臺灣博碩士論文加值系統

在針對養殖型八放珊瑚Briareum excavatum所含化學成分的研究中分離出三十二個briarane型式的雙萜化合物1‒32，其中化合物1‒18為新化合物，化合物19‒32為已知化合物。所有化合物的化學構造均由光譜數據分析而確定，而化合物briaexcavatins I (1)、U (13)、W (15)以及已知化合物excavatolides C (19)、E (20)的結構更進一步以X-ray單晶繞射實驗確認。化合物13與20的絕對立體構型則分別藉由X-ray單晶繞射實驗以及Mosher酯化反應修飾而確定。化合物briaexcavatin Y (17)是在briarane型態骨架的化合物中，第一個在C-8/9具有epoxy官能基的化合物。在此次研究也討論在C-11,12具有epoxy官能基的briarane化合物在13C NMR化學位移與結構立體位向的關係。在細胞毒殺活性試驗方面，briaexcavatin S (11)和已知化合物excavatolide C (19)、Z (24)對於人類淋巴瘤細胞CCRF-CEM具有微弱的細胞毒殺活性，另外化合物
briaexcavatin J (2) 和已知化合物excavatolide C (19)對於直腸腫瘤細胞DLD-1也顯示有微弱的細胞毒殺活性；在抗發炎活性試驗方面，excavatolide Z (24)和briaexcavatolides
O (26)、P (27)對於超氧自由基的產生顯示有中等的抑制活性；而在抑制彈性蛋白酶產生的試驗中briaexcavatin V (14) 、excavatolide Z (24)、briaexcavatolide O (26)、
11-hydroxybrianthein U (30)顯示具有中等的抑制效果；另外briaexcavatin Z (18)卻發現有中等的促進彈性蛋白酶的產生情形。

In the continuing search for novel substances from marine invertebrates originally distributed in Taiwan waters. The octocoral Briareum excavatum was transplanted to the culturing tanks located in the NMMBA for its interesting chemical constituents. This study had led to the isolation of 32 briarane derivatives 1–32, including 18 new compounds,
briaexcavatins I–Z (1–18) from the cultured B. excavatum. The structures of compounds
1–32 were determined by spectroscopic methods and the structures of briaexcavatins I (1), U (13), W (15) and the known compound excavatolides C (19) and E (20) were confirmed by X-ray data analysis. The absolute configurations of briaranes 13 and 20 were determined by X-ray diffraction analysis and modified Mosher’s method, respectively. It is noteworthy
to mention that briaexcavatin Y (17) represents the first example of a briarane possessing a C-8/9 epoxy group. The relationships between 13C NMR chemical shifts and the conformations of the briaranes possessing an 11,12-epoxy group are described.
In biological activity experiments, briaranes 11, 19, and 24 exhibited weak cytotoxicity toward CCRF-CEM tumor cells and compounds 2 and 19 showed weak
cytotoxicity toward DLD-1 tumor cells, respectively. Moreover some of these briaranes such as compounds 24, 26, and 27 have displayed mild inhibitory effects on superoxide anion generation by human neutrophils. Compounds 14, 24, 26, and 30 showed mild inhibitory effects on human neutrophil elastase release. Compound 18 exhibited mild
activity to enhance human neutrophil elastase release.

中文摘要 XVII

英文摘要 XVIII

壹、緒論 1
第一節、前言 1
第二節、研究動機 2
第三節、Briareum屬軟珊瑚文獻回顧 5
貳、生物材料與研究方法 35
第一節、生物材料的採集與分類 35
第二節、生物樣品的萃取與分離流程 37
第三節、Mosher’s 酯化反應 40
參、實驗器材與有機溶劑 41
第一節、儀器 41
第二節、有機溶劑 42
肆、生物活性試驗 44
第一節、細胞毒殺活性測試 44
第二節、抗發炎活性測試 45
伍、結果與討論 49
第一節、軟珊瑚Briareum excavatumn所含成分之研究 49
(一)、Briaexcavatin I (1)之結構解析 49
(二)、Briaexcavatin J (2)之結構解析 61
(三)、Briaexcavatin K (3)之結構解析 71
(四)、Briaexcavatin L (4)之結構解析 81
(五)、Briaexcavatin M (5)之結構解析 91
(六)、Briaexcavatin N (6)之結構解析 103
(七)、Briaexcavatin O (7)之結構解析 115
(八)、Briaexcavatin P (8)之結構解析 127
(九)、Briaexcavatin Q (9)之結構解析 137
(十)、Briaexcavatin R (10)之結構解析 149
(十一)、Briaexcavatin S (11)之結構解析 159
(十二)、Briaexcavatin T (12)之結構解析 169
(十三)、Briaexcavatin U (13)之結構解析 181
(十四)、Briaexcavatin V (14)之結構解析 193
(十五)、Briaexcavatin W (15)之結構解析 205
(十六)、Briaexcavatin X (16)之結構解析 217
(十七)、Briaexcavatin Y (17)之結構解析 227
(十八)、Briaexcavatin Z (18)之結構解析 237
(十九) Excavatolide C (19)之結構解析 247
(二十) Excavatolide E (20)之結構解析 249
(二十一) Excavatolide D (21)之結構解析 255
(二十二) Excavatolide F (22)之結構解析 259
(二十三) Excavatolide M (23)之結構解析 263
(二十四) Excavatolide Z (24)之結構解析 267
(二十五) Briaexcavatolide L (25)之結構解析 271
(二十六) Briaexcavatolide O (26)之結構解析 275
(二十七) Briaexcavatolide P (27)之結構解析 279
(二十八) Briaexcavatolide W (28)之結構解析 283
(二十九) Briaexcavatolide U (29)之結構解析 287
(三十) 11-Hydroxybrianthein U (30)之結構解析 291
(三十一) Pachyclavulide A (31)之結構解析 295
(三十二) Briareolide B (32)之結構解析 299
第二節、化合物實驗數據整理 303
第三節、化合物生物活性試驗結果 307
陸、結論 311
柒、參考文獻 315
捌、附錄 321
附錄一、X-ray解析資料 321

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