蒲枝凹顶藻、鸭毛藻及鸭毛藻共生真菌次生代谢产物研究
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摘要
本文对蒲枝凹顶藻(Laurencia nidifica)、鸭毛藻(Symphyocladia latiuscula)和鸭毛藻共生真菌哈茨木霉(Trichoderma harzianum EN-85)的次生代谢产物进行了研究。综合利用各种色谱学方法(正相硅胶柱层析、反相硅胶柱层析、凝胶Sephadex LH-20柱层析、半制备HPLC,制备薄层层析等)和波谱学技术(IR、UV、EI-MS、ESI-MS、HR-ESI-MS、1D-NMR、2D-NMR等)共分离、鉴定了55个化合物,发现9个新化合物。
蒲枝凹顶藻主要分布于夏威夷群岛,我们在开展海藻资源调查时于2008年首次发现其在我国南海海域的分布并对其次生代谢产物进行了研究。从中分离鉴定了21个化合物,其中有4个新化合物,包括1个charmigrane型倍半萜(LS8),2个bisabolane型倍半萜(LS9,LS10)和1个C15多聚乙酰(LS17)。对其中的LS1、LS3、LS6、LS7、LS8、LS12、LS13和LS17进行了抗菌活性测试。发现LS6对白菜黑斑病菌(Alternaria brassicae(berk.) Sace)有一定抑制活性;LS7对大肠杆菌(Escherichia coli)、金黄色葡萄球菌(Staphylococcus aureus)、白菜黑斑病菌(A. brassicae)和苹果轮纹病菌(Physalospora piricola Nose)均有弱的抑制活性;LS8对金黄色葡萄球菌(S. aureus)有弱的活性;LS12对金黄色葡萄球菌(S. aureus)和苹果轮纹病菌(P. piricola)有弱的活性。
对采集自山东威海海域的鸭毛藻进行了次生代谢产物研究。从中分离鉴定了13个化合物(9个为溴酚类化合物),其中有1个新化合物(SL1)。对其中的溴酚类化合物进行了抑制蛋白酪氨酸磷酸酯酶(PTP1B)活性筛选,发现化合物SL6、SL7,SL8具有很好的PTP1B抑制活性,IC50分别为3.9, 4.3, 3.5μmol/L,优于阳性对照正钒酸钠(IC50为4.6μmol/L),具有潜在的发展成抗糖尿病药物的研究价值。
研究了鸭毛藻共生真菌哈茨木霉(Trichoderma harzianum EN-85)的次生代谢产物。共分离鉴定了21个化合物,其中有4个新化合物,分别为两个倍半萜(FS2、FS4),一个二萜(FS14)和一个链状多烯醇类化合物(FS15)。对其粗提物和次生代谢产物进行了活性筛选。发现粗提物对白菜黑斑病菌(A. brassicae)和苹果轮纹病菌(P. piricola)具有一定的抑制作用。对分离得到的化合物FS1、FS3, FS4、FS8-FS10和FS12-FS15进行了抗菌试验。化合物FS3和FS4对苹果轮纹病菌(P.piricola)和棉花枯萎病菌(Fusarium oxysporium)有弱的抑制活性。
本文通过对蒲枝凹顶藻、鸭毛藻以及鸭毛藻共生真菌的次生代谢产物研究,不仅丰富了海洋天然产物的资源库,同时也发现了一些具有潜在抗糖尿病活性的溴酚物质和一些抗农业病害菌的真菌代谢产物,为海洋生物资源的利用提供了一定的科学依据。
In the present dissertation, the secondary metobolites from the marine red algal Laurencia nidifica and Symphyocladia latiuscula as well as the algal-derived symbiotic Trichoderma harzianum EN-85 were investigated. Repeated column chromatography on silica gel, Rp-18, ploymide, and Sephadex LH-20, prep-TLC, and semi-preparative HPLC were used to separate the compounds. Elucidation of the structures was performed by IR, UV, EI-MS, ESI-MS, HR-ESI-MS, 1D NMR and 2D NMR. A total of 55 compounds were separated and identified, with 9 of them were found as new compounds.
The marine red algal Laurencia nidifica was discovered for the first time in South China Sea. A total of 21 compounds were separated and identified from this species, including four new structures (one charmigrane sesquiterpene LS8, two bisabolene sesquiterpenes LS9 and LS10, and one C15-acetogein LS17). Compounds LS1, LS3, LS6, LS7, LS8, LS12, LS13, and LS17 were tested for the antimicrobial activity. Among them, compounds LS6 and LS7 exhibited weak inhibition against Alternaria brassicae (berk.) Sace and against Escherichia coli, Staphylococcus aureus, A. brassicae and Physalospora piricola Nose, respectively, while LS8 and LS12 exhibited weak inhibition against S. aureus and against S. aureus and P. piricola, respectively.
Another marine red algal Symphyocladia latiuscula was collected at the coast of Weihai in Shandong province. A total of 13 compounds were isolated and identified from the species including one new compound (SL1). Compounds SL2-SL9 were evaluated the activity against the protein tyrosine phosphatase 1B (PTP1B). Bromophenols SL6, SL7, and SL8 displayed potent activity with IC50 values 3.9, 4.3, and 3.5μmol/L, respectively, which might be used as a potential source for developing anti-diabetes drug.
The fungus Trichoderma harzianum EN-85 was isolated from the marine red algal Symphyocladia latiuscula and was identified by molecular biology methods. A total of 21 compounds were isolated and indentified from this fungal stain including 4 new compounds (two sesquiterpenes FS2 and FS4, one diterpene FS14, and one other compound FS15). The antimicrobial activity was evaluated. The inhibition on the A. brassicae and P. piricola were observed. Compounds FS1, FS3, FS4, FS8-FS10, and FS12-FS15 were tested the antimicrobial activity, and FS3 and FS4 exhibited weak inhibition against P. piricola and Fusarium oxysporium.
In conclusion, phytochemical examination of the marine red algal L. nidifica, S. latiuscula and from the symbiotic fungus T. harzianum EN-85 led to the identification of 9 new compounds, which enriched the marine natural products library. Some compounds with PTP1B inhibitory activity and with anti-microbial activity were discovered.
蒲枝凹顶藻主要分布于夏威夷群岛,我们在开展海藻资源调查时于2008年首次发现其在我国南海海域的分布并对其次生代谢产物进行了研究。从中分离鉴定了21个化合物,其中有4个新化合物,包括1个charmigrane型倍半萜(LS8),2个bisabolane型倍半萜(LS9,LS10)和1个C15多聚乙酰(LS17)。对其中的LS1、LS3、LS6、LS7、LS8、LS12、LS13和LS17进行了抗菌活性测试。发现LS6对白菜黑斑病菌(Alternaria brassicae(berk.) Sace)有一定抑制活性;LS7对大肠杆菌(Escherichia coli)、金黄色葡萄球菌(Staphylococcus aureus)、白菜黑斑病菌(A. brassicae)和苹果轮纹病菌(Physalospora piricola Nose)均有弱的抑制活性;LS8对金黄色葡萄球菌(S. aureus)有弱的活性;LS12对金黄色葡萄球菌(S. aureus)和苹果轮纹病菌(P. piricola)有弱的活性。
对采集自山东威海海域的鸭毛藻进行了次生代谢产物研究。从中分离鉴定了13个化合物(9个为溴酚类化合物),其中有1个新化合物(SL1)。对其中的溴酚类化合物进行了抑制蛋白酪氨酸磷酸酯酶(PTP1B)活性筛选,发现化合物SL6、SL7,SL8具有很好的PTP1B抑制活性,IC50分别为3.9, 4.3, 3.5μmol/L,优于阳性对照正钒酸钠(IC50为4.6μmol/L),具有潜在的发展成抗糖尿病药物的研究价值。
研究了鸭毛藻共生真菌哈茨木霉(Trichoderma harzianum EN-85)的次生代谢产物。共分离鉴定了21个化合物,其中有4个新化合物,分别为两个倍半萜(FS2、FS4),一个二萜(FS14)和一个链状多烯醇类化合物(FS15)。对其粗提物和次生代谢产物进行了活性筛选。发现粗提物对白菜黑斑病菌(A. brassicae)和苹果轮纹病菌(P. piricola)具有一定的抑制作用。对分离得到的化合物FS1、FS3, FS4、FS8-FS10和FS12-FS15进行了抗菌试验。化合物FS3和FS4对苹果轮纹病菌(P.piricola)和棉花枯萎病菌(Fusarium oxysporium)有弱的抑制活性。
本文通过对蒲枝凹顶藻、鸭毛藻以及鸭毛藻共生真菌的次生代谢产物研究,不仅丰富了海洋天然产物的资源库,同时也发现了一些具有潜在抗糖尿病活性的溴酚物质和一些抗农业病害菌的真菌代谢产物,为海洋生物资源的利用提供了一定的科学依据。
In the present dissertation, the secondary metobolites from the marine red algal Laurencia nidifica and Symphyocladia latiuscula as well as the algal-derived symbiotic Trichoderma harzianum EN-85 were investigated. Repeated column chromatography on silica gel, Rp-18, ploymide, and Sephadex LH-20, prep-TLC, and semi-preparative HPLC were used to separate the compounds. Elucidation of the structures was performed by IR, UV, EI-MS, ESI-MS, HR-ESI-MS, 1D NMR and 2D NMR. A total of 55 compounds were separated and identified, with 9 of them were found as new compounds.
The marine red algal Laurencia nidifica was discovered for the first time in South China Sea. A total of 21 compounds were separated and identified from this species, including four new structures (one charmigrane sesquiterpene LS8, two bisabolene sesquiterpenes LS9 and LS10, and one C15-acetogein LS17). Compounds LS1, LS3, LS6, LS7, LS8, LS12, LS13, and LS17 were tested for the antimicrobial activity. Among them, compounds LS6 and LS7 exhibited weak inhibition against Alternaria brassicae (berk.) Sace and against Escherichia coli, Staphylococcus aureus, A. brassicae and Physalospora piricola Nose, respectively, while LS8 and LS12 exhibited weak inhibition against S. aureus and against S. aureus and P. piricola, respectively.
Another marine red algal Symphyocladia latiuscula was collected at the coast of Weihai in Shandong province. A total of 13 compounds were isolated and identified from the species including one new compound (SL1). Compounds SL2-SL9 were evaluated the activity against the protein tyrosine phosphatase 1B (PTP1B). Bromophenols SL6, SL7, and SL8 displayed potent activity with IC50 values 3.9, 4.3, and 3.5μmol/L, respectively, which might be used as a potential source for developing anti-diabetes drug.
The fungus Trichoderma harzianum EN-85 was isolated from the marine red algal Symphyocladia latiuscula and was identified by molecular biology methods. A total of 21 compounds were isolated and indentified from this fungal stain including 4 new compounds (two sesquiterpenes FS2 and FS4, one diterpene FS14, and one other compound FS15). The antimicrobial activity was evaluated. The inhibition on the A. brassicae and P. piricola were observed. Compounds FS1, FS3, FS4, FS8-FS10, and FS12-FS15 were tested the antimicrobial activity, and FS3 and FS4 exhibited weak inhibition against P. piricola and Fusarium oxysporium.
In conclusion, phytochemical examination of the marine red algal L. nidifica, S. latiuscula and from the symbiotic fungus T. harzianum EN-85 led to the identification of 9 new compounds, which enriched the marine natural products library. Some compounds with PTP1B inhibitory activity and with anti-microbial activity were discovered.
引文
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