槲寄生化学成分的研究 Ⅶ.槲寄生新甙Ⅶ的分离和结构

自中药槲寄生中分离得到一个新的黄酮甙,经波谱测定及水解试验,确定其结构为鼠李秦素-3-O-β-D-芹糖基(1→2)-[6″-(3-羟基-3-甲基戊二酸半酯)]葡萄糖甙,命名为槲寄生新甙Ⅶ(viscumneoside Ⅶ).     

槲寄生化学成分的研究——Ⅲ.槲寄生新甙Ⅲ,Ⅴ,Ⅵ的结构

自槲寄生(Viscum coloratum(Kom.) Nakai)中分离得到五个黄酮甙。经光谱和化学分析确定Ⅰ为异鼠李素-3-O-β-D-葡萄糖甙,Ⅱ为异鼠李素-7-O-β-D-葡萄糖甙,Ⅲ为高圣草素-7-O-β-D-芹菜糖基(1→2)-β-D-葡萄糖甙;Ⅴ为高圣草素-7-O-β-D-芹菜糖(1→5)-β-D-芹菜糖(1→2)-β-D-葡萄糖甙;Ⅵ为高圣草素-7-O-β-D-(6″-乙酰)-葡萄糖甙。化合物Ⅲ,Ⅴ,Ⅵ为三个新的双氢黄酮甙,分别命名为槲寄生新甙Ⅲ(viscumneoside Ⅲ),槲寄生新甙Ⅴ(viscumneoside Ⅴ)和槲寄生新甙Ⅵ(viscumneoside Ⅵ)。Ⅰ和Ⅱ亦系首次从该植物中发现。     

槲寄生化学成分的研究——Ⅲ.槲寄生新甙Ⅲ,Ⅴ,Ⅵ的结构

自槲寄生(Viscum coloratum(Kom.) Nakai)中分离得到五个黄酮甙。经光谱和化学分析确定Ⅰ为异鼠李素-3-O-β-D-葡萄糖甙,Ⅱ为异鼠李素-7-O-β-D-葡萄糖甙,Ⅲ为高圣草素-7-O-β-D-芹菜糖基(1→2)-β-D-葡萄糖甙;Ⅴ为高圣草素-7-O-β-D-芹菜糖(1→5)-β-D-芹菜糖(1→2)-β-D-葡萄糖甙;Ⅵ为高圣草素-7-O-β-D-(6″-乙酰)-葡萄糖甙。化合物Ⅲ,Ⅴ,Ⅵ为三个新的双氢黄酮甙,分别命名为槲寄生新甙Ⅲ(viscumneoside Ⅲ),槲寄生新甙Ⅴ(viscumneoside Ⅴ)和槲寄生新甙Ⅵ(viscumneoside Ⅵ)。Ⅰ和Ⅱ亦系首次从该植物中发现。     

槲寄生化学成分的研究——Ⅳ.槲寄生新甙Ⅳ的结构

前文曾报道从槲寄生中分离及确定五个新黄酮甙的结构。本文报道另一新黄酮化合物(Ⅳ)的分离和结构测定。槲寄生(Viscum coloratura(Kom)Nakai)生药的乙醇提取物,分别用石油醚、醋酸乙酯和正丁醇萃取,正丁醇萃取物经聚酰胺细粉和硅胶低压柱层析,分离得到Ⅳ。通过光谱分析和水解试验,确定Ⅳ的结构为鼠李秦素-3-0-β-D-(6″-β-羟基-β-甲基戊二酸半酯)-葡     

槲寄生化学成分的研究Ⅰ~△

自槲寄生(Viscum coloratum(Komar.)Nakai)中分离得到六个黄酮类化合物。确定其中的F_4、F_(10)为两个新黄酮甙,分别命名为槲寄生新甙Ⅰ(Viscumneoside Ⅰ)和槲寄生新甙Ⅱ(Viscumneoside-Ⅱ)。另外四个为已知化合物,分别鉴定为鼠李秦素3-O-β-D 葡萄糖甙(F_1);高圣草素-7-O-β-D-葡萄糖甙(F_2);鼠李秦素(F_6)和高圣草素(F_7)。F_1和 F_6系首次从该种植物中得到。     

槲寄生化学成分的研究——Ⅷ.2,3-丁二醇单葡萄糖甙的分离和结构

前文曾报道从中药槲寄生Viscum coloratum(Kom.)Nakai中分得黄酮、三萜和有机酸等化合物。现又从槲寄生的乙醇提取物中,经大孔吸附树脂层析和反复硅胶柱层析分得化合物Ⅷ～Ⅺ,经波谱分析和水解试验,确定Ⅷ的结构为2,3-丁二醇单葡萄糖甙;Ⅸ的结构为紫丁香甙;Ⅹ的结构为五加甙E;Ⅺ的结构为紫丁香甙元-O-β-D-芹糖基(1→2)葡萄糖甙。Ⅷ为一新结构的醇甙。     

甘草叶中酚酸和黄酮甙类成分的分离鉴定

自甘草(Glycyrrhiza uralensis Fiseh)的干燥叶中分离到7个甙类成分,经化学方法和光谱分析确定结构为原儿茶酸-1-O-β-D-呋喃木糖酯甙(1-O-protocatechuyl-β-D-xylopyranose,Ⅰ)、洋芹素-6,8-C-二葡萄糖甙(vicenin-2,Ⅱ)、异鼠李素-3-O-芸香糖甙(narcissin,Ⅲ)、山柰酚-3-O-芸香糖甙(nicotiflorin,Ⅳ)、山柰酚-3-O-β-D-葡萄糖甙(astragalin,Ⅴ)、槲皮素-3-O-芸香糖甙(rutin,Ⅵ)和槲皮素-3-O-β-D-葡萄糖甙(isoquercitrin,Ⅶ)。其中,Ⅰ是新化合物,命名为乌拉尔新甙(uralenneoside);Ⅲ在本属植物中为首次报道;Ⅲ～Ⅶ在乌拉尔甘草中首次分得。Ⅱ～Ⅶ都是已知活性成分。     

枫香槲寄生化学成分的分离与结构鉴定

目的进一步研究枫香槲寄生的化学成分，寻找抗心血管病的活性成分。方法应用柱色谱法进行分离、纯化，根据理化性质和光谱数据鉴定结构。结果得到5个化合物：反式桂皮酸(trans-cinnamic acid)(I)，齐墩果酸(oleanolic acid)(II)，白杨素(chrysin)(III)，圣草酚(eriodictyol)(IV)，枫香槲寄生苷(V) 。结论V为新化合物，I-IV均为首次从枫香槲寄生中分离得到，其中I,III,IV为首次从桑寄生科植物中分离得到。     

扁枝槲寄生化学成分研究（Ⅱ）

从扁枝槲寄生(Viscum articulatum Burm.f)中分得的另外三种黄酮类化合物,经理化性质及光谱分析鉴定为高圣草素-7-O-β-D-葡萄糖甙-4′-O-βD-(5-′′′桂皮酰基)-芹菜糖(F_1),乔松素-7-O-β-D芹菜糖(1→2)-β-D-葡萄糖甙(F5),乔松素-7-O-β-D-芹菜糖(1→5)-β-D-芹菜糖(1→2)-β-D-葡萄糖甙,三者均为首次报道的新黄酮甙。     

槲寄生化学成分的研究Ⅱ

槲寄生(Viscum coloratum(Komar)Nakai)的乙醇提取物,再经丙酮分离得到八个化合物,其中七个分别鉴定为β-乙酰香树脂醇(Ⅰ)、β-香树脂醇(Ⅱ)、羽扇豆醇(Ⅲ)、齐墩果酸(Ⅳ)、β-谷甾醇(Ⅴ)、白桦脂酸(Ⅵ)和胡萝卜甙(Ⅷ)。后二个化合物系首次从槲寄生中分得。     

Genetic polymorphisms modify the response of factor VII to oral contraceptive use: an example of gene-environment interaction

Elevated plasma levels of factor VII and fibrinogen are risk factors for cardiovascular disease, especially arterial thrombosis. Oral contraceptive use increases factor VII and fibrinogen plasma levels. It has been described that DNA polymorphisms are associated with the plasma levels of hemostatic variables and their regulation. The R/Q353 polymorphism in the factor VII gene and the -455G/A polymorphism in the fibrinogen beta-gene are associated with plasma levels of factor VII and fibrinogen, respectively. We analysed data of a randomised study (n = 95) in which two types of oral contraceptives were compared with regard to their effect on factor VII and fibrinogen, in which we also determined R/Q353 and -455G/A polymorphisms. Women were allocated randomly to either receiving a monophasic oral contraceptive containing 75 micrograms of gestodene and 20 micrograms of ethinyl estradiol, or 150 micrograms of desogestrel and 20 micrograms of ethinyl estradiol. Blood was taken before treatment and after 3 and 6 months of oral contraceptive use. Factor VII and fibrinogen increased significantly after 3 and 6 months of oral contraceptive use; the increase in factor VII was higher in the desogestrel group than in the gestodene group at 3 and 6 months. For fibrinogen, there were no intergroup differences at 3 and 6 months. At baseline, an association between genotype and plasma factor VII and fibrinogen levels was observed. In multivariate analysis, the R/Q353 polymorphism and the type of oral contraceptive were determinants of the effect on the change in factor VII, with the highest increase in women carrying the Q allele and using the desogestrel-containing oral contraceptive, and the lowest increase in women with the RR genotype who use the gestodene-containing oral contraceptive. For fibrinogen, no interaction among type of oral contraceptive, -455G/A polymorphism, and change in plasma levels was observed. We conclude that an individual's genetic variation may contribute to the response of plasma factor VII to oral contraceptive use.     

苦马豆根和茎中一个新黄酮苷

目的研究苦马豆根和茎的化学成分。方法采用反复硅胶柱色谱、Sephadex LH-20色谱进行化合物的分离,根据波谱数据鉴定化合物结构。结果从95%乙醇提取物正丁醇萃取部分得到8个化合物,鉴定为：异鼠李素-3-O-［6″-(3-羟基-3-甲基戊二酸单酯)-β-D-吡喃葡糖苷］(I)、槲皮苷(II)、正丁基-β-D-吡喃果糖苷(III)、尼克酸(IV)、丁二酸(V)、赤藓醇(VI)、D-甘露醇(VII)和尿嘧啶核苷(VIII)。结论化合物I为新化合物,化合物I-VI均为首次从本属植物中得到。     

茜草中抗菌活性成分的研究

从茜草根中分得十二个化合物。通过理化性质及光谱分析,确定了八个已知化合物和一个新化合物(Ⅴ),Ⅴ的结构为1,3,6-三羟基-2-甲基蒽醌-3-O-(O-6′-乙酰基)-β-D-吡喃葡萄糖甙(▽)。     

文冠果果壳中一个新生物碱

目的研究文冠果果壳的化学成分。方法通过硅胶柱色谱、制备型薄层色谱进行化合物的分离，利用多种波谱技术鉴定化合物结构。结果分离得到10个化合物，鉴定为：2-甲基-6-(2′，3′，4′-三羟基丁基)吡嗪(I)、cleomiscosin D(II)、柚皮素(III)、圣草素(IV)、山柰酚(V)、槲皮素(VI)、芦丁(VII)、5，7-二羟基色原酮(VIII)、酪醇(IX)、1-O-甲基-肌-肌醇(X)。结论化合物I为一新化合物；化合物II，IV，V和VII～X均为首次从该属植物中分离得到。     

Cimifoetisides VI and VII Two new cyclolanostanol triterpene glycosides from the aerial parts of Cimicifuga foetida

Two new cyclolanostanol triterpene glycosides, cimifoetiside VI (1) and cimifoetiside VII (2), and one known compound were isolated from the aerial parts of Cimicifuga foetida L. On the basis of spectral and chemical evidences, the structures of 1 and 2 were elucidated to be (23R,24S)-24-O-acetylisodahurinol-3-O-beta-d-galactopyranoside and (23R,24R)-24-O-acetylshengmanol-3-O-beta-d-glucopyranosyl-(1' --> 2')-beta-d-xylopyranoside. The known compound was identified as (23R,24R)-24-O-acetylshengmanol-3-O-beta-d-galactopyranoside (3).     

Decrease in blood coagulation factors II (prothrombin), VII, IX and X in the rat after a single oral dose of butylated hydroxytoluene

Male Sprague-Dawley rats were given butylated hydroxytoluene (BHT) in a dose of 800 mg/kg body weight orally, and 0.5-72 hr later plasma concentrations of factors II, VII, IX and X and hepatic levels of BHT and BHT quinone methide (2,6-di-tert-butyl-4-methylene-2,5-cyclohexadienone) were determined. Levels of factors II, VII, X and IX were reduced 36-60 hr after BHT treatment, but by 72 hr, those most affected (VII and IX) showed some recovery and X had returned to normal. Hepatic levels of BHT reached a maximum 3 hr (a major peak) and 24 hr after BHT dosing and BHT quinone methide reached a maximum at 6 and 24 hr (a major peak). In rats given BHT orally in doses of 200, 400 and 800 mg/kg, factors II, VII and X decreased after 48 hr only in rats given the highest dosage, but factor IX was more susceptible to BHT and showed a dose-dependent decrease. Phylloquinone (1 mg/rat) injected ip 24 hr after the administration of 800 mg BHT/kg maintained normal levels of factors VII and X and an almost normal level of factor IX, but had little effect on the level of factor II. In studies of the effects of drug-metabolizing-enzyme modifiers, neither ip pretreatment with 75 mg phenobarbital sodium/kg for 3 days nor the feeding of 1% cysteine in the diet throughout the experiment prevented the decrease in vitamin-K-dependent factors by 800 mg BHT/kg, but 2-day ip pretreatment with 60 mg cobaltous chloride/kg/day maintained normal levels of factors II and VII and reduced the BHT effect on factors IX and X. SKF 525A (50 mg/kg) injected ip either 30 min before or 12 hr after BHT treatment partially prevented the decrease in factors II, VII and X, or in all four factors, respectively. Thus the decrease in vitamin K-dependent factors may be the same with a single oral dose of BHT as with dietary BHT, and the anticoagulant effect may require the metabolic activation of BHT.     

茜草中蒽醌类成分的研究

从茜草Rubia cordifolia L.根的乙醇提取物中分得七个蒽醌类化合物,经理化性质及光谱分析,分别鉴定为1,3,6-三羟基-2-甲基蒽醌(Ⅰ),1-羟基蒽醌(Ⅱ),1,2,4-三羟基蒽醌(Ⅲ),1,3,6-三羟基-2-甲基蒽醌-3-O-β-D-吡喃葡萄糖甙(Ⅳ),1,2-二羟基蒽醌-2-O-β-D-吡喃木糖(1→6)-β-D-吡喃葡萄糖甙(Ⅴ),1,3-二羟基-2-羟甲基蒽醌-3-O-β-D-吡喃木糖(1→6)-β-D-吡喃葡萄糖甙(Ⅵ)及1,3,6-三羟基-2-甲基蒽醌-3-O-β-D-吡喃木糖(1→2)-β-D-(6'-O-乙酰基)吡喃葡萄糖甙(Ⅶ).其中Ⅶ为一新化合物。     

Etofibrate decreases factor VII and fibrinogen levels in patients with polymetabolic syndrome.

Etofibrate is a hypolipemic drug belonging to the fibrate class. By improving the lipid profile, these drugs often exert a favorable influence on hemostatic risk factors of ischemic heart disease. We present a pilot study on the influence of etofibrate on lipids and lipoproteins in serum, as well as on factor VII and fibrinogen. The study group was comprised of 18 males, aged 52.5 +/- 7.3 years, with hypertriglyceridemia or mixed hyperlipoproteinemia and other risk factors of atherosclerosis, particularly insulin-dependent diabetes and arterial hypertension. The group was further divided into two subgroups depending on the coexistence of arterial hypertension. All patients received etofibrate 500 mg daily for 3 months. In comparison with initial values, a decrease in the following was noted for the whole study group: triglyceride level (226.0 +/- 27.1 vs. 288.0 +/- 51.9 mg/dl; p < 0.05), percent LDL-cholesterol (72.4 +/- 1.8 vs. 75.8 +/- 1.7; p < 0.05), apolipoprotein B (111.2 +/- 4.6 vs. 115.3 +/- 5.4 mg/dl; p < 0.05), atherogenic indices: LDL/HDL (5.06 +/- 0.58 vs. 5.95 +/- 0.50; p < 0.02) and apolipoprotein B and A (apoB/apoA) (0.92 +/- 0.04 vs. 1.02 +/- 0.06; p < 0.05). There was an increase in percent HDL-cholesterol (14.7 +/- 1.1 vs. 12.8 +/- 0.7; p < 0.05) and apoA (121.0 +/- 4.8 vs. 111.2 +/- 2.4 mg/dl; p < 0.05). A marked decrease in the level of factor VII (FVIIc) (114 +/- 5.9 vs. 136 +/- 5.3%; p < 0.001) and fibrinogen (2.95 +/- 0.17 vs. 3.58 +/- 0.17 g/l; p < 0.01) was found. Fibrinogen levels fell notably (3.09 +/- 0.30 vs. 3.87 +/- 0.34 g/l; p < 0.05) in the subgroup with arterial hypertension, and F1 + 2 markers tended to decline (2.32 +/- 0.53 vs. 2.74 +/- 0.37 nmol/l; NS). Patients with normals arterial pressure maintained their fibrinogen levels (3.23 +/- 0.24 vs. 3.36 +/- 0.26 g/l; NS). A positive correlation between FVIIc and F1 + 2 was observed during treatment. All results were expressed as arithmetic means +/- SE. The present study has demonstrated that etofibrate has hypolipemic, antithrombotic and antiatherosclerotic properties in patients with polymetabolic syndrome.     

Inhibitors of autoactivation of plasma hyaluronan-binding protein (factor VII activating protease)

Plasma hyaluronan-binding protein (PHBP), a serine protease that can activate coagulation factor VII and prourokinase, circulates in a single-chain form (pro-PHBP) and autoproteolytically converts to an active two-chain form with the aid of an effector such as spermidine and heparin. It has been postulated that PHBP plays roles in regulating inflammation, vascular function, fibrosis and atherosclerosis. From the comprehensive screening of natural sources for inhibitors of spermidine-induced pro-PHBP autoactivation, we identified several compounds with a polyphenol feature. Of these inhibitors, tannic acid (IC(50)=0.020 μM), delphinidin (IC(50)=0.079 μM), hamamelitannin (IC(50)=0.19 μM), (-)-epicatechin gallate (IC(50)=0.24 μM), and 3,5-di-O-caffeoylquinic acid (IC(50)=1.0 μM) were potent and selective, and did not inhibit heparin-induced pro-PHBP autoactivation and the active form of PHBP at concentrations 100 times higher than the respective IC(50) values. From evaluation of the activities of related compounds, it has been suggested that a compound with multiple aromatic rings with plural phenolic hydroxyl substituents exhibits potent activity. The inhibitory actions of delphinidin, hamamelitannin, (-)-epicatechin gallate and 3,5-di-O-caffeoylquinic acid were attenuated by catechol, a minimum polyphenol unit. Thus, it is likely that pro-PHBP binds these potent inhibitors through its site(s) that recognize a catechol-like structure. Our results would facilitate understanding of the molecular mechanism of pro-PHBP autoactivation and rational design of a compound for suppressing unregulated pro-PHBP activation.     

西洋参茎叶总皂苷碱降解成分西洋参茎叶总皂苷碱降解成分

目的研究西洋参茎叶总皂苷碱降解成分。方法采用硅胶柱色谱并结合HPLC进行分离纯化，通过波谱分析鉴定化合物的结构。结果从西洋参茎叶总皂苷碱降解产物中分离得到9种成分，分别鉴定为：20(S)-原人参二醇(I)，20(S)-达玛-25(26)-烯-3β,12β,20-三醇(II)，24(R)-ocotillol (III)，20(S)-原人参三醇(IV)，20(S)-达玛-25(26)-烯-3β,6α,12β,20-四醇(V)，达玛-20(21),24-二烯-3β,12β-二醇(VI)，达玛-20(21),24-二烯-3β,6α,12β-三醇(VII)，20(S),24(S)-达玛-25(26)-烯-3β,6α,12β,20,24-五醇(VIII)，20(S)-达玛-23-烯-25-过氧羟基-3β,6α,12β,20-四醇(IX)。结论碱降解20位S构型未改变。V，VII，VIII，IX为4个新化合物，并利用2D-NMR技术对新化合物的氢和碳的化学位移进行了归属。其中I对HCT-8人结肠癌细胞具有较强的细胞毒活性。