本研究是從台灣小琉球所採集的紅藻 Laurencia tristicha 的有機萃取物中尋找具有生物活性的化學成分。從此紅藻的研究中總共得到了 18 個天然化合物 1–18，其中包含了 8 個新的 chamigrane-type sesquiterpenes 類化合物 1–8，1個新的 cuparane-type sesquiterpene 類化合物 9，以及九個已知化合物，其中化合物2為新骨架化合物。所有化合物的化學構造均由光譜數據分析 (MS, 1D and 2D NMR) 和比對文獻上已知化合物的光譜分析資料而決定。化合物 12 經由 X-ray 晶體繞射來證明其化合物之結構。此外，化合物 10 及 11 為首次在天然物中發現的化合物。
本研究中將獲得的化合物 1–18 分別對於人類肺腺癌細胞 (A549)，人類結腸癌細胞 (DLD−1)，人類前列腺癌细胞株 (LN-Cap) 進行癌細胞株的細胞毒殺活性測試，結果顯示化合物 13 對於人類肺腺癌細胞 (A549) 有毒殺活性，半抑制濃度為 (IC50) 16.0 ± 3.3 μg/mL。在抗發炎的活性試驗中，化合物 15 和 16 可有效抑制超氧陰離子產生並降低彈性蛋白酶釋放的活性，另外化合物3、6、13和18 能有效的抑制超氧陰離子產生，而化合物 17 則是對於彈性蛋白酶有較佳的抑制活性。在抗菌活性測試的部分化合物 12、14和17 分別對於腸內產氣桿菌有抑菌活性，而化合物 3、11、14、15和17 則對於粘質沙雷氏菌有抑菌活性，化合物 3、14、15 和 17 對於小腸結腸炎耶爾森菌有抑制活性。

In order to discover bioactive secondary metabolites, we have studied the chemical constituents from the organic extracts of red algae Laurencia tristicha. This study resulted the isolation of nineteen compounds, including eight new chamigrane-type sesquiterpenes 1–8 and one new cuparane-type sesquiterpene 9 along with nine known compounds. Among them, compound 2 possess new skeleton.The structures of isolated were determined on the basis of extensive spectroscopic analyses (IR, MS, 1D and 2D NMR) and comparison of spectral data with those of related known compounds. The relative configuration of compound 12 was further supported by a single-crystal X-ray diffraction analysis. In addition compound 10 and 11 were isolation for the first time from natural sources.
The cytotoxicity of compounds 1–19 against the A549 (human lung epithelial cell line), DLD-1 (human colon adenocarcinoma), and LN-Cap (human prostate cancer cells) tumor cell lines were determined. The results showd that compound 13 exhibited cytotoxicity against the A549 cell line with an IC50 value of 16.0 ± 3.3 μg/mL. In anti-inflammation assay compounds 15 and 16 displayed strong inhibition of superoxide anion generation and elastase release, compounds 3、6、13 and 18 show strong inhibition of superoxide anion generation and compound 17 displayed strong inhibition of elastase release. Furthermore, compounds 12, 14 and 17 showed antibacterial activity against Enterobacter aerogenes (ATCC13048), compounds 3, 11, 14, 15 and 17 showed activity against Serratia marcescens (ATCC25419), and compounds 3, 14, 15 and 17 showed activity against Yersinia enterocolitica (ATCC23715).

目 錄 頁 次
論文審定書i

誌謝ii

中文摘要 iii
英文摘要 iv
化合物 118 化學結構 v
第一章、緒論 1
第一節、前言 1
第二節、研究背景與目的 2
第三節、文獻回顧 3
第二章、生物材料與研究方法 31
第一節、研究流程 31
第二節、Laurencia tristicha 樣品採集時間、地點、分類地位及
分離流程 33
2.2.1 Laurencia tristicha 樣品採集時間、地點、分類地位 33
2.2.2 Laurencia tristicha 樣品的萃取分離 34
第三節、實驗設備儀器及材料 36
2.3.1實驗設備儀器 36
2.3.2實驗材料 37
第三章、化合物之結構證明 39
第一節：紅藻 Laurencia tristicha 所分離之化合物結構解析 39
(一)、Tristichone A (1) 化合物結構之解析 39
(二)、Tristichone B (2) 化合物結構造之解析 48
(三)、Tristichol A (3) 化合物結構之解析 57
(四)、Tristichol B (4) 化合物結構之解析 66
(五)、Tristichol C (5) 化合物結構之解析 75
(六)、Tristichol D (6) 化合物結構之解析 85
(七)、Tristichone C (7) 化合物結構之解析 94
(八)、Tristichone D (8) 化合物結構之解析 103
(九)、4α-hydroxybromocuparene (9) 化合物結構之解析 112
(十)、Tristichone E (10) 化合物結構之解析 121
(十一)、Tristichone F (11) 化合物結構之解析 125
(十二)、Ma'ilione (12) 化合物結構之解析 129
(十三)、(1(15)Z,2Z,4S,8R,9S)-8,15-Dibromochamagra -1(15),2,11(12)- trien-9-ol (13) 化合物結構之解析 133
(十四)、1(15)E,2Z,4S,8R,9S)-8,15-dibromochamagra-1(15),2,11 (12)-trien-9-ol (14) 化合物結構之解析 137
(十五)、Ma’iliohydrin (15) 化合物結構造之解析 141
(十六)、Isorigidol (16) 化合物結構之解析 145
(十七)、allo-Isoobtusol (17) 化合物結構之解析 149
(十八)、Majusculone (18) 化合物結構之解析 153
第二節：化合物物理性質及圖譜數據整理 157
第四章、生物活性試驗方法 160
第一節：生物活性試驗方法 160
(一)、細胞毒殺檢測原理及方法 160
(二)、抗發炎活性試驗原理及方法 162
(三)、抗菌活性試驗原理及方法 164
第二節：生物活性試驗結果 165
(一)、細胞毒殺活性試驗結果 165
(一)、抗發炎活性試驗結果 166
(三)、抗菌活性試驗結果 168
第五章、結論 169
第六章、參考文獻 172
附錄(一) 化合物 12 之 X–ray 實驗數據 179
圖 次
Figure 2-1. Laurencia tristicha 實驗流程圖 32
Figure 2-2. Laurencia tristicha 圖 33
Figure 2-3. Laurencia tristicha 紅藻的分離流程 35
Figure 3-1-1. 1H–1H COSY and HMBC correlations for 1. 40
Figure 3-1-2. Selective NOESY correlations for 1. 40
Figure 3-1-3. IR spectrum of 1. 42
Figure 3-1-4. ESIMS spectrum of 1. 42
Figure 3-1-5. HRESIMS spectrum of 1. 43
Figure 3-1-6. 1H-NMR spectrum of 1 in CDCl3. 43
Figure 3-1-7. 1H-NMR (1.6~2.7 ppm) spectrum of 1 in CDCl3. 44
Figure 3-1-8. 13C-NMR spectrum of 1 in CDCl3. 44
Figure 3-1-9. DEPT spectrum of 1 in CDCl3. 45
Figure 3-1-10. HSQC spectrum of 1 in CDCl3. 45
Figure 3-1-11. 1H–1H COSY spectrum of 1 in CDCl3. 46
Figure 3-1-12. HMBC spectrum of 1 in CDCl3. 46
Figure 3-1-13. NOESY spectrum of 1 in CDCl3. 47
Figure 3-2-1. Selective NOESY correlations for 2. 49
Figure 3-2-2. 1H–1H COSY and HMBC correlations for 2. 50
Figure 3-2-3. IR spectrum of 2. 51
Figure 3-2-4. ESIMS spectrum of 2. 51
Figure 3-2-5. HRESIMS spectrum of 2. 52
Figure 3-2-6. 1H-NMR spectrum of 2 in CDCl3. 52
Figure 3-2-7. 1H-NMR (1.7~4.6 ppm) spectrum of 2 in CDCl3. 53
Figure 3-2-8. 13C-NMR spectrum of 2 in CDCl3. 53
Figure 3-2-9. DEPT spectrum of 2 in CDCl3. 54
Figure 3-2-10. HSQC spectrum of 2 in CDCl3. 54
Figure 3-2-11. 1H–1H COSY spectrum of 2 in CDCl3. 55
Figure 3-2-12. HMBC spectrum of 2 in CDCl3. 55
Figure 3-2-13. NOESY spectrum of 2 in CDCl3. 56
Figure 3-3-1. 1H–1H COSY and HMBC correlations for 3. 58
Figure 3-3-2. Selective NOESY correlations for 3. 58
Figure 3-3-3. IR spectrum of 3. 60
Figure 3-3-4. ESIMS spectrum of 3. 60
Figure 3-3-5. HRESIMS spectrum of 3. 61
Figure 3-3-6. 1H-NMR spectrum of 3 in CDCl3. 61
Figure 3-3-7. 1H-NMR (1.4~2.8 ppm) spectrum of 3 in CDCl3. 62
Figure 3-3-8. 1H-NMR (4.0~6.2 ppm) spectrum of 3 in CDCl3. 62
Figure 3-3-9. 13C-NMR spectrum of 3 in CDCl3. 63
Figure 3-3-10. DEPT spectrum of 3 in CDCl3. 63
Figure 3-3-11. HSQC spectrum of 3 in CDCl3. 64
Figure 3-3-12. 1H–1H COSY spectrum of 3 in CDCl3. 64
Figure 3-3-13. HMBC spectrum of 3 in CDCl3. 65
Figure 3-3-14. NOESY spectrum of 3 in CDCl3. 65
Figure 3-4-1. 1H–1H COSY and selective HMBC correlations for 4. 67
Figure 3-4-2. Selective NOESY correlations for 4. 67
Figure 3-4-3. IR spectrum of 4. 69
Figure 3-4-4. ESIMS spectrum of 4. 69
Figure 3-4-5. HRESIMS spectrum of 4. 70
Figure 3-4-6. 1H-NMR spectrum of 4 in CDCl3. 70
Figure 3-4-7. 1H-NMR (1.2~2.8 ppm) spectrum of 4 in CDCl3. 71
Figure 3-4-8. 1H-NMR (4.0~6.0 ppm) spectrum of 4 in CDCl3. 71
Figure 3-4-9. 13C-NMR spectrum of 4 in CDCl3. 72
Figure 3-4-10. DEPT spectrum of 4 in CDCl3. 72
Figure 3-4-11. HSQC spectrum of 4 in CDCl3. 73
Figure 3-4-12. 1H–1H COSY spectrum of 4 in CDCl3. 73
Figure 3-4-13. HMBC spectrum of 4 in CDCl3. 74
Figure 3-4-14. NOESY spectrum of 4 in CDCl3. 74
Figure 3-5-1. 1H–1H COSY and HMBC correlations for 5. 76
Figure 3-5-2. Selective NOESY correlations for 5. 76
Figure 3-5-3. IR spectrum of 5. 78
Figure 3-5-4. ESIMS spectrum of 5. 78
Figure 3-5-5. HRESIMS spectrum of 5. 79
Figure 3-5-6. 1H-NMR spectrum of 5 in CDCl3. 79
Figure 3-5-7. 1H-NMR (1.0~2.0ppm) spectrum of 5 in CDCl3. 80
Figure 3-5-8. 1H-NMR (2.0~2.7 ppm) spectrum of 5 in CDCl3. 80
Figure 3-5-9. 1H-NMR (2.5~6.5 ppm) spectrum of 5 in CDCl3. 81
Figure 3-5-10. 13C-NMR spectrum of 5 in CDCl3. 81
Figure 3-5-11. DEPT spectrum of 5 in CDCl3. 82
Figure 3-5-12. HSQC spectrum of 5 in CDCl3. 82
Figure 3-5-13. 1H–1H COSY spectrum of 5 in CDCl3. 83
Figure 3-5-14. HMBC spectrum of 5 in CDCl3. 83
Figure 3-5-15. NOESY spectrum of 5 in CDCl3. 84
Figure 3-6-1. 1H–1H COSY and selective HMBC correlations for 6. 86
Figure 3-6-2. Selective NOESY correlations of 6. 86
Figure 3-6-3. IR spectrum of 6. 88
Figure 3-6-4. ESIMS spectrum of 6. 88
Figure 3-6-5. HRESIMS spectrum of 6. 89
Figure 3-6-6. 1H-NMR spectrum of 6 in CDCl3. 89
Figure 3-6-7. 1H-NMR (1.5~6.0 ppm) spectrum of 6 in CDCl3. 90
Figure 3-6-8. 13C-NMR spectrum of 6 in CDCl3. 90
Figure 3-6-9. DEPT spectrum of 6 in CDCl3. 91
Figure 3-6-10. HSQC spectrum of 6 in CDCl3. 91
Figure 3-6-11. 1H–1H COSY spectrum of 6 in CDCl3. 92
Figure 3-6-12. HMBC spectrum of 6 in CDCl3. 92
Figure 3-6-13. NOESY spectrum of 6 in CDCl3. 93
Figure 3-7-1. 1H–1H COSY and selective HMBC correlations for 7. 95
Figure 3-7-2. Selective NOESY correlations of 7. 95
Figure 3-7-3. IR spectrum of 7. 97
Figure 3-7-4. ESIMS spectrum of 7. 97
Figure 3-7-5. HRESIMS spectrum of 7. 98
Figure 3-7-6. 1H-NMR spectrum of 7 in CDCl3. 98
Figure 3-7-7. 1H-NMR (1.0~2.6 ppm) spectrum of 7 in CDCl3. 99
Figure 3-7-8. 13C-NMR spectrum of 7 in CDCl3. 99
Figure 3-7-9. DEPT spectrum of 7 in CDCl3. 100
Figure 3-7-10. HSQC spectrum of 7 in CDCl3. 100
Figure 3-7-11. 1H–1H COSY spectrum of 7 in CDCl3. 101
Figure 3-7-12. HMBC spectrum of 7 in CDCl3. 101
Figure 3-7-13. NOESY spectrum of 7 in CDCl3. 102
Figure 3-8-1. 1H–1H COSY and selective HMBC correlations for 8. 104
Figure 3-8-2. Selective NOESY correlations of 8. 104
Figure 3-8-3. IR spectrum of 8. 106
Figure 3-8-4. ESIMS spectrum of 8. 106
Figure 3-8-5. HRESIMS spectrum of 8 107
Figure 3-8-6. 1H-NMR spectrum of 8 in CDCl3. 107
Figure 3-8-7. 1H-NMR (1.1~2.8 ppm) spectrum of 8 in CDCl3. 108
Figure 3-8-8. 13C-NMR spectrum of 8 in CDCl3. 108
Figure 3-8-9. DEPT spectrum of 8 in CDCl3. 109
Figure 3-8-10. HSQC spectrum of 8 in CDCl3. 109
Figure 3-8-11. 1H–1H COSY spectrum of 8 in CDCl3. 110
Figure 3-8-12. HMBC spectrum of 8 in CDCl3. 110
Figure 3-8-13. NOESY spectrum of 8 in CDCl3. 111
Figure 3-9-1. 1H–1H COSY and selective HMBC correlations for 9. 113
Figure 3-9-2. Selective NOESY correlations of 9. 113
Figure 3-9-3. IR spectrum of 9. 115
Figure 3-9-4. ESIMS spectrum of 9. 115
Figure 3-9-5. HRESIMS spectrum of 9 116
Figure 3-9-6. 1H-NMR spectrum of 9 in CDCl3. 116
Figure 3-9-7. 1H-NMR spectrum of 9 in CDCl3. 117
Figure 3-9-8. 13C-NMR spectrum of 9 in CDCl3. 117
Figure 3-9-9. DEPT spectrum of 9 in CDCl3. 118
Figure 3-9-10. HSQC spectrum of 9 in CDCl3. 118
Figure 3-9-11. 1H–1H COSY spectrum of 9 in CDCl3. 119
Figure 3-9-12. HMBC spectrum of 9 in CDCl3. 119
Figure 3-9-13. NOESY spectrum of 9 in CDCl3. 120
Figure 3-10-1. Plausible reaction to derive compounds 10 and 11. 122
Figure 3-10-2. ESIMS spectrum of 10. 123
Figure 3-10-3. 1H-NMR spectrum of 10. 123
Figure 3-10-4. 13C-NMR spectrum of 10. 124
Figure 3-11-1. ESIMS spectrum of 11. 127
Figure 3-11-2. 1H NMR spectrum of 11. 127
Figure 3-11-3. 13C NMR spectrum of 11. 128
Figure 3-12-1. X-ray crystal structure of 12. 130
Figure 3-12-1. ESIMS spectrum of 12. 131
Figure 3-12-2. 1H-NMR spectrum of 12. 131
Figure 3-12-3. 13C-NMR spectrum of 12. 132
Figure 3-13-1. ESIMS spectrum of 13. 135
Figure 3-13-2. 1H-NMR spectrum of 13. 135
Figure 3-13-3. 13C-NMR spectrum of 13. 136
Figure 3-14-1. ESIMS spectrum of 14. 139
Figure 3-14-2. 1H-MR spectrum of 14. 139
Figure 3-14-3. 13C-MR spectrum of 14. 140
Figure 3-15-1. ESIMS spectrum of 15. 143
Figure 3-15-2. 1H-NMR spectrum of 15. 143
Figure 3-15-3. 13C-NMR spectrum of 15. 144
Figure 3-16-1. ESIMS spectrum of 16. 147
Figure 3-16-2. 1H-NMR spectrum of 16. 147
Figure 3-16-3. 13C-NMR spectrum of 16. 148
Figure 3-17-1. ESIMS spectrum of 17. 151
Figure 3-17-2. 1H-NMR spectrum of 17. 151
Figure 3-17-3. 13C-NMR spectrum of 17. 152
Figure 3-18-1. ESIMS spectrum of 18. 155
Figure 3-18-2. 1H-NMR spectrum of 18. 155
Figure 3-18-3. 13C-NMR spectrum of 18. 156
Figure 4-1. Alamar Blue reduction. 160
表 次
Table 1-1.藻類 Laurencia tristicha 所含天然化合物其生物活性文獻回顧
3
Table 1-2.藻類 Laurencia 屬所含 Chemigrane 類化合物其生物活性文獻回顧 11
Table 1-3. 藻類 Laurencia 屬所含 Cuparene 類化合物其生物活文獻回顧
27
Table 3-1. 1H and 13C NMR Data, HMBC and NOESY Correlations of 1. 41
Table 3-2. 1H and 13C NMR Data, HMBC and NOESY Correlations of 2. 50
Table 3-3. 1H and 13C NMR Data, HMBC and NOESY Correlations of 3. 59
Table 3-4. 1H and 13C NMR Data, HMBC and NOESY Correlations of 4. 68
Table 3-5. 1H and 13C NMR Data, HMBC and NOESY Correlations of 5. 77
Table 3-6. 1H and 13C NMR Data, HMBC and NOESY Correlations of 6. 87
Table 3-7. 1H and 13C NMR Data, HMBC and NOESY Correlations of 7. 96
Table 3-8. 1H and 13C NMR Data, HMBC and NOESY Correlations of 8. 105
Table 3-9. 1H and 13C NMR Data, HMBC and NOESY Correlations of 9. 114
Table 3-10. 1H and 13C NMR Data of 10. 122
Table 3-11. 1H and 13C NMR Data of 11. 126
Table 3-12. 1H and 13C NMR Data of 12. 130
Table 3-13. 1H and 13C NMR Data of 13. 134
Table 3-14. 1H and 13C NMR Data of 14. 138
Table 3-15. 1H and 13C NMR Data of 15. 142
Table 3-16. 1H and 13C NMR Data of 16. 146
Table 3-17. 1H and 13C NMR Data of 17. 150
Table 3-18. 1H and 13C NMR Data of 18. 154
Table 4-1. 化合物 1–18 之細胞毒殺活性數據 165
Table 4-2. Effects of compounds on superoxide anion generation in FMLP/CB-induced human neutrophils. 166
Table 4-3. Effects of compounds on elastase release in FMLP/CB-induced human neutrophils. 167
Table 4-4. 化合物 1–8、10–18 之抗菌活性數據 168

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