火绒草中的黄酮苷类成分

目的研究火绒草[Leontopodium leontopodioides(Wild.)Beauv.]中黄酮苷类化学成分。方法采用反复硅胶柱色谱法、Sephadex LH-20柱色谱法、ODS柱色谱法和反复重结晶等方法进行分离纯化,并通过理化常数测定和波谱分析鉴定了其化学结构。结果从体积分数为60%的火绒草乙醇溶液提取物中分离得到5个化合物,并鉴定其结构为:芹菜素-7-O-β-D-吡喃葡萄糖苷(apigenin-7-O-β-D-glu-copyranoside1)、木犀草素-4′-O-β-D-吡喃葡萄糖苷(luteolin-4′-O-β-D-glucopyranoside2)、6-羟基-木犀草素-7-O-β-D-吡喃葡萄糖苷(6-hydroxyluteolin-7-O-β-D-glucopyranoside3)、6-羟基-芹菜素-7-O-β-D-吡喃葡萄糖苷(6-hydroxyapigenin-7-O-β-D-glucopyranoside4)、槲皮素-3-O-β-D-吡喃葡萄糖苷(quercetin-3-O-β-D-glucopyranoside5)。结论化合物4,5为首次从火绒草属植物中分离得到,化合物2,3为首次从本植物火绒草中分离得到。     

北葶苈子中黄酮苷类成分的分离与鉴定

目的对北葶苈子的黄酮苷类成分进行研究,为该植物资源开发利用提供依据。方法综合应用大孔吸附树脂、硅胶、Sephadex LH-20和ODS等柱色谱以及HPLC制备法对北葶苈子化合物进行分离纯化,利用理化性质与核磁共振波谱数据鉴定化合物的结构。结果从体积分数为50%的北葶苈子乙醇溶液提取物中分离鉴定了7个单体成分,分别为芹菜素-7-O-β-D-吡喃葡萄糖醛酸苷(apigenin-7-O-β-D-pyranglycuronide,1)、木犀草素-7-O-β-D-葡萄糖醛酸苷(luteolin-7-O-β-D-glycuronide,2)、(+)-4'-O-methylcatechin-7-O-β-D-glucopyranoside,3)、山奈酚-3-O-β-D-葡萄糖醛酸苷(kaempferol-3-O-β-D-glycuronide,4)、山奈酚-3-O-β-D-葡萄糖(1→2)-β-D-葡萄糖苷(kaempferol-3-O-β-D-glucosyl(1→2)-β-D-glucoside,5)、山奈酚-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基7-O-β-D-吡喃葡萄糖苷(kaempferol-3-O-β-D-glucopyranosyl(1→2)-β-D-glucopyranosyl-7-O-β-D-glucopyranoside,6)及kaempferol 2G-glucosylgentiobioside(7)。结论在对北葶苈子的化学成分进行研究的过程中,分离鉴定了7个黄酮苷类化合物。化合物1~7均为首次从独行菜属中分离得到,并首次对化合物7的核磁数据进行报道。     

酸浆宿萼的黄酮苷类化学成分

目的研究茄科植物酸浆(Physalis alkekengiL.var.francheti(Mast.)Makino)宿萼的化学成分。方法用体积分数为80%的乙醇溶液加热回流提取,回收乙醇,浓缩后用水混悬,依次用环己烷、乙酸乙酯、正丁醇萃取;将正丁醇层通过聚酰胺柱色谱,Sephadex LH-20柱色谱、反相ODS开放柱色谱及反相制备HPLC等手段,共分离得到5个黄酮苷类化合物;利用其理化性质和波谱学分析数据,鉴定化合物结构。结果分离得到的5个黄酮苷类化合物,分别鉴定为木犀草素-7-O-β-D-葡萄糖苷(1),木犀草素-4′-O-β-D-葡葡萄糖苷(2),槲皮素-3-O-β-D-葡葡萄糖苷(3),槲皮素-7,3-二-O-β-D-葡葡萄糖苷(4),木犀草素7,3′-二-O-β-D-葡葡萄糖苷(5)。结论木犀草素-4′-O-β-D-葡萄糖苷(2),槲皮素-3,7-二-O-β-D-葡萄糖苷(4),木犀草素7,3′-二-O-β-D-葡萄糖苷(5)为首次从该属植物中分离得到,槲皮素-3-O-β-D-葡萄糖苷(3)为首次从该植物中分离得到。     

金银忍冬叶的化学成分研究

目的 研究金银忍冬叶Lonicera macckii (Rupr.) Maxim.的化学成分.方法 采用硅胶柱色谱、Sephadex LH-2柱色谱、重结晶等方法进行分离纯化,根据理化性质和波谱数据鉴定化合物的结构.结果 从金银忍冬叶中分离鉴定了12个化合物,分别为山柰酚(1)、芹菜素(2)、金丝桃苷(3)、芹菜素-7-O-β-D-吡喃葡萄糖苷(4)、金圣草素-4′-O-β-D-葡萄糖苷(5)、木犀草素-7-O-β-D-吡喃葡萄糖苷(6)、裂环马钱素酸(7)、獐牙菜苷(8)、3,5-O-二咖啡酰基奎宁酸甲酯(9)、齐墩果酸(10),胡萝卜苷(11)、β-谷甾醇(12).结论 化合物1～6、8～12为首次从该植物中分离得到,化合物5为首次从该属植物中分离得到.     

浮萍中黄酮类化学成分的分离与鉴定

目的研究浮萍Spirodela polyrrhiza(L.)Schleid.的化学成分。方法采用正相和反相硅胶柱色谱以及半制备型HPLC进行分离纯化,根据理化性质和波谱数据鉴定化合物的结构。结果分离得到了5个黄酮苷类化合物,分别鉴定为芹菜素8-C-(2″-O-阿魏酰基)-β-D-葡萄糖苷(apigenin-8-C-(2″-O-feruoyl-)-β-D-glucoside,1),荭草素(rietin,2),牡荆素(vitexin,3),木犀草素7-O-β-D-葡萄糖苷(luteolin7-O-β-D-glucoside,4),芹菜素7-O-β-D-葡萄糖苷(apigenin7-O-β-D-glucoside,5)。结论化合物1为一个新化合物,化合物2和3为首次自该植物中分离得到。     

棉团铁线莲黄酮类成分研究

目的研究棉团铁线莲Clematis hexapetalaPall.的干燥根及根茎的化学成分。方法利用溶剂提取,硅胶柱色谱和高效液相色谱等手段进行分离、纯化,根据理化性质和波谱数据进行结构鉴定。结果分离鉴定了12个黄酮类化合物,分别为3,5,6,7,8,3′,4′-七甲氧基黄酮(1),nobiletin(2),liquiritigenin(3),橙皮素(4),柚皮素(5),7,4′-二羟基-二氢黄酮-7-O-β-D-葡萄糖苷(6),5,7,4′-三羟基-3′-甲氧基黄酮醇-7-O-α-L-鼠李糖(1→6)-β-D-葡萄糖苷(7),6-hydroxybiochainA(8),芒柄花素(9),大豆素(10),染料木素(11),鸢尾苷(12)。结论以上化合物均为首次从该植物中分离得到。     

火绒草正丁醇层化学成分的分离与鉴定

目的研究中药火绒草正丁醇层的化学成分。方法采用反复硅胶柱色谱法、Sephadex LH-20柱色谱法和反复重结晶等进行分离纯化,并通过波谱分析技术鉴定其化学结构。结果从火绒草中分离得到5个化合物,分别鉴定为:木犀草素-3′-O-β-D-葡萄糖苷(luteolin-3′-O-β-D-glucoside,1)、山奈酚-3-O-β-D-葡萄糖苷(kaempferol-3-O-β-D-glucoside,2)、金圣草素-4′-O-β-D-葡萄糖苷(chrysoeri-ol-4′-O-β-D-glucoside,3)、甘草苷(liquiritin,4)、腺苷(adenosine,5)。结论化合物2~5为首次从火绒草属植物中分离得到,化合物1为首次从火绒草中分离得到。     

怀菊花化学成分的研究

目的 研究菊科植物怀菊花 Chrysanthemum morifolium Ramat. ‘huaiju’ cv. nov. 的化学成分。方法 采用各种色谱技术进行分离,根据波谱数据鉴定结构。结果 从怀菊花中分离得到10个黄酮类化合物,分别鉴定为木犀草素 (1)、芹菜素 (2)、金合欢素 (3)、香叶木素 (4)、香叶木素 7-O-β-D-葡萄糖苷 (5)、木犀草素 7-O-β-D-葡萄糖苷 (6)、金合欢素 7-O-β-D-葡萄糖苷 (7)、金合欢素 7-O-(6’’-O-乙酰基)-β-D-葡萄糖苷 (8)、蒙花苷 (9)、芹菜素 7-O-β-D-葡萄糖苷 (10)。结论 本研究首次对怀菊花化学成分进行系统研究,化合物1~10均为首次从该植物中分离得到。     

维药两色金鸡菊花化学成分的分离与鉴定

目的研究维药两色金鸡菊花的化学成分,以期更好地开发利用金鸡菊。方法采用聚酰胺、Sephadex LH-20和ODS柱色谱等分离手段进行化学成分的分离纯化,根据理化性质及波谱数据鉴定其化学结构。结果从两色金鸡菊花醇提取物的乙酸乙酯萃取部分中分离得到8个化合物,分别鉴定为山柰酚-7-O-β-D-吡喃葡萄糖苷(kaempferol-7-O-β-D-glucopyranoside,1)、3',4',7-三羟基黄酮-7-O-β-D-吡喃葡萄糖苷(3',4',7-trihydroxyflavone-7-O-β-D-glucopyranoside,2)、槲皮素-7-O-β-D-吡喃葡萄糖苷(quercetin-7-O-β-D-glucopyranoside,3)、6,7,3',4'-四羟基橙酮(6,7,3',4'-tetrahydroxyaurone,4)、3',5',5-三羟基二氢黄酮-7-O-β-D-吡喃葡萄糖苷(3',5',5-trihydroxyflavanone-7-O-β-D-glucopyranoside,5)、紫铆花素-4'-O-β-D-吡喃葡萄糖苷(butein-4'-O-β-D-glucopyranoside,6)、奥卡宁(okanin,7)、马里苷(marein,8)。结论化合物1~5为首次从金鸡菊属植物中分离得到,化合物6为首次从该两色金鸡菊花中分离得到。     

忍冬叶中黄酮类成分的分离与鉴定

目的为忍冬(Lonicera japonicaThunb.)叶中黄酮类化学成分药效学物质基础提供依据。方法采用反复硅胶柱色谱法、Sephadex LH-20柱色谱法等对忍冬叶进行分离纯化,并通过理化常数测定和波谱分析对分离得到的化合物进行结构鉴定。结果从忍冬叶75%乙醇提取物中分离得到7个黄酮类化合物,并鉴定其结构分别为5,7,4′-三羟基-8-甲氧基黄酮(5,7,4′-trihydroxy-8-me-thoxyflavone,1)、木犀草素(luteolin,2)、苜蓿素(tricin,3)、山萘酚-7-O-β-D-吡喃葡萄糖苷(kaempferol-7-O-β-D-glucopyranoside,4)、木犀草素-7-O-β-D-吡喃葡萄糖苷(luteolin-7-O-β-D-glu-copyranoside,5)、洋芹素-7-O-β-D-吡喃葡萄糖苷(apigenin-7-O-β-D-glucopyranoside,6)、香叶木素-7-O-β-D-吡喃葡萄糖苷(diosmetin-7-O-β-D-glucopyranoside,7)。结论化合物1、4为首次从忍冬属植物中分离得到,化合物3、6、7为首次从植物忍冬中分离得到。     

Trichloroethylene. I. Carcinogenicity of trichloroethylene.

Trichloroethylene (TCE) as an industrial pollutant may damage human health and can be considered as carcinogen. TCE has been detected in the environment and in various human organs, e.g., liver, kidney and brain etc. There are histological alterations such as depletion of glycogen and hydropic degeneration in the liver, however, other signs of TCE effects can be found in various organs as well. TCE and its metabolites, e.g., trichlorethanol, trichloro-acetic acid and epoxides were recently identified as strong mutagens in Ames mutagenicity test inducing frameshift and base-substitution mutations. TCE induced predominantly hepatocellular carcinoma after long term administration in mice. In these animals, kidneys and liver were supposed to be primary target organs with low epoxy-hydrolase activity. A high level of mitotic gene conversion (or gene rearrangement) was indicated by the metabolism of TCE after repeated administration. Purified TCE by was a weak mutagen in the presence of S9 microsomal fraction of rats and as a consequence, the carcinogenic activity was low in the kidney of rats. However, a dose related increase of Leydig cell tumors was found in male rats.     

Trichloroethylene. II. Mechanism of carcinogenicity of trichloroethylene.

The cancer inducing effect of trichloroethylene (TCE) was studied by various methods. DNA complexing activity and apoptosis inhibition were found to be the key elements of the carcinogenicity of TCE and its metabolites. The ability of TCE to interact with DNA was low, but its incorporation into the RNA and DNA of the brain, testis, pancreas, kidney, liver, lung and spleen, cannot be excluded. Exposure to TCE and its metabolites provides a selective growth advantage to spontaneously occurring mutations in some K- and H-ras oncogenes (as non specific results of secondary DNA or RNA damage). The amount of DNA-TCE adducts was higher in mouse hepatocytes than in rat hepatocytes. These differences may explain the species difference in carcinogenicity of TCE, which was dose dependent (due to metabolism) in mice but independent in rats. The blood level kinetics of TCE confirmed the faster metabolic rate in mice, including peroxisome proliferation and induction in hepatocytes. Dichloroacetic- and trichloroacetic acid were found to be hepatic carcinogens in mice, and the specificity depends on peroxisome proliferation induction. Possibly, TCE and related compounds down regulated apoptosis in mouse liver, and the reduced ability to remove initiated cells by apoptosis could be responsible for liver cancer induction by TCE.     

Studies in antifertility agents. 11. Secosteroids. 5. Synthesis of 9,11-secoestradiol.

9,11-Secoestradiol (9) and 11-hydroxy-9,11-secoestradiol (12) have been synthesized starting from 17-acetoxyestradiol 3-methyl ether (1) and found to possess significant antifertility activity in rats. 3-Methoxy-9,11-seco-9-oxo-17beta-acetoxyestra-1,3,5(10)-trien-11-oic acid (2), prepared by CrO3 oxidation of 1, on hydrogenolysis gave methyl 17beta-hydroxy-3-methoxy-9,11-secoestra-1,3,5(10)-triene-11-carboxylate (3). The 17-O-THP derivative of 3 was treated with LiAlH4 to give 17beta-(O-tetrahydropyranyl)-3-methoxy-11-hydroxy-9,11-secoestra-1,3,5(10)-triene (5). The 11-O-mesylate of 5 on LiAlH4 reduction followed by mild acid treatment and demethylation under alkaline conditions gave 9. LiAlH4 reduction of 3 gave 9,11-seco-11-hydroxyestradiol 3-methyl ether (11) which on demethylation gave 9,11-seco-11-hydroxyestradiol (12).     

Metabolism of benzothiazole. I. Identification of ring-cleavage products.

1. The metabolic fate of benzothiazole in guinea pig has been investigated following i.p. administration at a dose of 30 mg/kg. 2. Five ring-cleavage products were identified in urinary extracts by g.l.c.-mass spectra. By reference to authentic compounds the three major metabolites were shown to be 2-methylmercaptoaniline (I), 2-methylsulphinylaniline (II) and 2-methylsulphonylaniline (III). On the basis of the mass spectrometric evidence the remaining two metabolites were postulated to be 2-methylsulphinylphenylhydroxylamine (IV) and 2-methylsulphonylphenylhydroxylamine (V). 3. I, II and III were present in conjugated and unconjugated forms; IV and V were identified only after hydrolysis with sulphatase.