台灣白及(Bletilla formosana (Hayata) Schltr.)為白及屬 (Bletilla)中在台灣唯一的特有種，傳統大陸白及 (Bletilla striata) 常被大量使用在中草藥上治療，使得大陸白及(Bletilla striata)的需求量增加及供應不足，而台灣白及 (Bletilla formosana)在台灣廣泛生長，希望可以替代大陸白及(Bletilla striata)在中草藥上使用。

在本研究中，從台灣白及的酒精萃取物中分離出10個新化合物與45個已知化合物，其中新化合物包含9個phenanthrenes類：bleformin A (238)、bleformin B (239)、bleformin C (240)、bleformin D (241)、bleformin E (242)、bleformin F (243)、bleformin G (244)、bleformin H (245)、bleformin I (246)、以及1個benzyl glycoside類：bleformin J (247)。已知化合物包含gastrodin (3), 4-hydroxy-benzaldehyde (7), batatasin III (18), 3′-O-methylbatatasin III (19), gigantol (20), 3-O-methylbatatasin III (21), 3, 3′-dihydroxy-4-(p-hydro-
xylbenzyl)-5-methoxybibenzyl (27), 5-O-methylshancigusin C (28), 3′, 5-di
hydroxy-2-(p-hydroxybenzyl)-3-methoxy-bibenzyl (30), 3, 3′-dihydroxy-2,
6-bis(p-hydroxybenzyl)-5-methoxy-bibenzyl (37), 2′, 6′-bis(p-hydroxy-
benzyl)-3′, 5-dimethoxy-3-hydroxybibenzyl (38), bulbocodin D (41), 2, 4-di-
methoxy-phenanthrene-3, 7-diol (65), nudol (72), 1-(4′-hydroxybenzyl)-4-
methoxy-phenanthrene-2, 7-diol (82), coelonin (95), erianthridin (97), 2, 7-
dihydroxy-1-(p-hydroxybenzyl)-4-methoxy-9, 10-dihydrophenanthrene (114), 3-(4-hydroxybenzyl)-4-methoxy-9, 10-dihydrophenanthrene-2, 7-diol (118), 2, 7-dihydroxy-1, 3-bi(p-hydroxybenzyl)-4-methoxy-9, 10-dihydrophenantrene (122), blestriarene A (126), blestriarene B (127), blestrianol A (135), gymconopin C (138), β-sitosterol glucoside (168), 1-(4-β-D-glucopyranosyl-
oxybenzyl) 4-methyl (2R)-2-isobutylmalate (189), militarine (192), dactylorhin A (193), shancigusin I (198), 5-(hydroxymethyl)-2-furaldehyde (219), 4-hydroxybenzyl ethyl ether (224), ethyl (E)-4-hydroxycinnamate (225), ethyl (Z)-4-hydroxycinnamate (226), 3-O-methyldihydropinosylvin (227), 2, 7-dihydroxy-3, 4, 6-trimethoxyphenanthrene (228), 2, 7-dihydroxy-
3, 4, 6-trimethoxy-9, 10-dihydrophenan-threne (229), phochinenin K (230), ephemeranthoquinone (231), densiflorol B (232), 4, 4′-dimethoxy-9, 10-dyhydro-[6, 1′-biphenanthrene]-2, 2′, 7, 7′-tetraol (233), cirrhopetalanthrin (234), agrostonin (235), (2S)-5, 2′-dihydroxy-7-methoxyflavanone (236), and β-sitosterol and stigmasterol mixture (237)以上化合物均經由光譜分析與文獻比對確認其結構。

在抗發炎實驗中，多數的化合物經超氧陰離子生成與彈性蛋白酶釋放的二個實驗中，大部分化合物的IC50活性範圍分別為0.2~6.5 μM與0.3~5.7 μM，其中實驗結果顯示，3, 3′-dihydroxy-2, 6-bis(p-hydroxybenzyl)-
5-methoxybibenzyl (37)、bleformin D (241)、blestriarene B (127)、phochinenin K (230) 與1-(4′-hydroxybenzyl)-4-methoxyphenanthrene-2, 7-diol (82) 具有顯著的抗發炎活性。從結構與活性先關性 (structure−activity relationships) 評估其抗發炎活性的強度，與發現順序為：phenanthrene類 > bibenzyl類 > biphenanthrene類。

在H4IIE 細胞經dexamethasone與 8-bromo-cAMP 誘導生成PEPCK mRNA表現量實驗中，化合物 4-hydroxybenzaldehyde (7)、batatasin III (18)、3′, 5-dihydroxy-2-(p-hydroxybenzyl)-3-methoxybibenzyl (30)、3, 3′-dihydr-
oxy-2, 6-bis (p-hydroxybenzyl)-5-methoxybibenzyl (37)、2′, 6′-bis(p-hydroxy-
benzyl)-3′, 5-dimethoxy-3-hydroxybibenzyl (38)、2, 4-dimethoxyphenan-
threne-3, 7-diol (65) 可抑制PEPCK mRNA的生成。

另外，在指紋圖譜比較上，對5種不同品種或產地的白及屬植物，分析其HPLC與UPLC圖譜時可以發現其含有成分呈現有意義的差異，也發現台灣白及與大陸白及比較其組成之成分的相似度甚高，因此，台灣白及可以考慮成為大陸白及的替代品使用。在2018年，台灣中藥典第三版中也新增了台灣白及為可正式使用的中藥基原。

Bletilla formosana (Hayata) Schltr. is the only member of the Bletilla genus found in Taiwan and is a perennial herb. The B. striata is usually used in traditional medicine therefore reduced the B. striata growing. However, Bletilla formosana (Hayata) Schlechter is the only variable species of Bletilla endemic in Taiwan. B. formosana is widely distributed throughout the island, and may be used as a substitute for B. striata.

In this study, nine new phenanthrenes and a new benzyl glycoside together with 45 known compounds were isolated from the ethanol extract of Bletilla formosana. And the new compounds were determined and named as: bleformin A (238), bleformin B (239), bleformin C (240), bleformin D (241), bleformin E (242), bleformin F (243), bleformin G (244), bleformin H (245), bleformin I (246), bleformin J (247). The 45 known compounds, gastrodin (3), 4-hydroxy-benzaldehyde (7), batatasin III (18), 3′-O-methylbatatasin III (19), gigantol (20), 3-O-methylbatatasin III (21), 3, 3′-dihydroxy-4-(p-hydroxylbenzyl)-5-meth-
oxybibenzyl (27), 5-O-methylshancigusin C (28), 3′, 5-dihydroxy-2-(p-hydroxybenzyl)-3-
methoxy-bibenzyl (30), 3, 3′-dihydroxy-2, 6-bis(p-hydroxybenzyl)-5-methoxy-bibenzyl (37), 2′, 6′-bis(p-hydroxybenzyl)-3′, 5-dimethoxy-3-hydroxybibenzyl (38), bulbocodin D (41), 1 2, 4-dimethoxy-phenanthrene-3, 7-diol (65), nudol (72), 1-(4′-hydroxybenzyl)-4-me-thoxy-phenanthrene-2, 7-diol (82), coelonin (95), erianthridin (97), 2, 7-dihydroxy-1-(p-hydroxybenzyl)-4-methoxy-9, 10-dihydrophenanthrene (114), 3-(4-hydroxybenzyl)-4-methoxy-9, 10-dihydrophenanthrene-2, 7-diol (118), 2, 7-dihydroxy-1, 3-bi(p-hydroxybenzyl)-4-methoxy-9, 10-dihydrophenantrene (122), blestriarene A (126), blestriarene B (127), blestrianol A (135), gymconopin C (138), β-sitosterol glucoside (168), 1-(4-β-D-glucopyranosyloxybenzyl) 4-methyl (2R)-2-isobutylmalate (189), militarine (192), dactylorhin A (193), shancigusin I (198), 5-(hydroxymethyl)-2-furaldehyde (219), 4-hydroxybenzyl ethyl ether (224), ethyl (E)-4-hydroxycinnamate (225), ethyl (Z)-4-hydroxycinnamate (226), 3-O-methyldihydropinosylvin (227), 2 2, 7-dihydroxy-3, 4, 6-trimethoxyphenanthrene (228), 3 2, 7-dihydroxy-3, 4, 6-trimethoxy-9, 10-dihydrophenan-threne (229), phochinenin K (230), ephemeranthoquinone (231), densiflorol B (232), 4, 4′-dimethoxy-9, 10-dyhydro-[6, 1′-biphenanthrene]-2, 2′, 7, 7′-tetraol (233), cirrhopetalanthrin (234), agrostonin (235), (2S)-5, 2′-dihydroxy-7-methoxyflavanone (236), and β-sitosterol and stigmasterol mixture (237) were identified by comparison of their physical and spectroscopic data (NMR, UV, IR and MS) with the reported values in the cited literatures.

In this study, most of the isolated compounds were evaluated for their anti-inflammatory activities. The results showed that IC50 values for the inhibition of superoxide anion generation and elastase release ranged from 0.23 ± 0.05 to 6.49 ± 1.41 μM and 0.27 ± 0.10 to 5.69 ± 0.43 μM, respectively. Therefore compounds 3, 3′-dihydroxy-2, 6-bis(p-hydroxybenzyl)-5-methoxybibenzyl (37), 1-(4′-hydroxybenzyl)-4-
methoxy-phenanthrene-2,7-diol (82), blestriarene B (127), bleformin D (242), and phochinenin K (230) have significant anti-inflammatory activity and could be a potential anti-inflammatory agent.

Structure−activity relationships of the isolated compounds were also investigated. The inhibitory potencies were determined as phenanthrenes > bibenzyls > biphenanthrenes.

In the PEPCK mRNA expression in H4IIE cells assay, 4-hydroxy-benzaldehyde (7), batatasin III (18), 3′, 5-dihydroxy-2-(p-hydroxybenzyl)-3-methoxybibenzyl (30), 3, 3′-dihydroxy-2, 6-bis-(p-hydroxybenzyl)-5-methoxybibenzyl (37), 2′, 6′-bis(p-hydroxyben-
zyl)-3′, 5-dimethoxy-3-hydroxyl-bibenzyl (38) and 2,4-dimethoxy-phenanthrene-3,7-diol (65) are active for suppression of dexamethasone and 8-bromo-cAMP induced PEPCK.

In the fingerprint of Bletilla species, the results of fingerprint of five species of Bletilla show that there are differences between HPLC/UV fingerprint and HPLC/MS fingerprint, indicating that although these five species belong to the Bletilla, the internal chemical composition is some different. The fingerprint of Bletilla species indicated that the compositions of B. formosana was similar to B. striata, and B. formosana could be uesd as substituted materia medicine in traditional Chinese medicine. In 2018, B. formosana was listed in the Taiwan Herbal Pharmacopeia (III), that B. formosana could be formally use in traditional Chinese medicine.

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