O,O′-二烷基-O″-(5-取代-3-苯并噻吩乙腈肟)磷酸酯及硫代磷酸酯的合成

合成了18个O,O′-二烷基-O″-(5-取代-3-苯并噻吩乙腈肟)磷酸酯及硫代磷酸酯类化合物(Ⅰ_1～18)。初步杀螺试验结果表明,其中5个化合物,即Ⅰ_2,3,7,11,12有明显的杀螺增效作用。     

制首乌中1个新的四羟基二苯乙烯苷的结构鉴定及其心血管活性研究

目的　从制首乌(Radix Polygoni multiflori Preparata)水溶性部分寻找心血管活性成分。方法　采用体外抑制血管平滑肌细胞(SMC)增殖活性跟踪筛选,利用Sephadex,反相硅胶柱色谱、HPLC对制首乌水溶性成分进行分离纯化,应用理化常数测定和光谱(UV,IR,MS,¹HNMR,¹³CNMR,2D-NMR)分析技术鉴定结构。结果　分离并鉴定了1个单体化合物2,3,5,4′-四羟基二苯乙烯-2-O-(6″-O-α-D-吡喃葡糖)-β-D-吡喃葡糖苷(I)。结论　I为新化合物,具有较强的抑制SMC增殖活性。     

海南含羞草中黄酮碳苷类化学成分的研究

目的研究海南含羞草(Mimosa pudica)的化学成分。方法利用Diaion HP-20，Toyopearl HW-40，MCI-Gel CHP-20，Sephadex LH-20，RP18及硅胶等柱色谱法对海南含羞草成分进行分离纯化，根据理化性质和光谱数据鉴定化合物的结构。结果分离鉴定了4个化合物：7,8,3′,4′-四羟基-6-C-［α-L-鼠李糖-(1→2)］-β-D-葡糖黄酮碳苷(I)，5,7,4′-三羟基-8-C-［α-L-鼠李糖(1→2)］-β-D-葡糖黄酮碳苷(II)，5,7,3′,4′-四羟基-6-C-［α-L-鼠李糖-(1→2)］-β-D-葡糖黄酮碳苷(III)，儿茶素(IV)。结论化合物I为新化合物，化合物II～IV为首次从该植物中分离得到。     

藤香树中二个新的脂肪硝基酚苷的鉴定藤香树中二个新的脂肪硝基酚苷的鉴定

目的研究藤香树Schisandra propinqua (Wall.) Baill var. intermidia A.C.Smith茎藤的化学成分。方法 应用多种色谱技术进行分离纯化，根据化合物的理化性质和光谱数据分析鉴定结构。结果分离得到7个化合物，分别鉴定为6′-O-α-L-arabinofuranosylthalictoside (1), 6′-O-β-D-apiofuranosylthalictoside (2), thalictoside (3), icariside D₂(4)， prinsepiol (5), (+)-1-hydroxypinoresinol (6)和(+)-medioresinol (7)。结论化合物1和2为新的脂肪硝基酚苷化合物，其余均为首次从藤香树中获得。     

O,O′-二烷基-O″-(5-取代-3-苯并噻吩乙腈肟)磷酸酯及硫代磷酸酯的合成

合成了18个O,O′-二烷基-O″-(5-取代-3-苯并噻吩乙腈肟)磷酸酯及硫代磷酸酯类化合物(Ⅰ_(1～18))。初步杀螺试验结果表明,其中5个化合物,即Ⅰ_(2,3,7,11,12)有明显的杀螺增效作用。     

拟人参皂苷F11在大鼠体内的药物代谢研究

目的探讨拟人参皂苷F11在大鼠体内的药物代谢产物及其过程.方法ip拟人参皂苷F₁₁后,应用TLC分析排泄物中的代谢产物,并利用制备薄层分离制备代谢产物,通过波谱解析(MS,¹HNMR,¹³CNMR,¹H-¹HCOSY)确定其结构.结果从粪便中分离鉴定了3种代谢产物,分别为拟人参皂苷R_T5,ocotillol和1个新的代谢产物F-3-1,并确定其结构为6-O-α-L-吡喃鼠李糖基(1-2)-β-D-吡喃葡糖基-(20S,23S,24R)-达玛-20(24)-环氧-3β,6α,12β,23,25-五醇(6-O-α-L-rhamnopyranosyl-(1-2)-β-D-glucopyranosyl-(20S,23S,24R)-dammar-20(24)-epoxy-3-β,6α,12β,23,25-pentanol).但在尿液和胆汁中并未发现任何代谢产物.结论拟人参皂苷F₁₁不被肝脏代谢,但胆汁排泄物可在肠道被代谢为水解和氧化产物.     

(9S)-12-亚甲基红霉素衍生物的合成及体外抗菌活性

目的合成新的具有抗菌活性的红霉素衍生物。方法以红霉素为原料，合成中间体2′-O,4″-O-二苯甲酰基-(9S)-9-O,11-O-异丙基-12-亚甲基红霉素与6,7-去氢-2′-O,4″-O-二苯甲酰基-(9S)-9-O,11-O-异丙基-12-亚甲基红霉素，进而合成相应(9S)-9-O,11-O-亚乙基-12-亚甲基衍生物。产物结构经¹³C NMR,FAB-MS确证。对所得化合物进行体外抗菌活性测定。结果制备11个红霉素衍生物，其中5个未见文献报道。化合物9和12进行了体外抗菌活性测定。结论化合物9和12表现出较弱的抗菌活性。     

喙果黑面神化学成分研究

目的研究大戟科植物喙果黑面神(Breynia rostrata Merr.)的化学成分。方法利用硅胶、凝胶等色谱技术分离纯化化学成分,根据化合物的理化性质和光谱数据进行结构鉴定。结果从喙果黑面神的正丁醇萃取部分分离得到4个化合物,分别鉴定为6-O-甲基丙酰基-α-D-吡喃葡糖(6-O-methylpropanoyl-α-D-glucopyranose,1);4″-苯酚基-6-O-甲基丙酰基-β-D-吡喃葡糖苷(4″-phenolic-6-O-methylpropanoyl-β-D-glucopyranoside,2);1-O-没食子酰基-β-D-吡喃葡糖苷(1-O-galloyl-β-D-glucopyranoside,3);熊果苷(arbutin,4)。结论化合物1和2为新化合物,3和4均为首次从该种植物分离得到。     

红芽大戟化学成分研究

目的研究茜草科植物红芽大戟(Knoxia corymbosa Willd．)的化学成分。方法利用硅胶、聚酰胺等色谱技术分离纯化,根据化合物的理化性质和光谱数据进行鉴定。结果从红芽大戟的正丁醇萃取部分分离得到4个黄酮醇苷成分,分别鉴定为:槲皮素-7-O-α-L-阿拉伯糖-3-O-β-D-6″-乙酰基吡喃葡糖苷(quercetin-7- O-α-L-arabinosyl-3-O-β-D-6″-acetylglucopyranoside,1);山奈酚-7-O-α-L-阿拉伯糖-3-O-β-D-吡喃葡糖苷(kaempferol-7-O-α-L-arabinosyl-3-O-β-D-glucopyranoside,2);槲皮素-3-O-β-D-吡喃葡糖苷(quercetin-3-O-β-D-glucopyranoside,3); 槲皮素-3-O-β-D-6″-乙酰基吡喃葡糖苷(quercetin-3-O-β-D-6″-acetylglucopyranoside,4)。结论化合物1为新化合物,其余均为首次从该种植物分到。     

O,O′-二烷基-O″-(取代苯乙腈肟)磷酸酯、硫代磷酸酯的合成及对氯硝柳胺的灭螺增效作用

合成了20个O,O′-二烷基-O″-(取代苯乙腈肟)磷酸酯、硫代磷酸酯,并分别与杀螺剂氯硝柳胺组成复方,进行室内杀螺试验。初步结果表明,化合物V_4,7,12,18有明显杀螺增效作用,其中V12可使氯硝柳胺的杀螺效果提高3.81倍。同时发现化合物V_2,7,10,13单独使用时,也有良好的杀螺作用。     

玄参的脂溶性化学成分

目的：研究中药玄参(Scrophularia　ningpoensis　Hemsl.)脂溶性部位的化学成分。方法：利用溶剂提取和硅胶等色谱方法对玄参乙醚可溶部位进行分离纯化,通过化学和光谱方法鉴定结构。结果：共分得10个化合物,分别鉴定为3-O-乙酰基-2-O-阿魏酰基-α-L-鼠李糖(I),3-O-乙酰基-2-O-对羟基肉桂酰基-α-L-鼠李糖(II),肉桂酸(III),4-羟基-3-甲氧基苯甲酸(IV),对甲氧基肉桂酸(V),4-羟基-3-甲氧基肉桂酸(VI),5-羟甲基糠醛(VII),熊果酸(VIII),β-谷甾醇(IX),β-谷甾醇葡糖苷(X)。结论：化合物I,II为新化合物。化合物IV,V,VII,VIII为首次从该植物中分得。玄参脂溶性部位含有较多的酚性化合物。     

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。     

国产沉香化学成分研究 Ⅳ.2-(2-苯乙基)色酮类化合物的分离与鉴定

自国产沉香(Lignum Aquilariae sinensis)[属瑞香科(Thymeleaceae)植物]的乙醇提取物的乙醚溶解部分中分离得到六个2-(2-苯乙基)色酮类化合物。经光谱(UV,IR,¹HNMR ¹³CNMR和MS)分析及化学合成,确定其中一个为新化合物,即6-羟基-2-[2-(4-甲氧基苯)乙基]色酮(Ⅴ)。其余五个为已知化合物,即2-(2-苯乙基)色酮,6-氧基-2-(2-苯乙基)色酮,6,7-二甲氧基-2-(2-苯乙基)色酮,6-甲氧基-2-[2-(3′-甲氧基苯)乙基]色酮和6-羟基-2-(2-苯乙基)色酮,这些化合物均是首次从该植物中分离得到。     

巴戟天和恩施巴戟的蒽醌化合物

从巴戟天(Morinda officinalis How.)根的氯仿提取物中,分离得八个蒽醌化合物,其中二个为新化合物,它们的结构为1,6-二羟基-2,4-二甲氧基蒽醌(1,6-dihydroxy-2,4-dimethoxyanthraquinone,V),1,6-二羟基-2-甲氧基蒽醌(1,6-dihydroxy-2-methoxy-anthraquinone,Ⅵ)。从恩施巴戟(Damnacanthus indicus Linn.)根的氯仿提取物中,分离得七个蒽醌化合物,其中一个为新化合物,其结构为1,4-二甲氧基-2α-羟基蒽醌(1,4-dimethoxy-2-hydroxyanthraquinone,ⅩⅢ)。     

Nitrosourea-induced DNA single-strand breaks.

Reaction of DNA with nitrosoureas in vitro results in extensive formation of alkali labile sites. Two types of single-strand scission (SSS) processes may be distinguished by their different rates: (1) type I SSS which occurs relatively fast at high pH, and (2) type II SSS which is a much slower process. Neither of these processes is affected by free radical traps. Dimethyl sulfate, which is known to alkylate DNA bases but not phosphate residues, shows no type I SSS but does show extensive type II SSS. That the latter process involves alkylation of bases followed by the formation of apurinic sites was confirmed by using endonuclease VI, an enzyme specific for apurinic positions. Reactions of chloroethylnitrosoureas with DNA produces both type I and type II SSS. Aliphatic amines produced in the decomposition of alkyl nitrosoureas do not contribute significantly to the scission of apurinic sites via Schiff base formation. However, this process may be significant for aryl nitrosoureas. Ethyl nitrosourea (ENU), 1, 3-bis(2-chloroethyl)nitrosourea (BCNU), and 3-cyclohexyl-1-(2-hydroxyethyl)-1-nitrosourea (CHNU) readily degrade poly A by phosphate alkylation, with rates that parallel their relative rates of decomposition. The relative rates of hydrolysis of triethylphosphate and β-hydroxyethyl diethyl phosphate parallel the type I SSS observed for ENU and CHNU with DNA. The type I SSS of DNA by these compounds appears to involve a similar phosphotriester formation and hydrolysis. The type I SSS is in accord with the observed extreme liability of β-hydroxyethyl diethyl phosphate which is attributed to participation of the OH group, and by the fact that methylation of the OH completely inhibits the type I SSS process.     

Mammalian cell transformation induced by chromium(VI) compounds in the presence of nitrilotriacetic acid

We used a soft agar assay on cultured Syrian hamster fibroblasts to determine the ability of nitrilotriacetic acid (NTA) and Cr(VI) compounds to induce malignant cell transformation. Induction of extended anchorage-independent growth was detected in BHK 21/c13 cells by scoring colonies of transformed cells visible to the naked eye 20-25 d after plating in growth medium containing agar. Survival was determined by plating cells in liquid medium without agar and by counting the number of macroscopic colonies after 7-10 d. Mitomycin C and 4-nitroquinoline 1-oxide were used as reference direct transforming agents, with clearly positive results. In our hands no increase of the spontaneous transformation rate of BHK cells was induced by NTA concentrations ranging from 2 X 10(-3) to 10(-2) M, although the survival index was significantly reduced above 4 X 10(-3) M NTA. Two Cr(VI) compounds, K2Cr2O7, which is highly soluble in water, and CaCrO4, which is partially soluble, were tested in the soft agar assay either in the absence or in the presence of NTA. When used alone, both compounds behaved as positive transforming agents. NTA increased 4 or 10 times the cytotoxicity and the transforming activity of CaCrO4 and K2Cr2O7, respectively. As the amounts of soluble Cr(VI) detectable in the K2Cr2O7 and CaCrO4 solutions were not increased in the presence of NTA, a synergistic interaction between NTA and soluble Cr(VI) is inferred.     

仙鹤草根芽中新二氢黄酮醇甙的结构研究

从仙鹤草根芽的苯提取物和丙酮提取物中分得三个化合物。通过理化性质,波谱数据(UV,IR,NMR,MS,GD,GC),化学降解和衍生物制备,两个已知化合物分别鉴定为软脂酸(Ⅷ)和胡萝卜甙(Ⅸ),一个新化合物确定为(2S,3S)-(一)-花旗松素-3-O-β-D-葡萄吡喃糖甙(Ⅹ)。     

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(▽)。     

Effects of triaryl phosphates on mouse and human nuclear receptors

The constitutively active receptor (CAR) is a crucial regulator of genes encoding for enzymes active in drug/steroid oxidation, conjugation, and transport. In our attempt to isolate the endogenous inhibitory ligand(s) for the mouse CAR, we found surprisingly that the inhibitory activity was associated with di- and tri-isopropylated phenyl phosphates that were present in livers of untreated mice. Trans-activation experiments in mammalian cells with synthetic compounds verified that mouse CAR was inhibited by various isopropylated phenyl phosphates (40-80%). Such triaryl phosphates are widely used as fire retardants, lubricants, and plasticizers, and some of them are known to disturb reproduction by currently unknown mechanisms. Equipped with the finding that these compounds could interact with mouse CAR, we proceeded to determine their functional effects on other nuclear receptors. Human CAR and pregnane X receptor (PXR) were variably activated (2-5-fold) by triaryl phosphates while mouse PXR, peroxisome proliferator-activated receptor-alpha, and vitamin D receptor were refractory. Among steroid hormone receptors, the human androgen receptor was inhibited by triphenyl phosphate and di-ortho-isopropylated phenyl phosphate (40-50%) and activated by di- and tri-para-substituted phenyl phosphates (2-fold). Our results add to the list of CAR and PXR activators and suggest steroid-dependent biological pathways that may contribute to the reproductive effects of triaryl phosphates.     

中药大血藤的酚性化合物

目的对中药大血藤干燥藤茎的化学成分进行研究。方法采用现代色谱技术分离化合物，运用现代波谱技术(IR，MS，¹H NMR，¹³C NMR，²DNMR)对所得化合物的结构进行鉴定。结果从大血藤的藤茎中分得10个酚类化合物，分别鉴定为1-O-(香草酸)-6-(3″,5″-二-O-甲基-没食子酰基)-β-D-葡糖苷(I)、(-)-表儿茶素(II)、阿魏酸-对羟基苯乙醇酯(III)、3-O-咖啡酰奎宁酸(IV)、3-O-咖啡酰奎宁酸甲酯(V)、罗布麻宁(VI)、香草酸(VII)、原儿茶酸(VIII)、3,4-二羟基-苯乙醇(IX)、4-羟基-苯乙醇(X)。结论化合物I为新化合物，化合物III～VI和VIII～X为首次从该植物中分得。