Two new selaginellin derivatives from Selaginella tamariscina (Beauv.) Spring

Two new selaginellin derivatives, selaginellins K (1) and L (2), were isolated from Selaginella tamariscina (Beauv.) Spring and characterized as 2-formyl-4,4′-dihydroxy-3-[(4-hydroxyphenyl)ethynyl]biphene and 4,4′-dihydroxy-2-methyl-3-[(4-hydroxyphenyl)ethynyl]biphene on the basis of their spectroscopic data including UV, IR, 1D, and 2D NMR as well as HR-ESI-MS spectroscopic analysis.     

卷柏的化学成分

目的研究卷柏[Selaginella tamariscina(Beauv.)Spring]的化学成分。方法采用硅胶柱色谱、ODS柱色谱、制备型HPLC等手段进行分离纯化,并利用波谱学方法鉴定化合物的结构。结果从卷柏乙醇提取物中分离得到13个化合物,分别鉴定为3β-羟基-7α-甲氧基-24β-乙基-胆甾-5-烯(1)、胆甾醇(2)、β-谷甾醇(3)、海棠果酸(4)、白桦脂酸(5)、5,4′-二羟基-7-甲氧基黄酮(6)、3-methoxychrysazin(7)、穗花杉双黄酮(8)、异柳杉双黄酮(9)、香草酸(10)、对甲氧基苯甲醛(11)、对羟基苯甲酸(12)、胡萝卜苷(13)。结论化合物1-2、4-7、10、13为本属植物中首次分离得到的化合物。     

Selaginellins I and J, two new alkynyl phenols, from Selaginella tamariscina (Beauv.) Spring

Selaginellins I (1) and J (2), two new compounds, were isolated from Selaginella tamariscina (Beauv.) Spring and were characterized as (R,S)-4-((2',4'-dihydroxy-4-(hydroxymethyl)-3-((4-hydroxyphenyl)ethynyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene)cyclohexa-2,5-dienone (1) and (R,S)-4-((3-((3,4-dihydroxyphenyl)ethynyl)-4'-hydroxy-4-(hydroxymethyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene)cyclohexa-2,5-dienone (2) on the basis of UV, IR, 1D and 2D NMR, and HR-ESI-MS spectroscopic analysis.     

Selaginellins I and J,two new alkynyl phenols,from Selaginella tamariscina (Beauv.) Spring

Selaginellins I (1) and J (2), two new compounds, were isolated from Selaginella tamariscina (Beauv.) Spring and were characterized as (R,S)-4-((2′,4′-dihydroxy-4-(hydroxymethyl)-3-((4-hydroxyphenyl)ethynyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene)cyclohexa-2,5-dienone (1) and (R,S)-4-((3-((3,4-dihydroxyphenyl)ethynyl)-4′-hydroxy-4-(hydroxymethyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene)cyclohexa-2,5-dienone (2) on the basis of UV, IR, 1D and 2D NMR, and HR-ESI-MS spectroscopic analysis.     

卷柏化学成分的分离与鉴定

目的研究卷柏属植物卷柏(Selaginella tamariscina(Beauv.)Spring)的化学成分。方法利用各种色谱法对卷柏的化学成分进行分离和纯化,通过理化性质和波谱数据分析进行结构鉴定。结果从卷柏中分离并鉴定了8个化合物,分别为尿苷(uridine,1)、垫状卷柏双黄酮(pulvinatabifla-vone,2)、selaginellin(3)、selaginellin C(4)、熊果苷(arbutin,5)、腺苷(adenosine,6)、β-谷甾醇(β-si-tosterol,7)、胡萝卜苷(daucosterol,8)。结论化合物1为首次从卷柏属植物中分离得到,化合物2~4为首次从卷柏中分离得到。     

Isolation and cytotoxic activity of selaginellin derivatives and biflavonoids from Selaginella tamariscina

Five selaginellin derivatives, including two new selaginellins termed selaginellins M (1) and N (2), and three previously identified compounds, selaginellin (3), selaginellin A (4), and selaginellin C (5), were isolated from the Selaginella tamariscina (Beauv.) Spring plant. In addition, four known biflavonoids, namely neocryptomerin ( 6), hinokiflavone (7), pulvinatabiflavone (8), and 7'- O-methylamentoflavone (9), were also isolated. The structures of new compounds 1 and 2 were elucidated by spectroscopic analysis. The cytotoxic activity of compounds 1- 9 was evaluated against a small panel of human cancer cell lines, including U251 (human glioma cells), HeLa (human cervical carcinoma cells), and MCF-7 (human breast cancer cells). The two new selaginellins, selaginellins M (1) and N (2), showed medium activity against the human cancer cell lines.     

Two new secolignans from Selaginella sinensis (Desv.) Spring

Two new secolignans, 3,4-trans-3-hydroxymethyl-4-[bis(4-hydroxyphenyl)methyl]butyrolactone (1) and 2,3-trans-3,4-trans-2-methoxy-3-hydroxymethyl-4-[bis(4-hydroxyphenyl)methyl]tetrahydrofuran (2), together with six known compounds, were isolated from the whole grass of Selaginella sinensis (Desv.) Spring. Their structures were elucidated by NMR and MS experiments.     

卷柏总黄酮提取工艺研究

目的:通过比较实验室和工业化生产车间制备的卷柏总黄酮提取物中总黄酮及穗花杉双黄酮含量,探讨实验室和工业生产制备的卷柏总黄酮的质量差异。方法:采用紫外分光光度法测定卷柏提取物中总黄酮的含量;采用HPLC法测定穗花杉双黄酮的含量,并分析卷柏总黄酮部位中的总黄酮的成分组成。结果:工业化生产车间制备的卷柏总黄酮提取物中各含量指标与实验室制备样品无显著差异。结论:工业化生产车间大生产条件下制备的卷柏总黄酮部位与实验室制备的卷柏总黄酮部位无显著差异,为进一步的新药研究和工业化生产提供了保障。     

Selaginellin M, a new selaginellin derivative from Selaginella pulvinata

A new selaginellin derivative, selaginellin M (1), together with one known compound, selaginellin E (2), was isolated from Selaginella pulvinata. The structure of the new compound was elucidated and named as (R,S)-4-((4'-hydroxy-4-((2-hydroxyethoxy)methyl))-3-((4-hydroxyphenyl)ethynyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene)cyclohexa-2,5-dienone on the basis of the spectroscopic data including UV, IR, 1D, and 2D NMR as well as HR-ESI-MS analysis.     

Selaginellin M,a new selaginellin derivative from Selaginella pulvinata

A new selaginellin derivative, selaginellin M (1), together with one known compound, selaginellin E (2), was isolated from Selaginella pulvinata. The structure of the new compound was elucidated and named as (R,S)-4-((4′-hydroxy-4-((2-hydroxyethoxy)methyl))-3-((4-hydroxyphenyl)ethynyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene)cyclohexa-2,5-dienone on the basis of the spectroscopic data including UV, IR, 1D, and 2D NMR as well as HR-ESI-MS analysis.     

卷柏中双黄酮类化学成分及卷柏属该类化合物的核磁共振特征

目的对卷柏属双黄酮类化合物的核磁共振特征进行归纳。方法应用核磁共振波谱法对卷柏[Selaginellatamariscina(Beauv.)Spring.]50%乙醇提取物中分离得到的5个双黄酮类化合物进行结构鉴定,并结合相关文献对卷柏属双黄酮类化合物的核磁共振特征进行归纳总结。结果首次初步归纳出卷柏属双黄酮类化合物核磁共振碳谱和氢谱的特征。结论通过总结卷柏属双黄酮类化合物的核磁共振特征规律,为快速鉴定该类化合物的结构以及进行核磁数据的归属提供依据。     

卷柏中单糖抗辐射作用的研究

目的：分析卷柏（Selaginella tamariscina）中糖类化学成分,观察其对中国仓鼠肺成纤维细胞（V79）和BALB/c小鼠的辐射防护作用,为探讨卷柏抗辐射作用机制提供参考依据。方法：薄层色谱法分析卷柏中糖类化学成分;V79细胞经木糖、果糖、阿拉伯糖处理24 h后接受60Co γ射线照射,分别观察细胞活力、克隆形成率和细胞周期;BALB/c小鼠接受6 Gy 60Co γ射线照射前1周给予木糖,观察受照射小鼠的 30 d存活率。结果：卷柏中含有葡萄糖、木糖、果糖、阿拉伯糖、海藻糖等;其中木糖、果糖、阿拉伯糖在20~200 μg?mL-1浓度范围内可剂量依赖地促进照射后V79细胞增殖,在200 μg?mL-1时可提高照射后V79细胞克隆形成率,增加S期细胞比例,缓解G2/M期阻滞,修正紊乱的细胞周期;照射前分别给予木糖100,500 mg?kg-1可剂量依赖地提高受照射小鼠存活率达20%,30%。结论：卷柏中的单糖类成分可提高受照射小鼠的30 d存活率,其机制可能是通过调节受照射后紊乱的细胞周期而发挥辐射防护作用。     

Vasorelaxation by amentoflavone isolated from Selaginella tamariscina

In the courses of in vitro screening for the vasorelaxant effect of the various extracts from medicinal plants, an ethyl acetate-soluble extract of Selaginella tamariscina was found to exhibit distinctive vasorelaxant activity. Further purifications of the extract as guided by in vitro vasorelaxant assay afforded an active biflavonoid, amentoflavone. Amentoflavone induced concentration-dependent relaxation of the phenylephrine-precontracted aorta, which disappeared by removal of functional endothelium. Pretreatment of the aortic tissues with N(G)-nitro- L-arginine methyl ester (L-NAME), methylene blue, or 1 H- -oxadiazolo[4,3- a]quinoxalin-1-one (ODQ) inhibited the relaxation induced by amentoflavone. Amentoflavone-induced relaxations were also markedly attenuated by addition of tetraethylammonium (TEA) or verapamil. However, the relaxant effect of amentoflavone was not blocked by pretreatment with indomethacin, glibenclamide, atropine, or propranolol. Incubation of endothelium-intact aortic rings with amentoflavone increased the production of cGMP, but this effect was blocked by endothelium-denudation or pretreatment with L-NAME or ODQ. These results suggest that amentoflavone relaxes vascular smooth muscle via endothelium-dependent nitric oxide-cGMP signaling, with possible involvement of non-specific K (+) and Ca (2+) channels. Abbreviations. EDRF:endothelium-derived relaxing factor EDHF:endothelium-derived hyperpolarizing factor NO:nitric oxide cGMP:guanosine 3',5'-cyclic monophosphate DMSO:dimethyl sulfoxide L-NAME: N(G)-nitro- L-arginine methyl ester ODQ:1 H-[1,2,4]-oxadiazole-[4,3- a]-quinoxalin-1-one IBMX:3-isobutyl-1-methylxanthine K (Ca):Ca (2+)-dependent K (+) channel K (ATP):adenosine triphosphate (ATP)-sensitive K (+) channel TEA:tetraethylammonium     

A new selaginellin derivative and a new triarylbenzophenone analog from the whole plant of Selaginella pulvinata

Abstract

Five selaginellin derivatives (1 and 3–6) including a new one, selaginellin T (1), and a new triarylbenzophenone analog, selagibenzophenone A (2), were isolated from the whole plants of Selaginella pulvinata. Their structures were determined by 1D- and 2D-NMR and HR-ESI-MS data. Selagibenzophenone A (2) is the first example of naturally occurring triarylbenzophenone. The results of the phosphodiesterase-4 (PDE4) inhibitory screening assays showed that compounds 1?6 exhibited potent activities with the IC₅₀ values in the range of 1.04?9.35 μM.     

Two new flavonoids from Selaginella uncinata

Two new flavonoids, uncinataflavones A (1) and B (2), along with one known compound 6-(5-carboxyl-2-methoxyphenyl)-apigenin (3), were isolated from Selaginella uncinata (Desv.) Spring. All these compounds belong to apigenin derivatives with aryl substituents at C-6 position. The structures of new compounds were elucidated on the basis of comprehensive spectroscopic analyses (UV, IR, 1D, and 2D NMR as well as HR-ESI-MS).     

卷柏中一个新木脂素苷的分离与鉴定

目的研究卷柏的化学成分。方法利用大孔吸附树脂、Sephadex LH-20、硅胶柱色谱进行分离纯化，根据化合物的理化性质和光谱数据鉴定结构。结果从卷柏中分离得到4个化合物，分别鉴定为(7S,8r)-7,8-二氢-7-(4-羟基-3,5-二甲氧基苯基)-8-羟甲基-［1′-(7′-羟基)乙基-5′-甲氧基］苯骈呋喃-4-O-β-D-葡糖苷(命名为卷柏苷C，化合物I)、D-甘露醇(化合物II)、酪氨酸(化合物III)、莽草酸(化合物IV)。结论化合物I为新化合物，化合物II和III为首次从卷柏属植物中分离得到,IV为首次从卷柏中分离得到。     

Selaginella tamariscina (Beauv.) possesses antimetastatic effects on human osteosarcoma cells by decreasing MMP-2 and MMP-9 secretions via p38 and Akt signaling pathways

Selaginella tamariscina is a traditional medicinal plant for treatment of some advanced cancers in the Orient. However, the effect of S. tamariscina on metastasis of osteosarcoma and the underlying mechanism remain unclear. We tested the hypothesis that S. tamariscina suppresses cellular motility, invasion and migration and also investigated its signaling pathways. This study demonstrates that S. tamariscina, at a range of concentrations (from 0 to 50 μg/mL), concentration-dependently inhibited the migration/invasion capacities of three osteosarcoma cell lines without cytotoxic effects. Zymographic and western blot analyses revealed that S. tamariscina inhibited the matrix metalloproteinase (MMP)-2 and MMP-9 enzyme activity, as well as protein expression. Western blot analysis also showed that S. tamariscina inhibits phosphorylation of p38 and Akt. Furthermore, SB203580 (p38 inhibitor) and LY294002 (PI3K inhibitor) showed the similar effects as S. tamariscina in U2OS cells. In conclusion, S. tamariscina possesses an antimetastatic activity in osteosarcoma cells by down-regulating MMP-2 and MMP-9 secretions and increasing TIMP-1 and TIMP-2 expressions through p38 and Akt-dependent pathways. S. tamariscina may be a powerful candidate to develop a preventive agent for osteosarcoma metastasis.     

翠云草中酚性成分的分离与鉴定

目的研究翠云草[Selaginella uncinata(Desv.) Spring]的化学成分。方法利用硅胶、Sephadex LH-20、ODS柱色谱及反相制备型HPLC等方法进行分离纯化,根据化合物的理化性质及波谱数据鉴定它们的结构。结果与结论从体积分数为60%的乙醇提取液中分离得到7个酚性成分。结构分别鉴定为:阿魏酸棕榈酸-16-醇酯(1)、对羟基桂皮酸(2)、对羟基苯乙酮(3)、香草醛(4)、香草酸(5)、丁香酸(6)、对羟基苯甲酸(7)。化合物1~3为首次从该属植物中分离得到,化合物1~7为首次从该种植物中分离得到。     

微波辅助提取兖州卷柏中的总黄酮

目的研究兖州卷柏黄酮成分的最佳提取条件。方法正交试验，确定提取兖州卷柏总黄酮的最优提取条件。结果462W时，用微波辅助法提取10min为最优提取条件。结论黄酮。优选微波辅助提取法，在单因素实验的基础上，通过总黄酮以70％乙醇为溶剂，料液比为1：20，功率为实验结果表明采用微波辅助法能有效提取兖州卷柏总