从灵芝发酵产物中获得,且具有不同程度的体外抗肿瘤活性。其中,化合物8和化合物10对L1210细胞增殖抑制的IC_(50)值分别为13.00μmol/L和16.88μmol/L,对K562细胞增殖亦有良好的抑制效果,是具有抗肿瘤潜力的天然产物。

The fermented products of Ganoderma lingzhi were obtained by large-scale submerged fermentation,and ten compounds were isolated by silica gel column chromatography,reversed-phase silica gel column chromatography and recrystallization.Through NMR and MS spectrum,they were identified as the mixture of(9S,10R,11E,13R)-9,10,13-trihydroxyoctadec-11-enoic acid(1)and(9S,10R,11E,13S)-9,10,13-trihydroxyoctadec-11-enoic acid(2),12 S^(*),13 S^(*)-dihydroxy-9-oxo-10(E)-octadecenoic acid(3),9R^(*),10R^(*)-dihydroxy-13-oxo-11(E)-octadecenoic acid(4),12S^(*),13R^(*)-dihydroxy-9-oxo-10(E)-octadecenoic acid(5),9S^(*),10R^(*)-dihydroxy-13-oxo-11(E)-octadecenoic acid(6),10(S)-hydroxy-8(Z)-octadecenoic acid(7),12-oxooctadeca-8,10-dienoic acid(8),9,12-dihydroxy-10-eicosenoic acid(9)and 9-oxooctadeca-10,12-dienoic acid(10).They were all unsaturated fatty acid compounds containing hydroxyl or ketone groups.These compounds were obtained for the first time from fermentation products of Ganoderma lingzhi,with antitumor activity in vitro to some extent.The IC_(50) values of compound 8 and compound 10 against tumor cells L1210 were 13.00μmol/L and 16.88μmol/L,respectively,and the effectiveness of them inhibiting the proliferation of K562 cells was also excellent.This result proved compound 8 and compound 10 were natural products with antitumor potential.