Structural and Biogenic Analysis of Bioactive Marine Natural Products

我把这个主题分成五个部分来研究。从红藻中分离得到两个新的卤代倍半萜、chamigane衍生物、10个已知化合物和2个伪产物。从红藻中分离到3个卤代单萜衍生物。这些化合物的结构经核磁共振和质谱鉴定，并提出了合理的反应途径。从褐藻中分离出9个新的氧脂素代谢物和几个已知的代谢物。虽然对枯草芽孢杆菌和金黄色葡萄球菌进行了生物活性研究，但不幸的是，这些化合物对其细菌的抑制作用不如万古霉素标准样品。从夏威夷海洋软体动物Pilinopsis speciosa中分离到两个新的环状沉积肽（kulokekahilide-1, -2），它们对小鼠淋巴细胞白血病细胞具有细胞毒性，IC_<50>分别为2.1 μg/mL和3.5 ng/mL。用Marfey法和手性高效液相色谱法测定了由沉积肽组成的氨基酸和羟基酸的绝对立体化学。为了考察活性与结构之间的关系，我们尝试了kulokekahilide-2的全合成。研究了深海生物豆角藻（caltogena soyoae）、海苔藻（Ifremeria nautilei）和海苔藻（Rimicaris kairei）的成分分析。没有得到新的化合物，但从它们的材料中分离出许多已知的化合物。很明显，深海生物的脂肪酸组成与浅海生物的不同。采用数据挖掘方法对大肠杆菌、枯草芽孢杆菌和金黄色葡萄球菌的活性化合物进行了筛选。从而发现了从类黄酮和萜烯衍生物中提取的活性分类规律

I divided the theme into five next items and studied it.1. From the red alga genus Laurencia nidifica, two new halogenated sesqiterpenes, chamigrane derivatives were obtained together with ten known compounds and two artifacts. Also, three halogenated monoterpenes, octodene derivatives were isolated from the red alga, Scinecia okamurae. The structures of these compounds were elucidated by NMR and mass spectroscopy, and plausible reaction pathways were proposed.2. Nine novel oxylipin metabolites together with several known ones were isolated from the brown alga, Eisenia bicyclis. Though bioactive investigation against B. subtilis and S. aureus, was done, unfortunately these compounds have poorer inhibition against their bacteria than a standard sample of vancomycin.3. Two new cyclic depsipeptides (kulokekahilide-1, -2) which showed cytotoxity against P388 murine lymphocytic leukemia cells with IC_<50> values of 2.1 μg/mL and 3.5 ng/mL were isolated from a marine mollusk Pilinopsis speciosa in Hawaii. The absolute stereochemistry of amino acids and hydroxy acids composed with depsipeptides were determined by Marfey analysis and chiral HPLC analysis. In order to examine the relationship between activity and structure, the total synthesis of kulokekahilide-2 was attempted.4. The analysis of components contained in deep-sea organisms, Calytogena soyoae, Ifremeria nautilei, and Rimicaris kairei was studied. No novel compounds were obtained but many known compounds were isolated from their materials. It was clear that fatty acids composition in deep-sea organisms was different from that in shallow-sea organisms.5. Data-mining method applied for the active compounds against E.coli, B.subtilis, and S.aureus. Thus, it was found that the classification rules of the activity were extracted from flavonoid and terpene derivatives