臺灣博碩士論文加值系統

中文摘要

本論文以初步活性篩選顯示具抗癌活性之姬蕨與水蕨為主題，並做進一步化學成分之分離與探討。水蕨全草以甲醇冷浸萃取，浸液經減壓濃縮後，以n-hexane、Ethyl acetate及H2O分配萃取，經初步藥理活性篩選確定活性部分為n-Hexane及Ethyl acetate層，利用各種不同之層析法，經分離與純化後得22個化合物：quercetin 3-O-β-D-glucopyranoside (174.2 mg) (CT-1)、ferulic acid (356.9 mg) (CT-2)、p-coumaric acid (11.7 mg) (CT-3)、3-(4-hydroxy-phenyl)-acrylic acid methyl ester (23.8 mg) (CT-4)、p-hydroxy benzaldehyde (7.5 mg) (CT-5)、β-sitosterol and β-stigmasterol mixture (19.8 mg) (CT-6)、stigmast-5-ene-3,7-dione.(6 mg) (CT-7)、pterosin Z (8.1 mg) (CT-8)、pterosin A (4 mg) (CT-9)、pterosin V (6 mg) (CT-10)、pterosin K (3.5 mg) (CT-11)、pteroside Z (80 mg) (CT-12)、pterosin D 3-O-β-D-glucopyranoside (209 mg) (CT-13)、12-chloro-pterosin D 3-O-β-D-glucopyranoside (14mg) (CT-14)*、ceratopteroside B (38 mg) (CT-15)、ceratopteroside C (36.6 mg) (CT-16)、ceratopteroside D (3.5 mg) (CT-17)*、ceratopteroside E (6 mg) (CT-18)*、6-O-p-coumaroyl-D-glucopyranoside (28 mg) (CT-19)、3-O-p-coumaroyl-D-glucopyranoside (33.3 mg) (CT-20)、4-O-p-coumaroyl-D-glucopyranoside (5 mg) (CT-21)、kaempherol 3-O-β-glucopyranoside (20 mg) (CT-22)。其中CT-14、CT-17、CT-18為pteroside類中之新化合物。其他如CT-1、CT-2、CT-3、CT-4、CT-5、CT-6、CT-7、CT-14、CT-17、CT-18、CT-20、CT-21、CT-22皆為本植物中首次發現之化合物。姬蕨全草鮮品之甲醇萃取物，經以n-Hexane、Ethyl acetate及H2O分配萃取，並取具有活性之水層，藉由各種層析法，共分離出6個化合物。利用各種光譜分析鑑定其主要架構，分別為：Caffeic acid (14 mg) (HP-1)、2R,3R pterosin-L-13-
O-β-D-glucopyranoside (26.8 mg) (HP-2)、7’, 8’-Dihydro-7’-
(4’-hydroxy-3’-methoxyphenyl)-3-(hydroxymethyl)-1-benzofuranpropanol 4’-O-β-glucopyranoside (29.1 mg) (HP-3)
、6, 7’-dihydroxyisolariciresinol 4’-O-β-glucopyranoside (49.1 mg)
(HP-4)*、(+)-Lariciresinol 4’-O-β-D-glucopyranoside (56.3 mg)
(HP-5)、(+)-Pinoresinol 4’-O-β-D-glucopyranoside (6 mg) (HP-6)。
其中HP-4為新化合物。其他如HP-1、HP-2、HP-3、HP-5、HP-6為本植物中首次發現之化合物，活性部分則尚待評估。

英文摘要

In the course of our preliminary anticancer screeing program, we found that the MeOH extract of Ceratopteris thalictroides (L.) Brongn and Hypolepis punctata (Thumb.) Mett. exhibited cytotoxic activity. Thus. It intrigued us to further chemical investigation of these two plants. The MeOH exctract of whole fresh ferns of C. thalictroides was divided into fractions soluble in hexane, ethyl acetate, and H2O. From EtOAc fraction 22 compounds were isolated by Diaion, Sephadex LH-20, ODS, and silica gel column chromatography. Based on the 1D, 2D NMR and HRMS spectroscopic techniques, the structures were characterized as : quercetin 3-O-β-D-glucopyranoside (CT-1)、ferulic acid (CT-2)、p-coumaric acid (CT-3)、3-(4-hydroxyphenyl)-acrylic acid methyl ester (CT-4)、p-hydroxy benzaldehyde (CT-5)、β-sitosterol and β-stigmasterol mixture (CT-6)、stigmast-5-ene-3,7-dione (CT-7)、pterosin Z (CT-8)、pterosin A (CT-9)、pterosin V (CT-10)、pterosin K (CT-11)、pteroside Z (CT-12)、pterosin D 3-O-β-D-glucopyranoside (CT-13)、12-chloro-pterosin D 3-O-β-D-glucopyranoside (CT-14)、ceratopteroside B (38 mg) (CT-15)、ceratopteroside C (CT-16)、ceratopteroside D (CT-17)、ceratopteroside E (CT-18)、6-O-p-coumaroyl-D-glucopyranoside (CT-19)、3-O-p-coumaroyl
-D-glucopyranoside (CT-20)、4-O-p-coumaroyl-D-glucopyranoside (CT-21)、kaempherol 3-O-β-glucopyranoside (CT-22).Among these, compounds CT-14, CT-17, and CT-18 are newly discovered. The others, CT-1~CT-7, CT-14, CT-17~CT-18, CT-20~CT-22 were isolated from C. thalictroides (L.) Brongn. for the first time.
Similarly, the MeOH extract of fresh plant of Hypolepis punctata was divided into fractions soluble in n-hexane, ethyl acetate and H2O. These fractions were subjected to various chromatography and cytotoxic screening. Totally, six compounds were isolated from this fern, and their structures were determined to be caffeic acid (HP-1)、2R,3R pterosin-L 13-O-β-D-glucopyranoside (HP-2)、7’,8’-Dihydro-7’-(4’-hydroxy-3’-methoxyphenyl)-3- (hydroxymethyl)-1 Benzofuranpropanol 4’-O-β-glucopyranoside (HP-3)、6, 7’-dihydroxyisolariciresinol 4’-O-β-glucopyranoside (HP-4)、(+)-Lariciresinol 4’-O-β-D-glucopyranoside (HP-5)、(+)-Pinoresinol 4’-O-β-D-glucopyranoside (HP-6)。Compound HP-4 is newly discovered, and the rest five compounds were first found in this fern.

目錄

目錄 ……………………………………………………………………I
圖表 …………………………………………………………………IV
中文摘要 ……………………………………………………………1
英文摘要 ……………………………………………………………3
基本骨架 …………………………………………… 5
名詞縮寫 …………………………………………… 8
緒論 ………………………………………………………………9
一、研究背景及目的 ……………………………………………9
二、蕨類之藥理活性探索 ……………………………………10
三、蕨類之成份研究 ………………………………………………15
四、水蕨之相關研究 ………………………………………………23
五、姬蕨之相關研究 ………………………………………………26
第一章 水蕨之成分研究 ……………………………………………30
第一節 抽提及分離 ……………………………………………30
第二節 化合物之構造決定 ……………………………………32
第一項 Flavonoid類化合物 ………………………32
1.1. CT-1: Quercetin 3-O--glucopyranoside ……………32
第二項 Phenolics類化合物 ………………………………38
2.1. CT-2: Ferulic acid ………………………………………38
2.2. CT-3: p-Coumaric acid …………………………………42
2.3. CT-4：3-(4-hydroxy-phenyl)-acrylic acid methyl ester ••• 46
3.1. CT-5: p-hydroxybenzaldehyde …………………………… 49
第三項 Steroid類化合物 ………………………………………51
4.1 . CT-6: β-Sitosterol and β-stigmasterol mixture …………51
4.2. CT-7: stigmast-5-ene-3,7-dione ………………………… 54
第四項 Pterosin類化合物 ……………………………………63
5.1. CT-8: Pterosin Z ……………………………………… 63
5.2. CT-9: Pterosin A ……………………………………… 65
5.3. CT-10: Pterosin V ……………………………………… 70
5.4. CT-11: Pterosin K ……………………………………… 73
第五項Pteroside類化合物 ……………………………………78
6.1. CT-12: Pteroside Z ………………………………… 78
6.2. CT-13: (3R)-pterosin D 3-O-β-D-glucopyranoside ••• 83
6.3 CT-14: 12-chloro-pterosin D 3-O-β-D-glucopyranoside ……………………………… 93
6.4 CT-15: Ceratopteroside B ……………………………106
6.5 CT-16: Ceratopterosin C ……………………………112
6.6 CT-17: Ceratopterosin D ……………………………118
6.7 CT-18: Ceratopterosin E ……………………………126
第七項 Phenylpropanoids glycoside ……………………………136
7.1 CT-19: 6-O-p-coumaroyl-D-glucopyranoside …………136
7.2 CT-20：3-O-p-coumaroyl-D-glucopyranoside …………141
7.3 CT-21：4-O-p-coumaroyl-D-glucopyranoside …………153
第八項 Flavonoid ………………………………………… 160
8.1. CT-22：Kaempherol 3-O-b –glucopyranoside ………160
第二章 姬蕨之成分研究 …………………………………………164
第一節 抽提及分離 ……………………………………………164
第二節 化合物構造之決定 ……………………………………166
第一項 Phenolics ……………………………………………… 166
1.1 HP-1: Caffeic acid …………………………………… 166
第二項 Pteroside類化合物 …………………………………169
2.1. HP-2: 2R, 3R-Pterosin-L 13-O-β-D-glucopyranoside
………………………………………………………… 169
第三項 Lignans …………………………………………… 178
3.1 HP-3: 7’,8’-Dihydro-7’-(4’-hydroxy-3’-methoxyphenyl)
-3-(hydroxymethyl)-1-benzofuranpropanol 4’-O-β
-glucopyranoside ………………………………… 178
3.2 HP-4: 6,7’-dihydroxyisolariciresinol 4’-O-- glucopyranoside ………………………………191
3.3 HP-5: (+)-Lariciresinol 4’-O--D-glucopyranoside …… 199
3.4 HP-6: (+)-Pinoresinol 4’-O--D-glucopyranoside …… 206
第三章 結論 ………………………………………………………215
第四章、實驗部分 ……………………………………………………219
4.1 儀器與材料 ………………………………………………219
4.2 層析法 ……………………………………………………219
4.3 相關實驗 …………………………………………………220
4.3.1 水蕨之抽提與分離 ……………………………………220
4.3.2 姬蕨之抽提與分離 ……………………………………221
4.3.3水蕨成分之物理性質 ……………………………………221
4.3.4姬蕨成分之物理性質 ………………………………… 231
參考文獻 ……………………………………………………………235


圖表

Scheme 1. Ptaquiloside (1)與最終致癌產物(4)之反應機轉 … p. 11
Chart. 1 Fractionation flow chart of Ceratopteris thalictroides (L.) Brongn. …………………………………………… p. 31
Chart. 2 Fractionation flow chart of Hypolepis punctata. ……… p. 165
Table. 1 Toxic effects of Pterosins and Pterosides on HeLa Cells and on mouse. ……………………………………………… p. 13
Table. 2 Pterosins 類之相關化合物. ………………………… p. 15
Table. 3 Pterosides 類之相關化合物. ……………………… p. 18
Table. 4 13C-NMR spectral data of Quercetin and CT-1 (d, ppm, in MeOH-d4, 125 MHz). ……………………………… p. 33
Table. 5 13C-NMR spectral data of Pterosin A (CT-9) and CT-11 ( , ppm, in MeOH-d4, 125 MHz) ……………………………………… p. 74
Table. 6 13C-NMR spectral data of Pterosin Z and CT-12 ( , ppm, in MeOH-d4, 125 MHz) ………………………………………………p. 79
Table. 7 13C-NMR spectral data of Pterosin D 3R-O--D-
glucopyranoside and CT-13 ( , ppm, in MeOH-d4, 125 MHz). ………………………………………………… p. 85
Table. 8 13C-NMR spectral data of CT-13, Pterosin K (CT-11), Spelosin, and CT-14 ( , ppm, in MeOH-d4, 125 MHz ). ……… p. 96
Table. 9 13C-NMR spectral data of CT-13, Ceratopteroside B, p-Coumaric acid, and CT-15 (  ppm, MeOH-d4, 125 MHz ) ………………………………………………… p.108
Table. 10 13C-NMR spectral data of Ceratopteroside C and CT-16 ( ppm, MeOH-d4, 125 MHz). ………………………p. 114
Table. 11 13C-NMR spectral data of CT-15、CT-16 and CT-17 ( ppm, MeOH-d4, 125 MHz). ………………………………p. 120
Table. 12 13C-NMR spectral data of Ceratopteroside B, CT-16, and CT-18 ( ppm, MeOH-d4, 125 MHz) ……………… p. 128
Table. 13 13C-NMR spectral data of 6-O-p-coumariyl-D-
glucopyranoside, CT-19, and CT-20 ( ppm, CD3OD).
……………………………………………………… p. 143
Table. 14 13C-NMR spectral data of 6-O-p-coumariyl-D-
glucopyranoside, CT-19, CT-20 and CT-21 ( ppm, CD3OD). …………………………………………… p. 154
Table. 15 13C-NMR spectral data of Kaempherol and CT-22 ( d ppm, Acetone-d6, 125 MHz). …………………………… p. 161
Table. 16 13C-NMR spectral data of (+)-Lariciresinol and HP-5 ( ppm, Methanol-d4, 125 MHz). …………………… p. 201
Table. 17 13C-NMR spectral data of (+)-Pinoresinol and HP-6 ( ppm, Methanol-d4, 125 MHz) …………………………p. 208
Table. 18 Isolated from MeOH extract of Hypolepis punctata ………………………………………………p. 215
Table. 19 Compounds isolated from the MeOH extract of Ceratopteris thalictroides ……………………………………… p. 216
Fig. 1 Donepezil (Aricept) …………………………………… p. 14
Fig. 2 水蕨形態圖 …………………………………………… p. 25
Fig. 3 姬蕨形態圖 ………………………………………………p. 29
Fig. 4 1H-NMR spectrum of CT-1 Quercetin (MeOH-d4, 500MHz) …………………………………………………p. 34
Fig. 5 13C-NMR spectrum of CT-1 (MeOH-d4, 125MHz) ……… p. 36
Fig.6 DEPT spectrum of CT-1 (MeOH-d4, 125MHz) ………… p. 37
Fig. 7 1H-NMR spectrum of CT-2 (Methanol-d4, 500 MHz) … p. 39
Fig. 8 13C-NMR spectrum of CT-2 (Methanol-d4, 125 MHz) … p. 40
Fig. 9 DEPT spectrum of CT-2 (Methanol-d4, 125 Mhz) ……… p. 41
Fig. 10 1H-NMR spectrum of CT-3 (Methanol-d4, 500 MHz) … p. 43
Fig. 11 13C-NMR spectrum of CT-3 (Methanol-d4, 125 MHz) … p. 44
Fig. 12 DEPT spectrum of CT-3 (Methanol-d4, 125 MHz) ……… p. 45
Fig. 13 1H-NMR-spectrum of CT-4 (Methanol-d4, 500 MHz) … p. 47
Fig. 14 13C-NMR-spectrum of CT-4 (Methanol-d4, 125 MHz) … p. 48
Fig. 15 1H-NMR-spectrum of CT-5 (Methanol-d4, 500 MHz) … p. 50
Fig. 16 1H-NMR-spectrum of CT-6 (CDCl3, 500 MHz) …………p. 52
Fig. 17 IR spectrum of CT-7 …………………………………… p. 55
Fig. 18 1H-NMR-spectrum of CT-7 (CDCl3, 500 MHz) ………… p. 56
Fig. 19 13C-NMR-spectrum of CT-7 (CDCl3, 125 MHz) …………p. 58
Fig. 20 COSY spectrum of CT-7 (CDCl3, 500 MHz) ……………p. 60
Fig. 21 HMQC spectrum of CT-7 (CDCl3, 500 MHz) …………p. 61
Fig. 22 HMBC spectrum of CT-7 (CDCl3, 500 MHz) …………p. 62
Fig. 23 1H-NMR spectrum of CT-8 (CDCl3, 500 MHz) ………p. 64
Fig. 24 1H-NMR spectrum of CT-9 (Methanol-d4, 500 MHz) ……p. 67
Fig. 25 13C-NMR spectrum of CT-9 (Methanol-d4, 125 MHz) … p. 69
Fig. 26 1H-NMR spectrum of CT-10 (Methanol-d4, 500 MHz) … p. 71
Fig. 27 IR spectrum of CT-11 …………………………… p. 75
Fig. 28 EI-MS spectrum of CT-11 ………………………… p. 75
Fig. 29 1H-NMR spectrum of CT-11 (Methanol-d4, 500 MHz) … p. 76
Fig. 30 13C-NMR spectrum of CT-11 (Methanol-d4, 500 MHz) … p. 77
Fig. 31 1H-NMR spectrum of CT-12 (Methanol-d4, 500 MHz) … p. 80
Fig. 32 13C-NMR spectrum of CT-12 (Methanol-d4, 125 MHz) … p. 81
Fig. 33 DEPT spectrum of CT-12 (Methanol-d4, 125 MHz) …… p. 82
Fig. 31 1H-NMR spectrum of CT-13 (Methanol-d4, 500 MHz) … p. 86
Fig. 32 13C-NMR spectrum of CT-13 (Methanol-d4, 125 MHz) … p. 88
Fig. 33 DEPT spectrum of CT-13 (Methanol-d4, 125 MHz) …… p. 89
Fig. 34 1H-1H COSY spectrum of CT-13 (Methanol-d4, 500 MHz)
……………………………………………………………p. 90
Fig. 35 HMQC spectrum of CT-13 (Methanol-d4 500 MHz) … p. 91
Fig. 36 HMBC spectrum of CT-13 (Methanol-d4 500 MHz) … p. 92
Fig. 37 LC-MS spectrum of CT-14 …………………………… p. 97
Fig. 38 IR spectrum of CT-14 ……………………………………p. 97
Fig 39. 1H-NMR spectrum of CT-14 (Methanol-d4 500 MHz) … p. 98
Fig. 40 13C-NMR spectrum of CT-14 (Methanol-d4, 125 MHz) …p. 100
Fig. 41 DEPT spectrum of CT-14 (Methanol-d4 125 MHz) … p. 101
Fig. 42 1H-1H COSY spectrum of CT-14 (Methanol-d4, 500 MHz)
……………………………………………………………p. 102
Fig. 43 HMQC spectrum of CT-14 (Methanol-d4 500 MHz) … p. 103
Fig. 44 HMBC spectrum of CT-14 (Methanol-d4 500 MHz) … p. 104
Fig. 45 1H-NMR spectrum of CT-15 (Methanol-d4, 500 MHz) … p. 109
Fig. 46 13C-NMR spectrum of CT-15 (Methanol-d4, 125 MHz)
……………………………………………………………p. 110
Fig. 47 DEPT spectrum of CT-15 (Methanol-d4, 125 MHz) … p. 111
Fig. 48 1H-NMR spectrum of CT-16 (Methanol-d4, 500 MHz)
……………………………………………………………p. 115
Fig. 49 13C-NMR spectrum of CT-16 (Methanol-d4, 125 MHz)
……………………………………………………………p. 116
Fig. 50 DEPT spectrum of CT-16 (Methanol-d4, 125 MHz) … p. 117
Fig. 51 1H-NMR spectrum of CT-17 (Methanol-d4, 500 MHz) … p. 121
Fig. 52 13C-NMR spectrum of CT-17 (Methanol-d4, 125 MHz)… p. 122
Fig. 53 HMQC spectrum of CT-17 (Methanol-d4, 500 MHz) … p. 123
Fig. 54 HMBC spectrum of CT-17 (Methanol-d4, 500 MHz) … p. 124
Fig. 55 LC-MS spectrum of CT-17 …………………………… p. 125
Fig. 56 1H-NMR spectrum of CT-18 (Methanol-d4, 500 MHz) … p. 129
Fig. 57 13C-NMR spectrum of CT-18 (Methanol-d4, 125 MHz)
……………………………………………………………p. 130
Fig. 58 COSY spectrum of CT-18 (Methanol-d4, 500 MHz) … p. 131
Fig. 59 HMQC spectrum of CT-18 (Methanol-d4, 500 MHz) … p. 132
Fig. 60 HMBC spectrum of CT-18 (Methanol-d4, 500 MHz) … p. 133
Fig. 61 LC-MS spectrum of CT-18 …………………………… p. 135
Fig. 62 1H-NMR spectrum of CT-19 (Methanol-d4, 500 MHz) … p. 137
Fig. 63 13C-NMR spectrum of CT-19 (Methanol-d4, 125 MHz)
……………………………………………………………p. 138
Fig. 64 DEPT spectrum of CT-19 (Methanol-d4, 125 MHz) … p. 140
Fig. 65 1H-NMR spectrum of CT-20 (Methanol-d4, 500 MHz) … p. 144
Fig. 66 13C-NMR spectrum of CT-20 (Methanol-d4, 125 MHz)… p. 146
Fig. 67 DEPT spectrum of CT-20 (Methanol-d4, 125 MHz) … p. 148
Fig. 68 COSY spectrum of CT-20 (Methanol-d4, 500 MHz) … p. 149
Fig. 69 HMQC spectrum of CT-20 (Methanol-d4, 500 MHz) … p. 150
Fig. 70 HMBC spectrum of CT-20 (Methanol-d4, 500 MHz) … p. 151
Fig. 71 1H-NMR spectrum of CT-21 (Methanol-d4, 500 MHz) … p. 155
Fig 72 13C-NMR spectrum of CT-21 (Methanol-d4, 125 MHz) … p. 156
Fig. 73 HMQC spectrum of CT-21 (Methanol-d4, 500 MHz) … p. 158
Fig. 74 HMBC spectrum of CT-21 (Methanol-d4, 500 MHz) … p. 159
Fig. 75 1H-NMR spectrum of CT-22 (Acetone-d6, 500 MHz) … p. 162
Fig. 76 13C-NMR spectrum of CT-22 (Acetone-d6, 125 MHz) … p. 163
Fig. 77 1H-NMR spectrum of HP-1 (Acetone-d6, 500 MHz) … p. 167
Fig. 78 13C-NMR spectrum of HP-1 (Acetone-d6, 125 MHz) … p. 168
Fig. 79 1H-NMR spectrum of HP-2 (Methanol-d4, 500 MHz) … p. 171
Fig. 80 13C-NMR spectrum of HP-2 (Methanol-d4, 125 MHz)… p. 173
Fig. 81 DEPT spectrum of HP-2 (Methanol-d4, 125 MHz) … p. 174
Fig. 82 COSY spectrum of HP-2 (Methanol-d4, 125 MHz) … p. 175
Fig. 83 HMQC spectrum of HP-2 (Methanol-d4, 500 MHz) … p. 176
Fig. 84 HMBC spectrum of HP-2 (Methanol-d4, 125 MHz) … p. 177
Fig. 85 1H-NMR spectrum of HP-3 (Methanol-d4, 500 MHz) … p. 182
Fig. 86 13C-NMR spectrum of HP-3 (Methanol-d4, 125 MHz) … p. 183
Fig. 87 DEPT spectrum of HP-3 (Methanol-d4, 125 MHz) … p. 184
Fig. 88 COSY spectrum of HP-3 (Methanol-d4, 500 MHz) … p. 185
Fig. 89 HMQC spectrum of HP-3 (Methanol-d4, 500 MHz) … p. 187
Fig. 90 HMBC spectrum of HP-3 (Methanol-d4, 500 MHz) … p. 188
Fig. 91 1H-NMR spectrum of HP-4 (Methanol-d4, 500 MHz) … p. 194
Fig. 92 13C-NMR spectrum of HP-4 (Methanol-d4, 125 MHz) … p. 195
Fig. 93 COSY spectrum of HP-4 (Methanol-d4, 500 MHz) … p. 196
Fig. 94 HMQC spectrum of HP-4 (Methanol-d4, 500 MHz) … p. 197
Fig. 95 HMBC spectrum of HP-4 (Methanol-d4, 500 MHz) … p. 198
Fig. 96 1H-NMR spectrum of HP-5 (Methanol-d4, 500 MHz) … p. 202
Fig. 97 13C-NMR spectrum of HP-5 (Methanol-d4, 125 MHz) … p. 203
Fig. 98 HMQC spectrum of HP-5 (Methanol-d4, 500 MHz) … p. 204
Fig. 99 HMBC spectrum of HP-5 (Methanol-d4, 500 MHz) … p. 205
Fig. 100 1H-NMR spectrum of HP-6 (Methanol-d4, 500 MHz)
…………………………………………………………p. 209
Fig. 101 13C-NMR spectrum of HP-6 (Methanol-d4, 125 MHz)
…………………………………………………………p. 211
Fig. 102 COSY spectrum of HP-6 (Methanol-d4, 500 MHz) … p. 212
Fig. 103 HMQC spectrum of HP-6 (Methanol-d4, 500 MHz) … p. 213
Fig. 104 HMBC spectrum of HP-6 (Methanol-d4, 500 MHz) … p. 214

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