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論文名稱 Title |
養殖型軟珊瑚 Klyxum simplex 與台灣野生型軟珊瑚
Cladiella hirsuta 所含Eunicellin-Based 雙萜化合物及生物活
性研究 Eunicellin-Based Diterpenoids from the Soft Corals of Cultured Klyxum simplex and Wild-Type Cladiella hirsuta and Their Bioactivities |
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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 |
468 |
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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 |
2011-10-05 |
繳交日期 Date of Submission |
2011-12-08 |
關鍵字 Keywords |
養殖型 simplex, hirsute, eunicellin, diterpenoid |
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統計 Statistics |
本論文已被瀏覽 5702 次,被下載 225 次 The thesis/dissertation has been browsed 5702 times, has been downloaded 225 times. |
中文摘要 |
本研究主要是從養殖型Klyxum simplex 與野生型珊瑚Cladiella hirsute的有機溶劑萃取物中尋找具有生物活性的化學成分。從養殖型軟珊瑚K.simplex 中分離出二十七個新的eunicellin-type diterpenoids 類化合物klysimplexins A–X (1–24) 和klysimplexin sulfoxides A–C (25–27),另外從野 生型軟珊瑚Cladiella hirsuta 中分離出八個新的eunicellin-type diterpenoids 類化合物hirsutalins C (28) 和F–L (29–35)。所有化合物的化學成分均藉由光譜數據的分析(IR、MS、1D、2D NMR 和X-ray)之光譜資料圖譜而決定。化合物1、3、12 和 22 的絕對立體構型,則經由Mosher’s 方法之酯化反應加以確定,此外化合物1 的結構則更經由X-ray 晶體繞射加以確立。在細胞毒殺活性測試結果顯示化合物2、8、17、20 和 29 對部分癌細胞株都具有中等的細胞毒殺活性。而化合物在濃度為10 μM 化合物10–14,18, 19, 25–28 和 31,可有效的抑制發炎蛋白質iNOS 的表現,其中化合物 18、19 和27 對於COX-2 也具有良好的抑制效果。 |
Abstract |
In order to discover new bioactive compounds, the chemical constituents from the organic extracts of the cultured soft coral Klyxum simplex and wild-type soft coral Cladiella hirsute were studied. 27 new eunicellin-based diterpenoids, klysimplexins A–X (1–24) and klysimplexin sulfoxides A–C (25–27), were isolated from a cultured soft coral Klyxum simplex. Furthermore, eight new eunicellin-base diterpenoids, hirsutalins C (28) and F–L (29–35), were isolated from the soft coral Cladiella hirsuta. The structures of compounds 1–35 were elucidated by spectroscopic methods, in particular 1D and 2D NMR experiments. The absolute stereochemistries of 1, 3, 12, and 22 were determined by Mosher’s method. The structure of 1 was further confirmed by a single-crystal X-ray diffraction analysis. The absolute configurations of 1, 3, 12, and 22 were determined by Mosher’s method. Compounds 2, 8, 17, 20, and 29 have been shown to exhibit cytotoxicity toward a limited panel of cancer cell lines. Compounds 10–14, 18, 19, 25–28, and 31 were found to display significant in vitro anti-inflammatory activity in LPS-stimulated RAW264.7 macrophage cells by inhibiting the expression of the iNOS protein. Compounds 18, 19, and 27 also could effectively reduce the level of the COX-2 protein. |
目次 Table of Contents |
Abstract (English) 1 Abstract (Chinese) 2 Chapter 1 Introduction 7 Chapter 2 Literature Review 10 Chapter 3 Experimental Section 40 Section I General Experimental Procedures 40 Section II Organism and Extraction 41 Section III Cytotoxicity Assay 49 Section IV Anti-inflammatory Assay 50 Chapter 4 Compound Identification 52 Structure Elucidation of Klysimplexin A (1) 52 Structure Elucidation of Klysimplexin B (2) 64 Structure Elucidation of Klysimplexin C (3) 73 Structure Elucidation of Klysimplexin D (4) 84 Structure Elucidation of Klysimplexin E (5) 93 Structure Elucidation of Klysimplexin F (6) 102 Structure Elucidation of Klysimplexin G (7) 111 Structure Elucidation of Klysimplexin H (8) 120 Structure Elucidation of Klysimplexin I (9) 130 Structure Elucidation of Klysimplexin J (10) 142 Structure Elucidation of Klysimplexin K (11) 148 Structure Elucidation of Klysimplexin L (12) 154 Structure Elucidation of Klysimplexin M (13) 166 Structure Elucidation of Klysimplexin N (14) 174 Structure Elucidation of Klysimplexin O (15) 183 Structure Elucidation of Klysimplexin P (16) 192 Structure Elucidation of Klysimplexin Q (17) 202 Structure Elucidation of Klysimplexin R (18) 212 Structure Elucidation of Klysimplexin S (19) 221 Structure Elucidation of Klysimplexin T (20) 230 Structure Elucidation of Klysimplexin U (21) 240 Structure Elucidation of Klysimplexin V (22) 250 Structure Elucidation of Klysimplexin W (23) 261 Structure Elucidation of Klysimplexin X (24) 271 Structure Elucidation of Klysimplexin Sulfoxide A (25) 281 Structure Elucidation of Klysimplexin Sulfoxide B (26) 291 Structure Elucidation of Klysimplexin Sulfoxide C (27) 301 Structure Elucidation of Hirsutalin C (28) 310 Structure Elucidation of Hirsutalin F (29) 320 Structure Elucidation of Hirsutalin G (30) 329 Structure Elucidation of Hirsutalin H (31) 338 Structure Elucidation of Hirsutalin I (32) 347 Structure Elucidation of Hirsutalin J (33) 357 Structure Elucidation of Hirsutalin K (34) 366 Structure Elucidation of Hirsutalin L (35) 375 Chapter 5 Bioactivities 384 Section I: Cytotoxicity Assay 384 Section II: Anti-inflammatory Assay 386 Chapter 6 Conclusion 390 Chapter 7 Physical Properties and Data collections 393 Chapter 8 Reaction and X-ray Data 403 Chapter 9 References 431 List of Figures Figure 3-1. The isolated processes of the cultured soft coral Klyxum simplex. 42 Figure 3-2. The isolated processes of the soft coral Cladiella hirsuta. 47 Figure 4-1-1. 1H-1H COSY and HMBC correlations for 1 53 Figure 4-1-2. Molecular structure of 1 based on X-ray analysis. 54 Figure 4-1-3. 1H NMR chemical shift differences (Δδ) for the MTPA esters of 1 55 Figure 4-1-4. IR spectrum of 1 57 Figure 4-1-5. ESIMS spectrum of 1 57 Figure 4-1-6. HRESIMS spectrum of 1 58 Figure 4-1-7. 1H NMR spectrum of 1 in Pyridine-d5 58 Figure 4-1-8. 1H NMR (3.3~6.3 ppm) spectrum of 1 in d5-Pyridine-d5 59 Figure 4-1-9. 13C NMR spectrum of 1 in d5-Pyridine-d5 59 Figure 4-1-10. DEPT spectrum of 1 in d5-Pyridine-d5 60 Figure 4-1-11. HSQC spectrum of 1 in d5-Pyridine-d5 60 Figure 4-1-12. COSY spectrum of 1 in d5-Pyridine-d5 61 Figure 4-1-13. HMBC spectrum of 1 in d5-Pyridine-d5 61 Figure 4-1-14. NOESY spectrum of 1 in d5-Pyridine 62 Figure 4-1-15. 1H-NMR spectrum for the S-MTPA ester of 1 in CDCl3 62 Figure 4-1-16. 1H-NMR spectrum for the R-MTPA ester of 1 in CDCl3 63 Figure 4-2-1. 1H–1H COSY and selective HMBC correlations of 2 65 Figure 4-2-2. Selected NOESY correlations of 2 65 Figure 4-2-3. IR spectrum of 2 67 Figure 4-2-4. ESIMS spectrum of 2 67 Figure 4-2-5. HRESIMS spectrum of 2 68 Figure 4-2-6. 1H NMR spectrum of 2 in d6-Benzene 68 Figure 4-2-7. 1H NMR (2.5~5.7 ppm) spectrum of 2 in d6-Benzene 69 Figure 4-2-8. 13C NMR spectrum of 2 in d6-Benzene 69 Figure 4-2-9. DEPT spectrum of 2 in d6-Benzene 70 Figure 4-2-10. HSQC spectrum of 2 in d6-Benzene 70 Figure 4-2-11. COSY spectrum of 2 in d6-Benzene 71 Figure 4-2-12. HMBC spectrum of 2 in d6-Benzene 71 Figure 4-2-13. NOESY spectrum of 2 in d6-Benzene 72 Figure 4-3-1. 1H–1H COSY and selective HMBC correlations of 3 74 Figure 4-3-2. Selected NOESY correlations of 3 74 Figure 4-1-3. 1H NMR chemical shift differences (Δδ) for the MTPA esters of 3 75 Figure 4-3-4. IR spectrum of 3 77 Figure 4-3-5. ESIMS spectrum of 3 77 Figure 4-3-6. HRESIMS spectrum of 3 78 Figure 4-3-7. 1H NMR spectrum of 3 in CDCl3 78 Figure 4-3-8. 1H NMR (2.6~4.5 ppm) spectrum of 3 in CDCl3 79 Figure 4-3-9. 13C NMR spectrum of 3 in CDCl3 79 Figure 4-3-10. DEPT spectrum of 3 in CDCl3 80 Figure 4-3-11. HSQC spectrum of 3 in CDCl3 80 Figure 4-3-12. COSY spectrum of 3 in CDCl3 81 Figure 4-3-13. HMBC spectrum of 3 in CDCl3. 81 Figure 4-3-14. NOESY spectrum of 3 in CDCl3 82 Figure 4-3-15. 1H-NMR spectrum for the S-MTPA ester of 3 in CDCl3 82 Figure 4-3-16. 1H-NMR spectrum for the R-MTPA ester of 3 in CDCl3 83 Figure 4-4-1. 1H–1H COSY and selective HMBC correlations of 4 85 Figure 4-4-2. Selected NOESY correlations of 4 85 Figure 4-4-3. IR spectrum of 4 87 Figure 4-4-4. ESIMS spectrum of 4 87 Figure 4-4-5. HRESIMS spectrum of 4 88 Figure 4-4-6. 1H NMR spectrum of 4 in CDCl3 88 Figure 4-4-7. 1H NMR (2.4~6.0 ppm) spectrum of 4 in CDCl3 89 Figure 4-4-8. 13C NMR spectrum of 4 in CDCl3 89 Figure 4-4-9. DEPT spectrum of 4 in CDCl3 90 Figure 4-4-10. HSQC spectrum of 4 in CDCl3 90 Figure 4-4-11. COSY spectrum of 4 in CDCl3 91 Figure 4-4-12. HMBC spectrum of 4 in CDCl3 91 Figure 4-4-13. NOESY spectrum of 4 in CDCl3 92 Figure 4-5-1. 1H–1H COSY and selective HMBC correlations of 5 94 Figure 4-5-2. Selected NOESY correlations of 5 94 Figure 4-5-3. IR spectrum of 5 96 Figure 4-5-4. ESIMS spectrum of 5 96 Figure 4-5-5. HRESIMS spectrum of 5 97 Figure 4-5-6. 1H NMR spectrum of 5 in CDCl3 97 Figure 4-5-7. 1H NMR (2.5~5.5 ppm) spectrum of 5 in CDCl3 98 Figure 4-5-8. 13C NMR spectrum of 5 in CDCl3 98 Figure 4-5-9. DEPT spectrum of 5 in CDCl3 99 Figure 4-5-10. HSQC spectrum of 5 in CDCl3 99 Figure 4-5-11. COSY spectrum of 5 in CDCl3 100 Figure 4-5-12. HMBC spectrum of 5 in CDCl3 100 Figure 4-5-13. NOESY spectrum of 5 in CDCl3 101 Figure 4-6-1. 1H–1H COSY and selective HMBC correlations of 6 103 Figure 4-6-2. Selected NOESY correlations of 6 103 Figure 4-6-3. IR spectrum of 6 105 Figure 4-6-4. ESIMS spectrum of 6 105 Figure 4-6-5. HRESIMS spectrum of 6 106 Figure 4-6-6. 1H NMR spectrum of 6 in CDCl3 106 Figure 4-6-7. 1H NMR (2.5~5.0 ppm) spectrum of 6 in CDCl3 107 Figure 4-6-8. 13C NMR spectrum of 6 in CDCl3 107 Figure 4-6-9. DEPT spectrum of 6 in CDCl3 108 Figure 4-6-10. HSQC spectrum of 6 in CDCl3 108 Figure 4-6-11. COSY spectrum of 6 in CDCl3 109 Figure 4-6-12. HMBC spectrum of 6 in CDCl3 109 Figure 4-6-13. NOESY spectrum of 6 in CDCl3 110 Figure 4-7-1 1H-1H COSY and selective HMBC correlations of 7 112 Figure 4-7-2. Selected NOESY correlations of 7 112 Figure 4-7-3. IR spectrum of 7 114 Figure 4-7-4. ESIMS spectrum of 7 114 Figure 4-7-5. HRESIMS spectrum of 7 115 Figure 4-7-6 1H NMR spectrum of 7 in CDCl3 115 Figure 4-7-7. 1H NMR (2.0~4.7 ppm) spectrum of 7 in CDCl3 116 Figure 4-7-8. 13C NMR spectrum of 7 in CDCl3 116 Figure 4-7-9. DEPT spectrum of 7 in CDCl3 117 Figure 4-7-10. HSQC spectrum of 7 in CDCl3 117 Figure 4-7-11. COSY spectrum of 7 in CDCl3 118 Figure 4-7-12. HMBC spectrum of 7 in CDCl3 118 Figure 4-7-13. NOESY spectrum of 7 in CDCl3 119 Figure 4-8-1. 1H-1H COSY and selective HMBC correlations of 8 119 Figure 4-8-2. Selected NOESY correlations of 8 122 Figure 4-8-3. IR spectrum of 8 124 Figure 4-8-4. ESIMS spectrum of 8 124 Figure 4-8-5. HRESIMS spectrum of 8 125 Figure 4-8-6. 1H NMR spectrum of 8 in CDCl3 125 Figure 4-8-7. 1H NMR (2.3~6.0 ppm) spectrum of 8 in CDCl3 126 Figure 4-8-8. 13C NMR spectrum of 8 in CDCl3 126 Figure 4-8-9. HSQC spectrum of 8 in CDCl3 127 Figure 4-8-10. COSY spectrum of 8 in CDCl3 127 Figure 4-8-11. HMBC spectrum of 8 in CDCl3 128 Figure 4-8-12. NOESY spectrum of 8 in CDCl3 128 Figure 4-8-13. 1H-NMR spectrum of acetylaction 8a in CDCl3 129 Figure 4-9-1. 1H-1H COSY and selective HMBC correlations of 9 131 Figure 4-9-2. IR spectrum of 9 135 Figure 4-9-3. ESIMS spectrum of 9 135 Figure 4-9-4. HRESIMS spectrum of 9 136 Figure 4-9-5. 1H NMR spectrum of 9 in CDCl3 136 Figure 4-9-6. 1H NMR (1.5~5.5 ppm) spectrum of 9 in CDCl3 137 Figure 4-9-7. 13C NMR spectrum of 9 in CDCl3 137 Figure 4-9-8. DEPT spectrum of 9 in CDCl3 138 Figure 4-9-9. HSQC spectrum of 9 in CDCl3 138 Figure 4-9-10. COSY spectrum of 9 in CDCl3 139 Figure 4-9-11. HMBC spectrum of 9 in CDCl3 139 Figure 4-9-12. NOESY spectrum of 9 in CDCl3 140 Figure 4-9-13. 1H NMR spectrum of base-catalyized hydrolysis 9 in CD3Cl3 140 Figure 4-9-3. LC-ESI MS/MS spectrum of 9 in CDCl3 141 Figure 4-10-1. ESIMS spectrum of 10 145 Figure 4-10-2. HRESIMS spectrum of 10 145 Figure 4-10-3. LC-ESI MS/MS spectrum of 10 in CDCl3 146 Figure 4-10-4. 1H NMR spectrum of 10 in CDCl3 146 Figure 4-10-5. 13C NMR spectrum of 10 in CDCl3 147 Figure 4-11-1. ESIMS spectrum of 11 151 Figure 4-11-2. HRESIMS spectrum of 11 151 Figure 4-11-3. LC-ESI MS/MS spectrum of 11 in CDCl3 152 Figure 4-11-4. 1H NMR spectrum of 11 in CDCl3 152 Figure 4-11-5. 1H NMR (2.0~5.7 ppm) spectrum of 11 in CDCl3 153 Figure 4-11-6. 13C NMR spectrum of 11 in CDCl3 153 Figure 4-12-1. 1H-1H COSY and selective HMBC correlations of 12 155 Figure 4-12-2. Selected NOESY correlations of 12 156 Figure 4-12-3. 1H NMR chemical shift differences (Δδ) for the MTPA esters of 12 157 Figure 4-12-4. IR spectrum of 12 159 Figure 4-12-5. ESIMS spectrum of 12 159 Figure 4-12-6. HRESIMS spectrum of 12 160 Figure 4-12-7. 1H NMR spectrum of 12 in CDCl3 160 Figure 4-12-8. 1H NMR (2.0~5.6 ppm) spectrum of 12 in CDCl3 161 Figure 4-12-9. 13C NMR spectrum of 12 in CDCl3 161 Figure 4-12-10. DEPT spectrum of 12 in CDCl3 162 Figure 4-12-11. HSQC spectrum of 12 in CDCl3 162 Figure 4-12-12. COSY spectrum of 12 in CDCl3 163 Figure 4-12-13. HMBC spectrum of 12 in CDCl3 163 Figure 4-12-14. NOESY spectrum of 12 in CDCl3 164 Figure 4-12-15. 1H-NMR spectrum for the S-MTPA ester of 12 in CDCl3 164 Figure 4-12-16. 1H-NMR spectrum for the R-MTPA ester of 12 in CDCl3 165 Figure 4-13-1. 1H-1H COSY and selective HMBC correlations of 13 167 Figure 4-13-2. Selected NOESY correlations of 13 167 Figure 4-13-3. IR spectrum of 13 169 Figure 4-13-4. ESIMS spectrum of 13 169 Figure 4-13-5. HRESIMS spectrum of 13 170 Figure 4-13-6. 1H NMR spectrum of 13 in CDCl3 170 Figure 4-13-7. 1H NMR (2.3~5.6 ppm) spectrum of 13 in CDCl3 171 Figure 4-12-8. 13C NMR spectrum of 13 in CDCl3 171 Figure 4-13-9. HSQC spectrum of 13 in CDCl3 172 Figure 4-13-10. COSY spectrum of 13 in CDCl3 172 Figure 4-13-11. HMBC spectrum of 13 in CDCl3 173 Figure 4-13-12. NOESY spectrum of 13 in CDCl3 173 Figure 4-14-1. 1H-1H COSY and selective HMBC correlations of 14 175 Figure 4-14-2. Selected NOESY correlations of 14 175 Figure 4-14-3. IR spectrum of 14 177 Figure 4-14-4. ESIMS spectrum of 14 177 Figure 4-14-5. HRESIMS spectrum of 14 178 Figure 4-14-6. 1H NMR spectrum of 14 in CDCl3 178 Figure 4-14-7. 1H NMR (2.0~5.8 ppm) spectrum of 14 in CDCl3 179 Figure 4-14-8. 13C NMR spectrum of 14 in CDCl3 179 Figure 4-14-9. DEPT spectrum of 14 in CDCl3 180 Figure 4-14-10. HSQC spectrum of 14 in CDCl3 180 Figure 4-14-11. COSY spectrum of 14 in CDCl3 181 Figure 4-14-12. HMBC spectrum of 14 in CDCl3 181 Figure 4-14-13. NOESY spectrum of 14 in CDCl3 182 Figure 4-15-1. 1H-1H COSY and selective HMBC correlations of 15 184 Figure 4-15-2. Selected NOESY correlations of 15 184 Figure 4-15-3. IR spectrum of 15 186 Figure 4-15-4. ESIMS spectrum of 15 186 Figure 4-15-5. HRESIMS spectrum of 15 187 Figure 4-15-6. 1H NMR spectrum of 15 in CDCl3 187 Figure 4-15-7. 1H NMR (3.3~5.7 ppm) spectrum of 15 in CDCl3 188 Figure 4-15-8. 13C NMR spectrum of 15 in CDCl3 188 Figure 4-15-9. DEPT spectrum of 15 in CDCl3 189 Figure 4-15-10. HSQC spectrum of 15 in CDCl3 189 Figure 4-15-11. COSY spectrum of 15 in CDCl3 190 Figure 4-15-12. HMBC spectrum of 15 in CDCl3 190 Figure 4-15-13. NOESY spectrum of 15 in CDCl3 191 Figure 4-16-1. 1H-1H COSY and selective HMBC correlations of 16 193 Figure 4-16-2. Selected NOESY correlations of 16 194 Figure 4-16-3. IR spectrum of 16 196 Figure 4-16-4. ESIMS spectrum of 16 196 Figure 4-16-5. HRESIMS spectrum of 16 197 Figure 4-16-6. 1H NMR spectrum of 16 in CDCl3 197 Figure 4-16-7. 1H NMR (2.2~5.7 ppm) spectrum of 16 in CDCl3 198 Figure 4-16-8. 13C NMR spectrum of 16 in CDCl3 198 Figure 4-16-9. DEPT spectrum of 16 in CDCl3 199 Figure 4-16-10. HSQC spectrum of 16 in CDCl3 199 Figure 4-16-11. COSY spectrum of 16 in CDCl3 200 Figure 4-16-12. HMBC spectrum of 16 in CDCl3 200 Figure 4-16-13. NOESY spectrum of 16 in CDCl3 201 Figure 4-17-1. 1H-1H COSY and selective HMBC correlations of 17 203 Figure 4-17-2. Selected NOESY correlations of 17 204 Figure 4-17-3. IR spectrum of 17 206 Figure 4-17-4. ESIMS spectrum of 17 206 Figure 4-17-5. HRESIMS spectrum of 17 207 Figure 4-17-6. 1H NMR spectrum of 17 in CDCl3 207 Figure 4-17-7. 1H NMR (3.3~6.3 ppm) spectrum of 17 in CDCl3 208 Figure 4-17-8. 13C NMR spectrum of 17 in CDCl3 208 Figure 4-17-9. DEPT spectrum of 17 in CDCl3 209 Figure 4-17-10. HSQC spectrum of 17 in CDCl3 209 Figure 4-17-11. COSY spectrum of 17 in CDCl3 210 Figure 4-17-12. HMBC spectrum of 17 in CDCl3 210 Figure 4-17-13. NOESY spectrum of 17 in CDCl3 211 Figure 4-18-1. 1H-1H COSY and selective HMBC correlations of 18 213 Figure 4-18-2. Selected NOESY correlations of 18 213 Figure 4-18-3. IR spectrum of 18 215 Figure 4-18-4. EIMS spectrum of 18 215 Figure 4-18-5. HREIMS spectrum of 18 216 Figure 4-18-6. 1H NMR spectrum of 18 in CDCl3 216 Figure 4-18-7. 1H NMR (3.0~5.4 ppm) spectrum of 18 in CDCl3 217 Figure 4-18-8. 13C NMR spectrum of 18 in CDCl3 217 Figure 4-18-9. DEPT spectrum of 18 in CDCl3 218 Figure 4-18-10. HSQC spectrum of 18 in CDCl3 218 Figure 4-18-11. COSY spectrum of 18 in CDCl3 219 Figure 4-18-12. HMBC spectrum of 18 in CDCl3 219 Figure 4-18-13. NOESY spectrum of 18 in CDCl3 220 Figure 4-19-1. 1H-1H COSY and selective HMBC correlations of 19 222 Figure 4-19-2. Selected NOESY correlations of 19 222 Figure 4-19-3. IR spectrum of 19 224 Figure 4-19-4. ESIMS spectrum of 19 224 Figure 4-19-5. HRESIMS spectrum of 19 225 Figure 4-19-6. 1H NMR spectrum of 19 in CDCl3 225 Figure 4-19-7. 1H NMR (2.0~4.8 ppm) spectrum of 19 in CDCl3 226 Figure 4-19-8. 13C NMR spectrum of 19 in CDCl3 226 Figure 4-19-9. DEPT spectrum of 19 in CDCl3 227 Figure 4-19-10. HSQC spectrum of 19 in CDCl3 227 Figure 4-19-11. COSY spectrum of 19 in CDCl3 228 Figure 4-19-12. HMBC spectrum of 19 in CDCl3 228 Figure 4-19-13. NOESY spectrum of 19 in CDCl3 229 Figure 4-20-1. 1H-1H COSY and selective HMBC correlations of 20 231 Figure 4-20-2. Selected NOESY correlations of 20 232 Figure 4-20-3. IR spectrum of 20 234 Figure 4-20-4. ESIMS spectrum of 20 234 Figure 4-20-5. HRESIMS spectrum of 20 235 Figure 4-20-6. 1H NMR spectrum of 20 in CDCl3 235 Figure 4-20-7. 1H NMR (3.3~5.6 ppm) spectrum of 20 in CDCl3 236 Figure 4-20-8. 13C NMR spectrum of 20 in CDCl3 236 Figure 4-20-9. DEPT spectrum of 20 in CDCl3 237 Figure 4-20-10. HSQC spectrum of 20 in CDCl3 237 Figure 4-20-11. COSY spectrum of 20 in CDCl3 238 Figure 4-20-12. HMBC spectrum of 20 in CDCl3 238 Figure 4-20-13. NOESY spectrum of 20 in CDCl3 239 Figure 4-21-1. 1H-1H COSY and selective HMBC correlations of 21 242 Figure 4-21-2. Selected NOESY correlations of 21 242 Figure 4-21-3. IR spectrum of 21 244 Figure 4-21-4. ESIMS spectrum of 21 244 Figure 4-21-5. HRESIMS spectrum of 21 245 Figure 4-21-6. 1H NMR spectrum of 21 in CDCl3 245 Figure 4-21-7. 1H NMR (3.0~5.7 ppm) spectrum of 21 in CDCl3 246 Figure 4-21-8. 13C NMR spectrum of 21 in CDCl3 246 Figure 4-21-9. DEPT spectrum of 21 in CDCl3 247 Figure 4-21-10. HSQC spectrum of 21 in CDCl3 247 Figure 4-21-11. COSY spectrum of 21 in CDCl3 248 Figure 4-21-12. HMBC spectrum of 21 in CDCl3 248 Figure 4-21-13. NOESY spectrum of 21 in CDCl3 249 Figure 4-22-1. 1H-1H COSY and selective HMBC correlations of 22 251 Figure 4-22-2. Selected NOESY correlations of 22 252 Figure 4-22-3. 1H NMR chemical shift differences (Δδ) for the MTPA esters of 22 252 Figure 4-22-4. IR spectrum of 22 254 Figure 4-22-5. ESIMS spectrum of 22 254 Figure 4-22-6. HRESIMS spectrum of 22 255 Figure 4-22-7. 1H NMR spectrum of 22 in CDCl3 255 Figure 4-22-8. 1H NMR (3.0~6.0 ppm) spectrum of 22 in CDCl3 256 Figure 4-22-9. 13C NMR spectrum of 22 in CDCl3 256 Figure 4-22-10. DEPT spectrum of 22 in CDCl3 257 Figure 4-22-11. HSQC spectrum of 22 in CDCl3 257 Figure 4-22-12. COSY spectrum of 22 in CDCl3 258 Figure 4-22-13. HMBC spectrum of 22 in CDCl3 258 Figure 4-22-14. NOESY spectrum of 22 in CDCl3 259 Figure 4-22-15. 1H-NMR spectrum for the S-MTPA ester of 22 in CDCl3 259 Figure 4-22-16. 1H-NMR spectrum for the R-MTPA ester of 22 in CDCl3 260 Figure 4-23-1. 1H-1H COSY and selective HMBC correlations of 23 262 Figure 4-23-2. Selected NOESY correlations of 23 263 Figure 4-23-3. IR spectrum of 23 265 Figure 4-23-4. ESIMS spectrum of 23 265 Figure 4-23-5. HRESIMS spectrum of 23 266 Figure 4-23-6. 1H NMR spectrum of 23 in CDCl3 266 Figure 4-23-7. 1H NMR (3.3~5.8 ppm) spectrum of 23 in CDCl3 267 Figure 4-23-8. 13C NMR spectrum of 23 in CDCl3 267 Figure 4-23-9. DEPT spectrum of 23 in CDCl3 268 Figure 4-23-10. HSQC spectrum of 23 in CDCl3 268 Figure 4-23-11. COSY spectrum of 23 in CDCl3 269 Figure 4-23-12. HMBC spectrum of 23 in CDCl3 269 Figure 4-23-13. NOESY spectrum of 23 in CDCl3 270 Figure 4-24-1. 1H-1H COSY and selective HMBC correlations of 24 272 Figure 4-24-2. Selected NOESY correlations of 24 273 Figure 4-24-3. IR spectrum of 24 275 Figure 4-24-4. ESIMS spectrum of 24 275 Figure 4-24-5. HRESIMS spectrum of 24 276 Figure 4-24-6. 1H NMR spectrum of 24 in CDCl3 276 Figure 4-24-7. 1H NMR (2.6~5.0 ppm) spectrum of 24 in CDCl3 277 Figure 4-24-8. 13C NMR spectrum of 24 in CDCl3 277 Figure 4-24-9. DEPT spectrum of 24 in CDCl3 278 Figure 4-24-10. HSQC spectrum of 24 in CDCl3 278 Figure 4-24-11. COSY spectrum of 24 in CDCl3 279 Figure 4-24-12. HMBC spectrum of 24 in CDCl3 279 Figure 4-24-13. NOESY spectrum of 24 in CDCl3 280 Figure 4-25-1. 1H-1H COSY and selective HMBC correlations of 25 283 Figure 4-25-2. Selected NOESY correlations of 25 283 Figure 4-25-3. IR spectrum of 25 285 Figure 4-25-4. ESIMS spectrum of 25 285 Figure 4-25-5. HRESIMS spectrum of 25 286 Figure 4-25-6. 1H NMR spectrum of 25 in CDCl3 286 Figure 4-25-7. 1H NMR (2.3~4.2 ppm) spectrum of 25 in CDCl3 287 Figure 4-25-8. 13C NMR spectrum of 25 in CDCl3 287 Figure 4-25-9. DEPT spectrum of 25 in CDCl3 288 Figure 4-25-10. HSQC spectrum of 25 in CDCl3 288 Figure 4-25-11. COSY spectrum of 25 in CDCl3 289 Figure 4-25-12. HMBC spectrum of 25 in CDCl3 289 Figure 4-25-13. NOESY spectrum of 25 in CDCl3 290 Figure 4-26-1. 1H-1H COSY and selective HMBC correlations of 26 292 Figure 4-26-2. Selected NOESY correlations of 26 293 Figure 4-26-3. IR spectrum of 26 295 Figure 4-26-4. ESIMS spectrum of 26 295 Figure 4-26-5. HRESIMS spectrum of 26 296 Figure 4-26-6. 1H NMR spectrum of 26 in CDCl3 296 Figure 4-26-7. 1H NMR (2.9~6.0 ppm) spectrum of 26 in CDCl3 297 Figure 4-26-8. 13C NMR spectrum of 26 in CDCl3 297 Figure 4-26-9. DEPT spectrum of 26 in CDCl3 298 Figure 4-26-10. HSQC spectrum of 26 in CDCl3 298 Figure 4-26-11. COSY spectrum of 26 in CDCl3 299 Figure 4-26-12. HMBC spectrum of 26 in CDCl3 299 Figure 4-26-13. NOESY spectrum of 26 in CDCl3 300 Figure 4-27-1. 1H-1H COSY and selective HMBC correlations of 27 302 Figure 4-27-2. Selected NOESY correlations of 27 302 Figure 4-27-3. IR spectrum of 27 304 Figure 4-27-4. ESIMS spectrum of 27 304 Figure 4-27-5. HRESIMS spectrum of 27 305 Figure 4-27-6. 1H NMR spectrum of 27 in CDCl3 305 Figure 4-27-7. 1H NMR (3.3~5.6 ppm) spectrum of 27 in CDCl3 306 Figure 4-27-8. 13C NMR spectrum of 27 in CDCl3 306 Figure 4-27-9. DEPT spectrum of 27 in CDCl3 307 Figure 4-27-10. HSQC spectrum of 27 in CDCl3 307 Figure 4-27-11. COSY spectrum of 27 in CDCl3 308 Figure 4-27-12. HMBC spectrum of 27 in CDCl3 308 Figure 4-27-13. NOESY spectrum of 27 in CDCl3 309 Figure 4-28-1. 1H-1H COSY and selective HMBC correlations of 28 312 Figure 4-28-2. Selected NOESY correlations of 28 312 Figure 4-28-3. IR spectrum of 28 314 Figure 4-28-4. ESIMS spectrum of 28 314 Figure 4-28-5. HRESIMS spectrum of 28 315 Figure 4-28-6. 1H NMR spectrum of 28 in CDCl3 315 Figure 4-28-7. 1H NMR (2.5~6.8 ppm) spectrum of 28 in CDCl3 316 Figure 4-28-8. 13C NMR spectrum of 28 in CDCl3 316 Figure 4-28-9. DEPT spectrum of 28 in CDCl3 317 Figure 4-28-10. HSQC spectrum of 28 in CDCl3 317 Figure 4-28-11. COSY spectrum of 28 in CDCl3 318 Figure 4-28-12. HMBC spectrum of 28 in CDCl3 318 Figure 4-28-13. NOESY spectrum of 28 in CDCl3 319 Figure 4-29-1. 1H-1H COSY and selective HMBC correlations of 29 321 Figure 4-29-3. IR spectrum of 29 323 Figure 4-29-4. ESIMS spectrum of 29 323 Figure 4-29-5. HRESIMS spectrum of 29 324 Figure 4-29-6. 1H NMR spectrum of 29 in CDCl3 324 Figure 4-29-7. 1H NMR (1.7~4.7 ppm) spectrum of 29 in CDCl3 325 Figure 4-29-8. 13C NMR spectrum of 29 in CDCl3 325 Figure 4-29-9. DEPT spectrum of 29 in CDCl3 326 Figure 4-29-10. HSQC spectrum of 29 in CDCl3 326 Figure 4-29-11. COSY spectrum of 29 in CDCl3 327 Figure 4-29-12. HMBC spectrum of 29 in CDCl3 327 Figure 4-29-13. NOESY spectrum of 29 in CDCl3 328 Figure 4-30-1. 1H-1H COSY and selective HMBC correlations of 30 330 Figure 4-30-2. Selected NOESY correlations of 30 330 Figure 4-30-3. IR spectrum of 30 332 Figure 4-30-4. ESIMS spectrum of 30 332 Figure 4-30-5. HRESIMS spectrum of 30 333 Figure 4-30-6. 1H NMR spectrum of 30 in CDCl3 333 Figure 4-30-7. 1H NMR (3.3~5.8 ppm) spectrum of 30 in CDCl3 334 Figure 4-30-8. 13C NMR spectrum of 30 in CDCl3 334 Figure 4-30-9. DEPT spectrum of 30 in CDCl3 335 Figure 4-30-10. HSQC spectrum of 30 in CDCl3 335 Figure 4-30-11. COSY spectrum of 30 in CDCl3 336 Figure 4-30-12. HMBC spectrum of 30 in CDCl3 336 Figure 4-30-13. NOESY spectrum of 30 in CDCl3 337 Figure 4-31-1. 1H-1H COSY and selective HMBC correlations of 31 338 Figure 4-31-2. Selected NOESY correlations of 31 339 Figure 4-31-3. IR spectrum of 31 341 Figure 4-31-4. ESIMS spectrum of 31 341 Figure 4-31-5. HRESIMS spectrum of 31 342 Figure 4-31-6. 1H NMR spectrum of 31 in CDCl3 342 Figure 4-31-7. 1H NMR (2.0~4.5 ppm) spectrum of 31 in CDCl3 343 Figure 4-31-8. 13C NMR spectrum of 31 in CDCl3 343 Figure 4-31-9. DEPT spectrum of 31 in CDCl3 344 Figure 4-31-10. HSQC spectrum of 31 in CDCl3 344 Figure 4-31-11. COSY spectrum of 31 in CDCl3 345 Figure 4-31-12. HMBC spectrum of 31 in CDCl3 345 Figure 4-31-13. NOESY spectrum of 31 in CDCl3 346 Figure 4-32-1. 1H-1H COSY and selective HMBC correlations of 32 348 Figure 4-32-2. Selected NOESY correlations of 32 349 Figure 4-32-3. IR spectrum of 32 351 Figure 4-32-4. ESIMS spectrum of 32 351 Figure 4-32-5. HRESIMS spectrum of 32 352 Figure 4-32-6. 1H NMR spectrum of 32 in CDCl3 352 Figure 4-32-7. 1H NMR (2.0~4.5 ppm) spectrum of 32 in CDCl3 353 Figure 4-32-8. 13C NMR spectrum of 32 in CDCl3 353 Figure 4-32-9. DEPT spectrum of 32 in CDCl3 354 Figure 4-32-10. HSQC spectrum of 32 in CDCl3 354 Figure 4-32-11. COSY spectrum of 32 in CDCl3 355 Figure 4-32-12. HMBC spectrum of 32 in CDCl3 355 Figure 4-32-13. NOESY spectrum of 32 in CDCl3 356 Figure 4-33-1. 1H-1H COSY and selective HMBC correlations of 33 358 Figure 4-33-2. Selected NOESY correlations of 33 358 Figure 4-33-3. IR spectrum of 33 360 Figure 4-33-4. ESIMS spectrum of 33 360 Figure 4-33-5. HRESIMS spectrum of 33 361 Figure 4-33-6. 1H NMR spectrum of 33 in CDCl3 261 Figure 4-33-7. 1H NMR (2.0~4.5 ppm) spectrum of 33 in CDCl3 362 Figure 4-33-8. 13C NMR spectrum of 33 in CDCl3 362 Figure 4-33-9. DEPT spectrum of 33 in CDCl3 363 Figure 4-33-10. HSQC spectrum of 33 in CDCl3 363 Figure 4-33-11. COSY spectrum of 33 in CDCl3 364 Figure 4-33-12. HMBC spectrum of 33 in CDCl3 364 Figure 4-33-13. NOESY spectrum of 33 in CDCl3 365 Figure 4-34-1. 1H-1H COSY and selective HMBC correlations of 34 366 Figure 4-34-2. Selected NOESY correlations of 34 367 Figure 4-34-3. IR spectrum of 34 369 Figure 4-34-4. ESIMS spectrum of 34 369 Figure 4-34-5. HRESIMS spectrum of 34 370 Figure 4-34-6. 1H NMR spectrum of 34 in CDCl3 370 Figure 4-34-7. 1H NMR (2.0~4.5 ppm) spectrum of 34 in CDCl3 371 Figure 4-34-8. 13C NMR spectrum of 34 in CDCl3 371 Figure 4-34-9. DEPT spectrum of 34 in CDCl3 372 Figure 4-34-10. HSQC spectrum of 34 in CDCl3 372 Figure 4-34-11. COSY spectrum of 34 in CDCl3 373 Figure 4-34-12. HMBC spectrum of 34 in CDCl3 373 Figure 4-34-13. NOESY spectrum of 34 in CDCl3 374 Figure 4-35-1. 1H-1H COSY and selective HMBC correlations of 35 376 Figure 4-35-2. Selected NOESY correlations of 35 376 Figure 4-35-3. IR spectrum of 35 378 Figure 4-35-4. ESIMS spectrum of 35 378 Figure 4-35-5. HRESIMS spectrum of 35 379 Figure 4-35-6. 1H NMR spectrum of 35 in CDCl3 379 Figure 4-35-7. 1H NMR (2.0~4.5 ppm) spectrum of 35 in CDCl3 380 Figure 4-35-8. 13C NMR spectrum of 35 in CDCl3 380 Figure 4-35-9. DEPT spectrum of 35 in CDCl3 381 Figure 4-35-10. HSQC spectrum of 35 in CDCl3 381 Figure 4-35-11. COSY spectrum of 35 in CDCl3 382 Figure 4-35-12. HMBC spectrum of 35 in CDCl3 382 Figure 4-35-13. NOESY spectrum of 35 in CDCl3 383 Figure 5-1. Effect of compounds 9–20 on iNOS and COX-2 protein expression of RAW264.7 macrophage cells by immunoblot analysis. 387 Figure 5-2. Effect of compounds 25–27 on iNOS and COX-2 protein expression of RAW264.7 macrophage cells by immunoblot analysis. 387 Figure 5-3. Effect of compounds 28–31 on iNOS protein expression of RAW264.7 macrophage cell by immunoblot analysis. |
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