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論文名稱 Title |
台灣產皮軟珊瑚Briareum sp.與柳羽珊瑚Pinnigorgia sp.化學成分及其生物活性之研究 Studies on the Chemical Constituents and Their Biological Activities from the Formosan Corals Briareum sp. and Pinnigorgia sp. |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
416 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2016-01-25 |
繳交日期 Date of Submission |
2016-02-14 |
關鍵字 Keywords |
彈性纖維蛋白酶、超氧自由基離子、柳羽珊瑚、皮軟珊瑚、環氧化酶-2、一氧化氮合成酶 Pinnigorgia, Briareum, superoxide anion, elastase, iNOS, COX-2 |
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統計 Statistics |
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中文摘要 |
本研究針對臺灣南部海域採集之皮軟珊瑚Briareum sp.所含二次代謝物進行研究,共分離純化共得三十七個化合物,包含二十四個新briarane-type的雙萜化合物briarenolides H–Y (1–18)、ZI–ZVI (19–24) 與13個已知化合物briaexcavatolides H (25)、F (28)、G (29)、P (32)、solenolides A (26)、C (27)、brianolide (30)、briaexcavatins P (31)、K (34)、N (35)、excavatolides M (33)、Z (36)、2β-acetoxy-2-(debutyryloxy) stecholide E (37),其中briarenolide J (3) 是第一個分別在C-6和C-12位置上接有氯原子的briarane類化合物。另外,從柳羽珊瑚Pinnigorgia sp. 中分離出三個新的固醇類化合物 pinnigorsterols A (38)、B (39)與pinnisterol A (40),其中化合物38為具有一組雙鍵位於C-8與C-9的固醇類化合物,化合物39與40則為9,11 secosteroid 類型化合物,化合物1–40的結構均是經由光譜資料分析和比對相關文獻化合物建立。 在抗發炎反應實驗中,化合物3、5、39與40具有顯著的抑制人類嗜中性白血球釋放超氧自由基離子 (superoxide anion) (IC50 = 7.73, 7.14, 3.12,1.70 μg/mL)與彈性蛋白酶 (elastase) (IC50 = 5.14, 6.86, 2.40, 1.02 μg/mL) 的活性,其中化合物38對彈性蛋白酶有專一性的顯著抑制效果 (IC50 = 4.47 μg/mL),並進一步發現化合物9、15與38–40對於脂多糖 (lipopolysaccharide, LPS) 誘發小鼠巨噬細胞 (RAW 264.7) 所產生的發炎性蛋白一氧化氮合成酶 (iNOS) (47.3, 41.9, 16.3, 14.5, 19.8%) 與環氧化酶-2 (COX-2) (35.6, 26.1, 37.1, 44.4 , 59.0%) 具有顯著抑制活性。 |
Abstract |
Studies on the secondary metabolites of the octocoral Briareum sp. collected off the coast of Southern Taiwan had led to the isolation of twenty-four new briarane analogues, including briarenolides H–Y (1–18) and ZI–ZVI (19–24), along with thirteen known compounds, briaexcavatolides H (25), F (28), G (29), P (32), solenolides A (26), C (27), brianolide (30), briaexcavatins P (31), K (34), N (35), excavatolides M (33), Z (36), and 2β-acetoxy-2-(debutyryloxy) stecholide E (37). It is worth noting that briarenolide J (3) is the first dichlorobriarane found to possess a chlorine atom at C-12. In addition, one new steroid pinnigorsterol A (38) and two new 9,11-secosterols pinnigorsterol B (39) and pinnisterol A (40) were obtained from a gorgonian identified as Pinnigorgia sp. The structures of metabolites 1–40 were established by spectroscopic methods and by comparison of the spectroscopic data with those of related metabolites. In the in vitro anti-inflammatory experiments, metabolites 3, 5, 39, and 40 have displayed significant inhibitory effects on superoxide anion generation (IC50 = 7.73, 7.14, 3.12, and 1.70 μg/mL) and elastase release (IC50 = 5.14, 6.86, 2.40, and 1.02 μg/mL) by human neutrophils. Sterol 38 showed an inhibitory effect on human neutrophil elastase release (IC50 = 4.47 μg/mL). Furthermore, compounds 9, 15 and 38–40 were found to inhibit the accumulation of the pro-inflammatory iNOS protein (47.3, 41.9, 16.3, 14.5, and 19.8%) and COX-2 protein (35.6, 26.1, 37.1, 44.4, and 59.0%) in the LPS- stimulated RAW264.7 macrophage cells. |
目次 Table of Contents |
目錄 頁次 中文摘要..........................................................i 英文摘要..........................................................ii 圖目錄............................................................vii 表目錄............................................................xvi 第一章 緒論......................................................1 第一節 前言..................................................1 第二節 研究動機..............................................4 第三節 Briareum屬所含天然物之文獻回顧.......................10 第四節 9,11-secosteroid天然物之文獻回顧.........................48 第二章 生物材料與分離流程.......................................60 第一節 生物樣品採集與分類.....................................60 第二節 生物樣品萃取與實驗流程…...............................62 第三章 實驗器材與有機溶劑.......................................68 第一節 儀器...................................................68 第二節 藥品試劑...............................................69 第四章 生物活性試驗 ............................................70 第一節 細胞毒殺測試...........................................70 第二節 抗發炎測試Ⅰ...........................................73 第三節 抗發炎測試Ⅱ...........................................76 第五章 結果與討論................................................78 第一節皮軟珊瑚Briareum sp.所含化學成分之結構解析.............78 (一)Briarenolide H (1) 之結構解析..............................78 (二)Briarenolide I (2) 之結構解析..............................88 (三)Briarenolide J (3) 之結構解析..............................98 (四)Briarenolide K (4) 之結構解析.............................108 (五)Briarenolide L (5) 之結構解析.............................118 (六)Briarenolide M (6) 之結構解析.............................128 (七)Briarenolide N (7) 之結構解析.............................138 (八)Briarenolide O (8) 之結構解析.............................148 (九)Briarenolide P (9) 之結構解析.............................158 (十)Briarenolide Q (10) 之結構解析............................168 (十一)Briarenolide R (11) 之結構解析..........................179 (十二)Briarenolide S (12) 之結構解析..........................189 (十三)Briarenolide T (13) 之結構解析..........................199 (十四)Briarenolide U (14) 之結構解析..........................209 (十五)Briarenolide V (15) 之結構解析..........................219 (十六)Briarenolide W (16) 之結構解析......................... 230 (十七)Briarenolide X (17) 之結構解析..........................241 (十八)Briarenolide Y (18) 之結構解析..........................251 (十九)Briarenolide ZI(19) 之結構解析......................... 261 (二十)Briarenolide ZII (20) 之結構解析........................271 (二十一)Briarenolide ZIII (21) 之結構解析.....................281 (二十二)Briarenolide ZIV (22) 之結構解析......................291 (二十三)Briarenolide ZV (23) 之結構解析.......................301 (二十四)Briarenolide ZVI (24) 之結構解析......................311 第二節 皮軟珊瑚Briareum sp.所含化學成分之已知化合物.........321 第三節 柳羽珊瑚Pinnigorgia sp.所含化學成分之結構解析........322 (三十八)Pinnigorsterol A (38) 之結構解析..................... 322 (三十九)Pinnigorsterol B (39) 之結構解析..................... 331 (四十)Pinnisterol A (40) 之結構解析...........................340 第四節 化合物實驗數據整理..................................349 第五節 化合物生物活性試驗結果..............................354 第六章 結論....................................................360 第七章 參考文獻................................................374 第八章 附錄....................................................389 圖目錄 Figure 1-2-1 2006年統計抗癌藥物來源示意圖。.............................4 Figure 1-2-2 海洋無脊椎動物所分離出的新化合物數量變化趨勢。.............6 Figure 1-2-3 刺絲胞動物門中所分離出具有生物活性的海洋化合物類別的比例。.7 Figure 1-2-4 Marine drugs on the market and conditions treated..........7 Figure 2-1-1 野生型皮軟珊瑚Briareum sp.之生態圖片......................60 Figure 2-1-2 野生型柳羽珊瑚Pinnigorgia sp.之生態圖片...................61 Scheme 2-2-1 Briareum sp. 皮軟珊瑚的分離流程 (I).......................63 Scheme 2-2-2 Briareum sp. 皮軟珊瑚的分離流程 (II.......................64 Scheme 2-2-3 Briareum sp. 皮軟珊瑚的分離流程 (III).....................65 Scheme 2-2-4 Pinnigorgia sp. 柳羽珊瑚的分離流程........................67 Figure 4-1-1 MTT轉變成formazan示意圖...................................72 Figure 4-2-1 抗發炎之Degranulation 試驗之實驗流程......................74 Figure 4-2-2 抗發炎之Superoxide anion試驗之實驗流程....................75 Figure 5-1-1-1 The 1H–1H COSY and selective HMBC correlations of 1......79 Figure 5-1-1-2 Selective NOESY correlations of 1.........................81 Figure 5-1-1-3 化合物1之IR圖譜...........................................83 Figure 5-1-1-4 化合物1之低解析ESIMS圖譜..................................83 Figure 5-1-1-5 化合物1之高解析ESIMS圖譜..................................84 Figure 5-1-1-6 化合物1之1H NMR圖譜.......................................84 Figure 5-1-1-7 化合物1之13C NMR圖譜......................................85 Figure 5-1-1-8 化合物1之DEPT圖譜.........................................85 Figure 5-1-1-9 化合物1之HSQC圖譜.........................................86 Figure 5-1-1-10 化合物1之1H–1H COSY圖譜..................................86 Figure 5-1-1-11 化合物1之HMBC圖譜.........................................87 Figure 5-1-1-12 化合物1之NOESY圖譜........................................87 Figure 5-1-2-1 The 1H–1H COSY and selective HMBC correlations of 2......89 Figure 5-1-2-2 Selective NOESY correlations of 2.........................91 Figure 5-1-2-3 化合物2之IR圖譜...........................................93 Figure 5-1-2-4 化合物2之低解析ESIMS圖譜..................................93 Figure 5-1-2-5 化合物2之高解析ESIMS圖譜..................................94 Figure 5-1-2-6 化合物2之1H NMR圖譜.......................................94 Figure 5-1-2-7 化合物2之13C NMR圖譜......................................95 Figure 5-1-2-8 化合物2之DEPT圖譜.........................................95 Figure 5-1-2-9 化合物2之HSQC圖譜.........................................96 Figure 5-1-2-10 化合物2之1H–1H COSY圖譜..................................96 Figure 5-1-2-11 化合物2之HMBC圖譜.........................................97 Figure 5-1-2-12 化合物2之NOESY圖譜........................................97 Figure 5-1-3-1 The 1H–1H COSY and selective HMBC correlations of 3.....100 Figure 5-1-3-2 Selective NOESY correlations of 3........................101 Figure 5-1-3-3 化合物3之IR圖譜..........................................103 Figure 5-1-3-4 化合物3之低解析ESIMS圖譜.................................103 Figure 5-1-3-5 化合物3之高解析ESIMS圖譜.................................104 Figure 5-1-3-6 化合物3之1H NMR圖譜......................................104 Figure 5-1-3-7 化合物3之13C NMR圖譜.....................................105 Figure 5-1-3-8 化合物3之DEPT圖譜........................................105 Figure 5-1-3-9 化合物3之HSQC圖譜........................................106 Figure 5-1-3-10 化合物3之1H–1H COSY圖譜.................................106 Figure 5-1-3-11 化合物3之HMBC圖譜........................................107 Figure 5-1-3-12 化合物3之NOESY圖譜.......................................107 Figure 5-1-4-1 The 1H–1H COSY and selective HMBC correlations of 4.....109 Figure 5-1-4-2 Selective NOESY correlations of 4........................111 Figure 5-1-4-3 化合物4之IR圖譜..........................................113 Figure 5-1-4-4 化合物4之低解析ESIMS圖譜.................................113 Figure 5-1-4-5 化合物4之高解析ESIMS圖譜.................................114 Figure 5-1-4-6 化合物4之1H NMR圖譜......................................114 Figure 5-1-4-7 化合物4之13C NMR圖譜.....................................115 Figure 5-1-4-8 化合物4之HSQC圖譜........................................115 Figure 5-1-4-9 化合物4之1H–1H COSY圖譜.................................116 Figure 5-1-4-10 化合物4之HMBC圖譜........................................116 Figure 5-1-4-11 化合物4之NOESY圖譜.......................................117 Figure 5-1-5-1 The 1H–1H COSY and selective HMBC correlations of 5.....120 Figure 5-1-5-2 Selective NOESY correlations of 5........................121 Figure 5-1-5-3 化合物5之IR圖譜..........................................123 Figure 5-1-5-4 化合物5之低解析ESIMS圖譜.................................123 Figure 5-1-5-5 化合物5之高解析ESIMS圖譜.................................124 Figure 5-1-5-6 化合物5之1H NMR圖譜......................................124 Figure 5-1-5-7 化合物5之13C NMR圖譜.....................................125 Figure 5-1-5-8 化合物5之HSQC圖譜........................................125 Figure 5-1-5-9 化合物5之1H–1H COSY圖譜.................................126 Figure 5-1-5-10 化合物5之HMBC圖譜........................................126 Figure 5-1-5-11 化合物5之NOESY圖譜.......................................127 Figure 5-1-6-1 The 1H–1H COSY and selective HMBC correlations of 6.....129 Figure 5-1-6-2 Selective NOESY correlations of 6........................131 Figure 5-1-6-3 化合物6之IR圖譜..........................................133 Figure 5-1-6-4 化合物6之低解析ESIMS圖譜.................................133 Figure 5-1-6-5 化合物6之高解析ESIMS圖譜.................................134 Figure 5-1-6-6 化合物6之1H NMR圖譜......................................134 Figure 5-1-6-7 化合物6之13C NMR圖譜.....................................135 Figure 5-1-6-8 化合物6之DEPT圖譜........................................135 Figure 5-1-6-9 化合物6之HSQC圖譜........................................136 Figure 5-1-6-10 化合物6之1H–1H COSY圖譜.................................136 Figure 5-1-6-11 化合物6之HMBC圖譜........................................137 Figure 5-1-6-12 化合物6之NOESY圖譜.......................................137 Figure 5-1-7-1 The 1H–1H COSY and selective HMBC correlations of 7.....140 Figure 5-1-7-2 Selective NOESY correlations of 7........................141 Figure 5-1-7-3 化合物7之IR圖譜..........................................143 Figure 5-1-7-4 化合物7之低解析ESIMS圖譜.................................143 Figure 5-1-7-5 化合物7之高解析ESIMS圖譜.................................144 Figure 5-1-7-6 化合物7之1H NMR圖譜......................................144 Figure 5-1-7-7 化合物7之13C NMR圖譜.....................................145 Figure 5-1-7-8 化合物7之HSQC圖譜........................................145 Figure 5-1-7-9 化合物7之1H–1H COSY圖譜.................................146 Figure 5-1-7-10 化合物7之HMBC圖譜........................................146 Figure 5-1-7-11 化合物7之NOESY圖譜.......................................147 Figure 5-1-8-1 The 1H–1H COSY and selective HMBC correlations of 8.....150 Figure 5-1-8-2 Selective NOESY correlations of 8........................151 Figure 5-1-8-3 化合物8 IR圖譜...........................................153 Figure 5-1-8-4 化合物8低解析ESIMS圖譜...................................153 Figure 5-1-8-5 化合物8之高解析ESIMS圖譜.................................154 Figure 5-1-8-6 化合物8之1H NMR圖譜......................................154 Figure 5-1-8-7 化合物8之13C NMR圖譜.....................................155 Figure 5-1-8-8 化合物8之DEPT圖譜........................................155 Figure 5-1-8-9 化合物8之HSQC圖譜........................................156 Figure 5-1-8-10 化合物8之1H–1H COSY圖譜.................................156 Figure 5-1-8-11 化合物8之HMBC圖譜........................................157 Figure 5-1-8-12 化合物8之NOESY圖譜.......................................157 Figure 5-1-9-1 The 1H–1H COSY and selective HMBC correlations of 9.....160 Figure 5-1-9-2 Selective NOESY correlations of 9........................161 Figure 5-1-9-3 化合物9之IR圖譜..........................................163 Figure 5-1-9-4 化合物9之低解析ESIMS圖譜.................................163 Figure 5-1-9-5 化合物9之高解析ESIMS圖譜.................................164 Figure 5-1-9-6 化合物9之1H NMR圖譜......................................164 Figure 5-1-9-7 化合物9之13C NMR圖譜.....................................165 Figure 5-1-9-8 化合物9之DEPT圖譜........................................165 Figure 5-1-9-9 化合物9之HSQC圖譜........................................166 Figure 5-1-9-10 化合物9之1H–1H COSY圖譜.................................166 Figure 5-1-9-11 化合物9之HMBC圖譜........................................167 Figure 5-1-9-12 化合物9之NOESY圖譜.......................................167 Figure 5-1-10-1 The 1H–1H COSY and selective HMBC correlations of 10....170 Figure 5-1-10-2 Selective NOESY correlations of 10.......................172 Figure 5-1-10-3 化合物10之IR圖譜.........................................174 Figure 5-1-10-4 化合物10之低解析ESIMS圖譜................................174 Figure 5-1-10-5 化合物10之高解析ESIMS圖譜................................175 Figure 5-1-10-6 化合物10之1H NMR圖譜.....................................175 Figure 5-1-10-7 化合物10之13C NMR圖譜....................................176 Figure 5-1-10-8 化合物10之DEPT圖譜.......................................176 Figure 5-1-10-9 化合物10之HSQC圖譜.......................................177 Figure 5-1-10-10化合物10之1H–1H COSY圖譜................................177 Figure 5-1-10-11化合物10之HMBC圖譜.......................................178 Figure 5-1-10-12化合物10之NOESY圖譜......................................178 Figure 5-1-11-1 The 1H–1H COSY and selective HMBC correlations of 11....181 Figure 5-1-11-2 Selective NOESY correlations of 11.......................182 Figure 5-1-11-3 化合物11之IR圖譜.........................................184 Figure 5-1-11-4 化合物11之低解析ESIMS圖譜................................184 Figure 5-1-11-5 化合物11之高解析ESIMS圖譜................................185 Figure 5-1-11-6 化合物11之1H NMR圖譜.....................................185 Figure 5-1-11-7 化合物11之13C NMR圖譜....................................186 Figure 5-1-11-8 化合物11之DEPT圖譜.......................................186 Figure 5-1-11-9 化合物11之HSQC圖譜.......................................187 Figure 5-1-11-10化合物11之1H–1H COSY圖譜................................187 Figure 5-1-11-11化合物11之HMBC圖譜.......................................188 Figure 5-1-11-12化合物11之NOESY圖譜......................................188 Figure 5-1-12-1 The 1H–1H COSY and selective HMBC correlations of 12....191 Figure 5-1-12-2 Selective NOESY correlations of 12.......................192 Figure 5-1-12-3 化合物12之IR圖譜.........................................194 Figure 5-1-12-4 化合物12之低解析ESIMS圖譜................................194 Figure 5-1-12-5 化合物12之高解析ESIMS圖譜................................195 Figure 5-1-12-6 化合物12之1H NMR圖譜.....................................195 Figure 5-1-12-7 化合物12之13C NMR圖譜....................................196 Figure 5-1-12-8 化合物12之HSQC圖譜.......................................196 Figure 5-1-12-9 化合物12之1H–1H COSY圖譜................................197 Figure 5-1-12-10化合物12之HMBC圖譜.......................................197 Figure 5-1-12-11化合物12之NOESY圖譜......................................198 Figure 5-1-13-1 The 1H–1H COSY and selective HMBC correlations of 13....201 Figure 5-1-13-2 Selective NOESY correlations of 13.......................202 Figure 5-1-13-3 化合物13之IR圖譜.........................................204 Figure 5-1-13-4 化合物13之低解析ESIMS圖譜................................204 Figure 5-1-13-5 化合物13之高解析ESIMS圖譜................................205 Figure 5-1-13-6 化合物13之1H NMR圖譜.....................................205 Figure 5-1-13-7 化合物13之13C NMR圖譜....................................206 Figure 5-1-13-8 化合物13之DEPT圖譜.......................................206 Figure 5-1-13-9 化合物13之HSQC圖譜.......................................207 Figure 5-1-13-10化合物13之1H–1H COSY圖譜................................207 Figure 5-1-13-11化合物13之HMBC圖譜.......................................208 Figure 5-1-13-12化合物13之NOESY圖譜......................................208 Figure 5-1-14-1 The 1H–1H COSY and selective HMBC correlations of 14....210 Figure 5-1-14-2 Selective NOESY correlations of 14.......................212 Figure 5-1-14-3 化合物14之IR圖譜.........................................214 Figure 5-1-14-4 化合物14之低解析ESIMS圖譜................................214 Figure 5-1-14-5 化合物14之高解析ESIMS圖譜................................215 Figure 5-1-14-6 化合物14之1H NMR圖譜.....................................215 Figure 5-1-14-7 化合物14之13C NMR圖譜....................................216 Figure 5-1-14-8 化合物14之DEPT圖譜.......................................216 Figure 5-1-14-9 化合物14之HSQC圖譜.......................................217 Figure 5-1-14-10化合物14之1H–1H COSY圖譜................................217 Figure 5-1-14-11化合物14之HMBC圖譜.......................................218 Figure 5-1-14-12化合物14之NOESY圖譜......................................218 Figure 5-1-15-1 The 1H–1H COSY and selective HMBC correlations of 15....221 Figure 5-1-15-2 Selective NOESY correlations of 15.......................223 Figure 5-1-15-3 化合物15之IR圖譜.........................................225 Figure 5-1-15-4 化合物15之低解析ESIMS圖譜................................225 Figure 5-1-15-5 化合物15之高解析ESIMS圖譜................................226 Figure 5-1-15-6 化合物15之1H NMR圖譜.....................................226 Figure 5-1-15-7 化合物15之13C NMR圖譜....................................227 Figure 5-1-15-8 化合物15之DEPT圖譜.......................................227 Figure 5-1-15-9 化合物15之HSQC圖譜.......................................228 Figure 5-1-15-10化合物15之1H–1H COSY圖譜................................228 Figure 5-1-15-11化合物15之HMBC圖譜.......................................229 Figure 5-1-15-12化合物15之NOESY圖譜......................................229 Figure 5-1-16-1 The 1H–1H COSY and selective HMBC correlations of 16....232 Figure 5-1-16-2 Selective NOESY correlations of 16.......................234 Figure 5-1-16-3 化合物16之IR圖譜.........................................236 Figure 5-1-16-4 化合物16之低解析ESIMS圖譜................................236 Figure 5-1-16-5 化合物16之高解析ESIMS圖譜................................237 Figure 5-1-16-6 化合物16之1H NMR圖譜.....................................237 Figure 5-1-16-7 化合物16之13C NMR圖譜....................................238 Figure 5-1-16-8 化合物16之HSQC圖譜.......................................238 Figure 5-1-16-9 化合物16之1H–1H COSY圖譜................................239 Figure 5-1-16-10化合物16之HMBC圖譜.......................................239 Figure 5-1-16-11化合物16之NOESY圖譜......................................240 Figure 5-1-17-1 The 1H–1H COSY and selective HMBC correlations of 17....242 Figure 5-1-17-2 Selective NOESY correlations of 17.......................244 Figure 5-1-17-3 化合物17之IR圖譜.........................................246 Figure 5-1-17-4 化合物17之低解析ESIMS圖譜................................246 Figure 5-1-17-5 化合物17之高解析ESIMS圖譜................................247 Figure 5-1-17-6 化合物17之1H NMR圖譜.....................................247 Figure 5-1-17-7 化合物17之13C NMR圖譜....................................248 Figure 5-1-17-8 化合物17之HSQC圖譜.......................................248 Figure 5-1-17-9 化合物17之1H–1H COSY圖譜................................249 Figure 5-1-17-10化合物17之HMBC圖譜.......................................249 Figure 5-1-17-11化合物17之NOESY圖譜......................................250 Figure 5-1-18-1 The 1H–1H COSY and selective HMBC correlations of 18....253 Figure 5-1-18-2 Selective NOESY correlations of 18.......................254 Figure 5-1-18-3 化合物18之IR圖譜.........................................256 Figure 5-1-18-4 化合物18之低解析ESIMS圖譜................................256 Figure 5-1-18-5 化合物18之高解析ESIMS圖譜................................257 Figure 5-1-18-6 化合物18之1H NMR圖譜.....................................257 Figure 5-1-18-7 化合物18之13C NMR圖譜....................................258 Figure 5-1-18-8 化合物18之DEPT圖譜.......................................258 Figure 5-1-18-9 化合物18之HSQC圖譜.......................................259 Figure 5-1-18-10化合物18之1H–1H COSY圖譜................................259 Figure 5-1-18-11化合物18之HMBC圖譜.......................................260 Figure 5-1-18-12化合物18之NOESY圖譜......................................260 Figure 5-1-19-1 The 1H–1H COSY and selective HMBC correlations of 19....263 Figure 5-1-19-2 Selective NOESY correlations of 19.......................264 Figure 5-1-19-3 化合物19之IR圖譜.........................................266 Figure 5-1-19-4 化合物19之低解析ESIMS圖譜................................266 Figure 5-1-19-5 化合物19之高解析ESIMS圖譜................................267 Figure 5-1-19-6 化合物19之1H NMR圖譜.....................................267 Figure 5-1-19-7 化合物19之13C NMR圖譜....................................268 Figure 5-1-19-8 化合物19之DEPT圖譜.......................................268 Figure 5-1-19-9 化合物19之HSQC圖譜.......................................269 Figure 5-1-19-10化合物19之1H–1H COSY圖譜................................269 Figure 5-1-19-11化合物19之HMBC圖譜.......................................270 Figure 5-1-19-12化合物19之NOESY圖譜......................................270 Figure 5-1-20-1 The 1H–1H COSY and selective HMBC correlations of 20....273 Figure 5-1-20-2 Selective NOESY correlations of 20.......................274 Figure 5-1-20-3 化合物20之IR圖譜.........................................276 Figure 5-1-20-4 化合物20之低解析ESIMS圖譜................................276 Figure 5-1-20-5 化合物20之高解析ESIMS圖譜................................277 Figure 5-1-20-6 化合物20之1H NMR圖譜.....................................277 Figure 5-1-20-7 化合物20之13C NMR圖譜....................................278 Figure 5-1-20-8 化合物20之HSQC圖譜.......................................278 Figure 5-1-20-9 化合物20之1H–1H COSY圖譜................................279 Figure 5-1-20-10化合物20之HMBC圖譜.......................................279 Figure 5-1-20-11化合物20之NOESY圖譜......................................280 Figure 5-1-21-1 The 1H–1H COSY and selective HMBC correlations of 21....283 Figure 5-1-21-2 Selective NOESY correlations of 21.......................284 Figure 5-1-21-3 化合物21之IR圖譜.........................................286 Figure 5-1-21-4 化合物21之低解析ESIMS圖譜................................286 Figure 5-1-21-5 化合物21之高解析ESIMS圖譜................................287 Figure 5-1-21-6 化合物21之1H NMR圖譜.....................................287 Figure 5-1-21-7 化合物21之13C NMR圖譜....................................288 Figure 5-1-21-8 化合物21之DEPT圖譜.......................................288 Figure 5-1-21-9 化合物21之HSQC圖譜.......................................289 Figure 5-1-21-10化合物21之1H–1H COSY圖譜................................289 Figure 5-1-21-11化合物21之HMBC圖譜.......................................290 Figure 5-1-21-12化合物21之NOESY圖譜......................................290 Figure 5-1-22-1 The 1H–1H COSY and selective HMBC correlations of 22....293 Figure 5-1-22-2 Selective NOESY correlations of 22.......................294 Figure 5-1-22-3 化合物22之IR圖譜.........................................296 Figure 5-1-22-4 化合物22之低解析ESIMS圖譜................................296 Figure 5-1-22-5 化合物22之高解析ESIMS圖譜................................297 Figure 5-1-22-6 化合物22之1H NMR圖譜.....................................297 Figure 5-1-22-7 化合物22之13C NMR圖譜....................................298 Figure 5-1-22-8 化合物22之DEPT圖譜.......................................298 Figure 5-1-22-9 化合物22之HSQC圖譜.......................................299 Figure 5-1-22-10化合物22之1H–1H COSY圖譜................................299 Figure 5-1-22-11化合物22之HMBC圖譜.......................................300 Figure 5-1-22-12化合物22之NOESY圖譜......................................300 Figure 5-1-23-1 The 1H–1H COSY and selective HMBC correlations of 23....303 Figure 5-1-23-2 Selective NOESY correlations of 23.......................304 Figure 5-1-23-3 化合物23之IR圖譜.........................................306 Figure 5-1-23-4 化合物23之低解析ESIMS圖譜................................306 Figure 5-1-23-5 化合物23之高解析ESIMS圖譜................................307 Figure 5-1-23-6 化合物23之1H NMR圖譜.....................................307 Figure 5-1-23-7 化合物23之13C NMR圖譜....................................308 Figure 5-1-23-8 化合物23之HSQC圖譜.......................................308 Figure 5-1-23-9 化合物23之1H–1H COSY圖譜................................309 Figure 5-1-23-10化合物23之HMBC圖譜.......................................309 Figure 5-1-23-11化合物23之NOESY圖譜......................................310 Figure 5-1-24-1 The 1H–1H COSY and selective HMBC correlations of 24....312 Figure 5-1-24-2 Selective NOESY correlations of 24.......................314 Figure 5-1-24-3 化合物24之IR圖譜.........................................316 Figure 5-1-24-4 化合物24之低解析ESIMS圖譜................................316 Figure 5-1-24-5 化合物24之高解析ESIMS圖譜................................317 Figure 5-1-24-6 化合物24之1H NMR圖譜.....................................317 Figure 5-1-24-7 化合物24之13C NMR圖譜....................................318 Figure 5-1-24-8 化合物24之HSQC圖譜.......................................318 Figure 5-1-24-9 化合物24之1H–1H COSY圖譜................................319 Figure 5-1-24-10化合物24之HMBC圖譜.......................................319 Figure 5-1-24-11化合物24之NOESY圖譜......................................320 Figure 5-2-38-1 The 1H–1H COSY and selective HMBC correlations of 38....323 Figure 5-2-38-2 The 13C-NMR chemical shifts of the side-chain of pinnigorsterol A (38), (22E,24S)-24-methyl-cholest-5-en-3-ol (A), and (22E,24R)-24-methylcholest-5-en-3-ol (B)....324 Figure 5-2-38-3 Selective NOESY correlations of 38.......................324 Figure 5-2-38-4 化合物38之IR圖譜.........................................326 Figure 5-2-38-5 化合物38之低解析ESIMS圖譜................................326 Figure 5-2-38-6 化合物38之高解析ESIMS圖譜................................327 Figure 5-2-38-8 化合物38之13C NMR圖譜....................................328 Figure 5-2-38-9 化合物38之DEPT圖譜.......................................328 Figure 5-2-38-10化合物38之HSQC圖譜.......................................329 Figure 5-2-38-11化合物38之1H–1H COSY圖譜................................329 Figure 5-2-38-12化合物38之HMBC圖譜.......................................330 Figure 5-2-38-13化合物38之NOESY圖譜......................................330 Figure 5-2-39-1 The 1H–1H COSY and selective HMBC correlations of 39....332 Figure 5-2-39-2 The 13C-NMR chemical shifts of the side-chain of pinnigorsterol B (39), (24S)-24-methyl-cholest-5-en-3-ol (A), and (24R)-24-methylcholest-5-en-3-ol (B)............333 Figure 5-2-39-3 Selective NOESY correlations of 39.......................333 Figure 5-2-39-4 化合物39之IR圖譜.........................................335 Figure 5-2-39-5 化合物39之低解析ESIMS圖譜................................335 Figure 5-2-39-6 化合物39之高解析ESIMS圖譜................................336 Figure 5-2-39-7 化合物39之1H NMR圖譜.....................................336 Figure 5-2-39-8 化合物39之13C NMR圖譜....................................337 Figure 5-2-39-9 化合物39之DEPT圖譜.......................................337 Figure 5-2-39-10化合物39之HSQC圖譜.......................................338 Figure 5-2-39-11化合物39之1H–1H COSY圖譜................................338 Figure 5-2-39-12化合物39之HMBC圖譜.......................................339 Figure 5-2-39-13化合物39之NOESY圖譜......................................339 Figure 5-2-40-1 The 1H–1H COSY and selective HMBC correlations of 40....341 Figure 5-2-40-2 Selective NOESY correlations of 40.......................342 Figure 5-2-40-3 化合物40之IR圖譜.........................................344 Figure 5-2-40-4 化合物40之低解析ESIMS圖譜................................344 Figure 5-2-40-5 化合物40之高解析ESIMS圖譜................................345 Figure 5-2-40-6 化合物40之1H NMR圖譜.....................................345 Figure 5-2-40-7 化合物40之13C NMR圖譜....................................346 Figure 5-2-40-8 化合物40之DEPT圖譜.......................................346 Figure 5-2-40-9 化合物40之HSQC圖譜.......................................347 Figure 5-2-40-10化合物40之1H–1H COSY圖譜................................347 Figure 5-2-40-11化合物40之HMBC圖譜.......................................348 Figure 5-2-40-12化合物40之NOESY圖譜......................................348 表目錄 Table 1-2-1Six marine natural products and fourteen marine natural products inspired compounds that are FDA-approved agents or in clinical trial with details of their collected source, predicted biosynthetic source, molecular target, and disease treated......................8 Table 1-3-1 Briareum asbestinum珊瑚的文獻回顧..............................................................10 Table 1-3-2 Briareum excavatum珊瑚的文獻回顧...............................................................14 Table 1-3-3 Briareum polyanthes珊瑚的文獻回顧..............................................................30 Table 1-3-4 Briareum stechei珊瑚的文獻回顧.................................................................31 Table 1-3-5 Briareum violacea珊瑚的文獻回顧................................................................35 Table 1-3-6 Briareum sp.珊瑚的文獻回顧.....................................................................36 Table 1-3-7 9,11-secosteroid類天然化合物文獻回顧...........................................................48 Table 5-1-1-1 The calculated distances (A) between selected protons with key NOESY correlations for 1....81 Table 5-1-1-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for1.................................82 Table 5-1-2-1 The calculated distances (A) between selected protons with key NOESY correlations for 2....91 Table 5-1-2-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 2................................92 Table 5-1-3-1 The calculated distances (A) between selected protons with key NOESY correlations for 3...101 Table 5-1-3-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 3...............................102 Table 5-1-4-1 The calculated distances (A) between selected protons with key NOESY correlations for 4...111 Table 5-1-4-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 4...............................112 Table 5-1-5-1 The calculated distances (A) between selected protons with key NOESY correlations for 5...121 Table 5-1-5-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 5...............................122 Table 5-1-6-1 The calculated distances (A) between selected protons with key NOESY correlations for 6...131 Table 5-1-6-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 6...............................132 Table 5-1-7-1 The calculated distances (A) between selected protons with key NOESY correlations for 7...141 Table 5-1-7-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 7...............................142 Table 5-1-8-1 The calculated distances (A) between selected protons with key NOESY correlations for 8...151 Table 5-1-8-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 8...............................152 Table 5-1-9-1 The calculated distances (A) between selected protons with key NOESY correlations for 9...161 Table 5-1-9-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 9...............................162 Table 5-1-10-1 The calculated distances (A) between selected protons with key NOESY correlations for10...172 Table 5-1-10-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 10..............................173 Table 5-1-11-1 The calculated distances (A) between selected protons with key NOESY correlations for 11..182 Table 5-1-11-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 11..............................183 Table 5-1-12-1 The calculated distances (A) between selected protons with key NOESY correlations for 12..192 Table 5-1-12-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 12..............................193 Table 5-1-13-1 The calculated distances (A) between selected protons with key NOESY correlations for 13..202 Table 5-1-13-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 13..............................203 Table 5-1-14-1 The calculated distances (A) between selected protons with key NOESY correlations for 14..212 Table 5-1-14-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 14..............................213 Table 5-1-15-1 The calculated distances (A) between selected protons with key NOESY correlations for 15..223 Table 5-1-15-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 15..............................224 Table 5-1-16-1 The calculated distances (A) between selected protons with key NOESY correlations for 16..234 Table 5-1-16-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 16..............................235 Table 5-1-17-1 The calculated distances (A) between selected protons with key NOESY correlations for 17..244 Table 5-1-17-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 17..............................245 Table 5-1-18-1 The calculated distances (A) between selected protons with key NOESY correlations for 18..254 Table 5-1-18-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 18..............................255 Table 5-1-19-1 The calculated distances (A) between selected protons with key NOESY correlations for 19..264 Table 5-1-19-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 19..............................265 Table 5-1-20-1 The calculated distances (A) between selected protons with key NOESY correlations for 20..274 Table 5-1-20-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 20..............................275 Table 5-1-21-1 The calculated distances (A) between selected protons with key NOESY correlations for 21..284 Table 5-1-21-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 21..............................285 Table 5-1-22-1 The calculated distances (A) between selected protons with key NOESY correlations for 22..294 Table 5-1-22-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 22..............................295 Table 5-1-23-1 The cal47culated distances (A) between selected protons with key NOESY correlations for 23.304 Table 5-1-23-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 23...............................305 Table 5-1-24-1 The calculated distances (A) between selected protons with key NOESY correlations for 24...314 Table 5-1-24-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 24...............................315 Table 5-2-38-1 The calculated distances (A) between selected protons with key NOESY correlations for 38...324 Table 5-2-38-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 38...............................325 Table 5-2-39-1 The calculated distances (A) between selected protons with key NOESY correlations for 39...333 Table 5-2-39-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for39................................334 Table 5-2-40-1 The calculated distances (A) between selected protons with key NOESY correlations for 40...342 Table 5-2-40-2 1H and 13C NMR data, 1H-1H COSY and HMBC correlations for 40...............................343 Table 5-4-1 Cytotoxic activity of compounds 1–24 and 38–40 for various human cancer cell lines for 72hr...............................................355 Table 5-4-2 Effect of compounds 1–24 and 38–40 on superoxide anion generation and elastase release by human neutrophils in response to FMLP/CB........357 Table 5-4-3 Effect of compounds 1–24 and 38–40 on pro-inflammatory iNOS and COX-2 protien expression in LPS-stimulated murine marcrophage cell line RAW264.7................................................................................................................................................359 Table 6-1 NMR chemical shifts for H-2, H-3, H-4 and C-2, C-3, C-4, C-5, C-16 of 2-hydroxybriaranes possessing (A) a Δ3,5(16) conjugated diene moiety.........................................................................................................................................361 Table 6-2 NMR chemical shifts for H-2, H-3, H-4 and C-2, C-3, C-4, C-5, C-6 of 2-hydroxybriaranes possessing (B) a Δ3,5 conjugated diene moiety. ........................................................................................................................................................362 Table 6-3 NMR chemical shifts for H-2, and C-2, C-3, C-4, C-5, C-16 of 2-acetoxybriaranes possessing (C) a Δ3,5(16) conjugated diene moiety. ........................................................................................................................................................362 Table 6-4 NMR chemical shifts for H-2, and C-2, C-3, C-4, C-5, C-6 of 2-acetoxybriaranes possessing (D) a Δ3, 5 conjugated diene moiety..................................................................................................................................................363 Table 6-5 13C NMR chemical shifts for natural briaranes possessing a CH3-20 group in α form....................................................................................................................................................365 Table 6-6 Table 6-6 13C NMR chemical shifts for natural briaranes possessing a CH3-20 group in β form....................................................................................................................................................365 |
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