巴戟天中蒽醌类化合物及生物活性研究

采用硅胶柱层析结合制备液相从巴戟天(Morinda officinalis)中分离得到8个蒽醌类化合物。根据化合物的波谱数据并与文献对照进行了结构鉴定,分别为2-羟甲基-3-羟基蒽醌(2-hydroxymethyl-3-hydroxyanthraquinone,1)、3-羟基-2-羟甲基-1-甲氧基蒽醌(3-hydroxy-2-hydroxymethyl-1-methoxyanthraquinone,2)、2-羟基-1-甲氧基蒽醌(2-hydroxy-1-methoxyanthraquinone,3)、3-羟基-1,2-二甲氧基蒽醌(3-hydroxy-1,2-dimethoxyanthraquinone,4)、甲基异茜草素-1-甲醚(rubiadin-1-methyl ether,5)、1,3-二羟基-2-甲氧基蒽醌(1,3-dihydroxy-2-methoxyanthraquinone,6)、1,3-二羟基-2-乙氧甲基蒽醌(ibericin,7)、1,2-二羟基-3-甲基蒽醌(1,2-dihydroxy-3-methylanthraquinone,8)。其中蒽醌(2)为首次从该植物中分得。利用MTT法对分离出的蒽醌的体外抗癌活性进行筛选,结果显示蒽醌(3)、(5)和(7)对肝癌细胞SMMC-7721增殖有明显的抑制作用,当蒽醌的浓度为400μmol/L时,蒽醌(3)、(5)和(7)对肝癌细胞的抑制率分别为44. 63%、20. 52%、54. 89%。     

月腺大戟根中有效成分乙素和丙素的结构研究

本文主要报道从月腺大戟(Euphorbia ebracteolata Hayata)根中分离出的对结核菌有抑制作用的晶Ⅵ(乙素)和晶Ⅶ(丙素)的化学结构。经化学反应及光谱鉴定,确定晶Ⅵ为2,4-二羟基-6-甲氧基-3-甲基-苯乙酮,晶Ⅶ为2-羟基-6-甲氧基-3-甲基-1-苯乙酮-4-6-葡萄糖甙。乙素为首次分离的天然产物,丙素为新的化合物。该植物提取物对结核病有明显疗效。     

西伯利亚百合花挥发油化学成分的研究

采用水蒸汽蒸馏法提取,运用毛细管气相色谱-质谱联用法结合计算机检索对西伯利亚百合花挥发性化学成分进行分析和鉴定,经毛细管色谱分离出49个峰,共确认了其中47种化合物,所鉴定化合物的含量占全油的99．89％。用气相色谱面积归一化法测定了各组分的相对百分含量,其化学成分主要为：( ／-)-1-甲基-4-(1-甲基乙烯)-环己烯(66．00％);3,7-二甲基-1,6-辛二烯-3-醇(19．37％);4-甲基-l-(1-甲基乙基)-3-环己烯-1-醇(3．33％);1-甲基-4-(1-甲基乙基)-1,4-环己二烯(2．72％);2-氨基苯甲酸-3,7-二甲基-1,6-辛二烯-3-酯(1．76％)。以上5种化合物占总挥发油的93．18％。     

灵芝—共生真菌的发酵液化学成分研究

从灵芝一共生真菌(Calcarisporium arbuscula Preuss)的发酵液中分离得到7个化合物,经波谱分析确定其结构分别为zythiostromic acid A(1),zythiostromolide(2),7,8-二甲基苯并[g]蝶啶-2,4(1H,3H)-二酮(7,8-dimethylbenzo[g]pteridine-2,4(1H,3H)-dione,3),麦角甾醇(ergosterol,4),琥珀酸(butane-dioic acid,5),狼毒甲素(5,5'-[oxybis(methylene)]bis-2-furancarboxaldehyde,6),5-羟甲基糠醛(5-hydrox-ylmethyl-2-furancarboxaldehyde,7).1,2,3首次从齿梗孢属真菌中分离得到.     

巴巴拉百合花的天然香气成分研究

采用水蒸气蒸馏法对巴巴拉百合花挥发油进行了提取．通过毛细管气相色谱-质谱联用法分离并鉴定了其化学成分．并用气相色谱面积归一化法测定了各成分的相对百分含量。共分离出62个峰,确定了其中60种化合物,所鉴定化合物的含量占全油的99．71％．主要化学成分为：萜二烯(59．43％);3,7-二甲基-1．6-辛二烯-3-醇(20．10％);(R)-4-甲基-1-(1-甲基乙基)-3-环己烯1醇(11．32％);3异丙烯基-5,5-二甲基环已烯(4．05％);2-氨基苯甲酸-3,7-二甲基-1,6-辛二烯-3-酯(3．52％);( )-α-萜品醇(p-薄荷-1-酮-8-醇)(2．22%);β-月桂烯(1．08％)。以上7种化合物占总挥发油的94．72％。     

竹叶兰化学成分的研究

从竹叶兰(Arundina graminifolia) 90%乙醇提取物中利用MCI、硅胶、大孔树脂通过柱色谱技术分离得到8个化合物,经波谱分析鉴定为4-(4-羟苄基)-3,4,5-三甲氧基环己-2,5-二烯酮(1)、apigenin 6,8-di-C-β-glucopyranoside (vicenin-2,2)、7-羟基-2,4-二甲氧基-9,10-二氢菲(orchinol,3)、7-羟基-2-甲氧基菲-1,4-二酮(densiflorol B,4)、1-(4-羟基-3,5-二甲氧基苯基)丙烷-1-酮(5)、正二十四饱和脂肪酸甘油酯-1(6)、β-谷甾醇(7)、胡萝卜苷(8),化合物1为新化合物,化合物2、5和6为首次从该植物中得到.     

柳叶白前化学成分研究

从柳叶白前根和茎中分离并鉴定了7个化合物,分别为β-谷甾醇（β-sitosterol,1）,2,4-二羟基苯乙酮（1-（2,4-dihydroxphenyl）ethanone,2）,间二苯酚（resorcinol,3）,4-羟基-3-甲氧基苯乙酮（1-（4-hydroxy-3-methoxyphenyl）e-hanone,4）,4-羟基苯乙酮（1-（4-hydroxyphenyl）ethanone,5）,齐墩果酸（oleanolic acid,6）,蔗糖（sucrose,7）。其中化合物2-7为首次从该植物中分得。     

岗松化学成分的研究

从岗松的石油醚和氯仿提取组分中分离得到7个化合物,根据NMR、HSQC、HMBC、IR和MS的数据分析及与文献对照,确定它们的结构为白桦脂酸(betulinic acid,1),齐墩果酸(oleanolic acid,2),没食子酸乙酯(ethyl sabre,3),5-羟基-6-甲基-7-甲氧基-二氢黄酮(5-hydroxy-6-methyl-7-methoxy-flavanone,4),5-羟基-7-甲氧基-8-甲基二氢黄酮(5-hydroxy-7-methoxy-8-methylflavanone,5),5-羟基-7-甲氧基-2-异丙基色原酮(5-hydroxy-7-methoxy-2-isopropylchromone,6)和β-谷甾醇(β-sitosterol,7).其中,化合物1～5和7为首次从该植物中分离得到.     

元宝草中一个新的二苯甲酮

为了研究元宝草(Hypericum sampsonii Hance)全草的化学成分,利用硅胶柱层析、Sephadex LH-20等色谱技术对元宝草三氯甲烷部位进行分离和纯化,共得到6个化合物,通过1H NMR、13C NMR、HMQC、HMBC等波谱技术分别鉴定为2,6-二羟基-4,3’,5’-三甲氧基二苯甲酮(1)、1,3,6-三羟基-2-甲基蒽醌(2)、山奈酚(3)、木犀草素(4)、3,4-二羟基苯甲酸乙酯(5)、β-谷甾醇(6),其中化合物1为新化合物,化合物2和5首次从该植物中分离得到。     

青蕨化学成分的研究

从青蕨的乙酸乙酯提取物中分离得到6个化合物,通过化学方法及波谱分析,分别将其结构鉴定为木香素Ⅲ(1),7-甲氧基鬼灯擎素(2),扶桑甾醇(3),5-(3′-甲基丁基)-8-甲氧基呋喃香豆素(4),2-(3′-羟基-3′-甲基)丁基-4-羟基-5-甲氧基苯酚-1-O-β-D匍吡喃糖苷(青蕨素Ⅰ)(5)和2-(3′-羟基-3′-甲基)丁基-4-羟基-3,6-二甲氧基苯酚-1-O-β-D-匍吡喃糖苷(青蕨素Ⅱ)(6)。化合物5和6为新化合物,化合物1,2,3和4为首次从该植物中分离得到。     

Evaluation of hepatic cytochrome P4502E1 in the species-dependent bioactivation of 4-vinylcyclohexene

4-Vinyl-1-cyclohexene (VCH), is converted by multiple forms of cytochrome P450 (CYP) to two monoepoxides (4-vinyl-1-cyclohexene 1,2-epoxide [VCH-1,2-epoxide], 4-vinyl-1-cyclohexene 7,8-epoxide [VCH-7,8-epoxide]), and 4-vinyl-1-cyclohexene diepoxide (VCD). A greater degree of formation of these epoxides by female B6C3F1 mice as compared to Fischer 344 rats correlates with the ovarian toxicity observed only in the mice. Understanding which isoforms of CYP are involved in VCH bioactivation will better explain the species-dependent ovotoxicity of VCH. Present studies focus on the role of CYP2E1, as this isoform is responsible for the bioactivation of several structurally related small molecular weight compounds, including 1,3-butadiene. Hepatic microsomes prepared from either mice or rats pretreated with the CYP inducer acetone demonstrated 2-fold increases in the formation of VCH-1,2-epoxide. However, incubations with microsomes from cyp2e1-deficient mice compared to those from wild type mice revealed no differences in the rates of bioactivation of VCH to the monoepoxides. Since repeated exposure to VCH is required for VCH-induced ovotoxicity, rodents were dosed with VCH for 5 or 10 d to observe effects on the hepatic concentration of CYP2E1 and/or associated activities. VCH pretreatment failed to increase the concentration of CYP2E1 or CYP2E1 activity in either species, as measured by immunoblotting analysis and p-nitrophenol hydroxylation. Based on these data, it is concluded that CYP2E1 does not play a role in the species differences between mice and rats in the bioactivation of VCH following repeated exposure to VCH. Other isoforms, such as those in CYP2A and CYP2B subfamilies, are likely involved in VCH bioactivation.     

藏药毛蕊杜鹃挥发油化学成分的GC-MS分析

目的：通过研究毛蕊杜鹃挥发油的化学成分,为毛蕊杜鹃的药用及开发利用提供依据.方法：采用水蒸气蒸馏法提取毛蕊杜鹃挥发油,用GC毛细管柱进行分离,归一化法测其相对含量,并用气相色谱-质谱法对化学成分进行鉴定.结果：共鉴定出38个化合物,鉴定出的化合物含量占总挥发油的92.96％.结论：毛蕊杜鹃挥发油主要成分为δ-杜松烯（相对含量为15.90％）;胡萝卜醇（15.09％）;α-杜松醇（15.02％）;τ-杜松醇（9.66％）;α-衣兰油烯（4.25％）;1,2,3,4,4a,5,6,8a-八氢-7-甲基-4-亚甲基-1-[1-甲基乙基]-萘（4.14％）;1,7-二甲基-4-异丙基-2,7-环癸二烯-1-羟基（3.27％）;石竹烯（2.86％）;5-甲基-9-亚甲基-2-异丙基-二环[4.4.0]癸-1-烯（2.62％）;1,4-二甲基-3-[2-甲基-1-丙烯-1-基]-4-乙烯基-1-环庚烯（2.42％）;γ-衣兰油烯（2.21％）;愈创醇（1.50％）;β-古芸烯（1.34％）.     

Phenolic derivatives from Wigandia urens with weak activity against the chemokine receptor CCR5

Three compounds, 2,3-dihydroxy-4-methoxy-6,6,9-trimethyl-6H-dibenzo[b,d]pyran (1), 8-methoxy-2-methyl-2-(4-methyl-3-pentenyl)-2H-1-benzopyran-6-ol (2) and 4-methoxy-3-(3-methyl-2-butenyl)-benzoic acid (3), have been isolated from Wigandia urens. The structures of compounds 1, 2 and 3 were determined from spectroscopic data and showed activity in a CCR5 assay with IC(50) values of 33, 46 and 26 muM respectively.     

四种植物精油对黑翅土白蚁触杀和驱避作用

为筛选出高效防治黑翅土白蚁的天然植物精油,减少有机合成农药的使用,该文研究了大蒜精油、肉桂油、丁香油和印楝素油四种植物精油对黑翅土白蚁的触杀效果和驱避作用。结果表明:大蒜精油、肉桂油和丁香油的浓度为5和10 mg·m L~(-1)时,处理2 h后,黑翅土白蚁的校正死亡率达100%,而相同浓度的印楝素油和对照处理的黑翅土白蚁校正死亡率低于5%。随着处理时间延长,浓度为1.25和2.5 mg·m L~(-1)的大蒜精油、肉桂油和丁香油处理6 h时,黑翅土白蚁的校正死亡率仍达100%,而此时对应的印楝素油和对照处理的黑翅土白蚁校正死亡率仅为10%,说明大蒜精油、肉桂油和丁香油对黑翅土白蚁具有较强的触杀效果。大蒜精油、丁香油和肉桂油在处理黑翅土白蚁2 h后LC_(50)值(半致死量)分别为1.572、1.05和1.03mg·m L~(-1),说明肉桂油对黑翅土白蚁的毒性相对最大,触杀效果最好。此外,10 mg·m L~(-1)的大蒜精油、肉桂油、丁香油和印楝素油的驱避试验表明,处理4、6、8和12 h后,大蒜精油、肉桂油和丁香油三精油处理区的黑翅土白蚁数均显著低于对照区的,驱避率总体93%,而对应的印楝素油的驱避率总体28.5%,表明大蒜精油、丁香油和肉桂油三种植物精油对黑翅土白蚁均有显著的驱避活性。综上可知,四种植物精油中大蒜精油、肉桂油和丁香油在防治黑翅土白蚁方面应用潜力很好,是开发绿色环保白蚁防治药剂的可选材料。     

Inhibitory effect of the compounds from the water extract of Curcuma longa on the production of PGE2 and NO in a macrophage cell line stimulated by LPS

ABSTRACT

We wished to search for the compounds contributing to the anti-inflammatory effects of the water extract of Curcuma longa (WEC). WEC was fractioned and the fractions were evaluated with regard to their inhibitory effect on the production of nitric oxide (NO) from the macrophage cell line stimulated by lipopolysaccharide. Compounds in the active fractions were isolated and identified. One isolated compound was identified as new: (6S)-2-methyl-5-hydroxy-6-(3-hydroxy-4-methylphenyl)-2-heptene-4-one (1). Four isolated compounds were identified as known: (6S)-2-methyl-6-(4-hydroxyphenyl)-2-heptene-4-one (4), bisabolone-4-one (5), curcumenone (6), and turmeronol A (8). Three isolated compounds were not identified their stereostructures but their planar structures: 2-methyl-6-(4-hydroxymethyl-phenyl)-2-heptene-4-one (2), 2-methyl-6-(2,3-epoxy-4-methyl-4-cyclohexene)-2-heptene (3), and 4-methylene-5-hydroxybisabola-2,10-diene-9-one (7). Compounds 1, 4, 7 and 8 inhibited production of prostaglandin E2 and NO. Others inhibited NO production only. These results (at least in part) show the active compounds contributing to the anti-inflammatory effects of WEC, and may be useful for elucidating its various beneficial physiologic effects.     

Benzofuranoid neolignans from Aniba simulans

Forteen neolignans, isolated from the benzene extract of Aniba simulans (Lauraceae) trunk wood, included the hitherto undescribed (2S, 3S, 5R)-5-allyl-5,7-dimethoxy-2-(3′,4′,5′-trimethoxyphenyl)-3-methyl-2,3,5,6-tetra-hydro-6-oxobenzofuran, (2R,3S,5R) -5-allyl-5-methoxy-2-(3′-methoxy-4′,5′-methylenedioxyphenyl)-3-methy1-2,3,5, 6-tetrahydro-6-oxobenzofuran, (2S,3S)-6-O-allyl -5-methoxy-2-(3′-methoxy-4′-5′-methylenedioxyphenyl)-3-methyl-2,3-dihydrobenzofuran, (2R,3S)-6-O-allyl-5-methoxy-2- (3′-methoxy-4′,5′-methylenedioxyphenyl)-3-methyl-2,3-dihydrobenzofuran and 7-allyl-6-hydroxy-5-methoxy-2-(3′-methoxy-4,5′ -methylenedioxyphenyl)-3-methylbenzofuran.     

Oxidative degradation of bilirubin produces vasoactive compounds.

Subarachnoid haemorrhage is often followed by haemolysis and concomitant oxidative stress, and is frequently complicated by pathological vasoconstriction or cerebral vasospasm. It is known that upregulation of haem oxygenase (HO-1) is induced by oxidative stress and results in release of biliverdin and bilirubin (BR), which are scavengers of reactive oxygen species (ROS). Here we report biomimetic studies aimed at modelling pathological conditions leading to oxidative degradation of BR. Oxidative degradation products of BR, formed by reaction with hydrogen peroxide (an ROS model system), demonstrated biological activity by stimulating oxygen consumption and force development in vascular smooth muscle from porcine carotid artery. Analogous biological activity was observed with vasoactive cerebrospinal fluid from subarachnoid haemorrhage patients. Three degradation products of BR were isolated: two were assigned as isomeric monopyrrole (C9H11N2O2) derivatives, 4-methyl-5-oxo-3-vinyl-(1, 5-dihydropyrrol-2-ylidene)acetamide and 3-methyl-5-oxo-4-vinyl-(1, 5-dihydropyrrol-2-ylidene)acetamide and the third was 4-methyl-3-vinylmaleimide (MVM), a previously isolated photodegradation product of biliverdin. Possible mechanisms of oxidative degradation of BR are discussed. Tentative assignment of these structures in the cerebrospinal fluid (CSF) of cerebral vasospasm patients has been made. It is proposed that one or more of the degradation products of biliverdin or bilirubin are involved in complications such as vasospasm and or pathological vasoconstriction associated with haemorrhage.     

First generation 5-vinyl-3-pyridinecarbonitrile PKCθ inhibitors

A series of 5-vinyl-3-pyridinecarbonitriles were synthesized and evaluated as PKCθ inhibitors. The systematic optimization of 4-[(4-methyl-1H-indol-5-yl)amino]-5-[(E)-2-phenylvinyl]-3-pyridinecarbonitrile 3 resulted in the identification of compound 23e as a potent PKCθ inhibitor with good selectivity over PKCδ.     

Neurotoxicity studies with the monoamine oxidase B substrate 1-methyl-3-phenyl-3-pyrroline

The neurotoxic properties of the parkinsonian inducing agent 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) are dependent on its metabolic activation in a reaction catalyzed by centrally located monoamine oxidase B (MAO-B). This reaction ultimately leads to the permanently charged 1-methyl-4-phenylpyridinium species MPP(+), a 4-electron oxidation product of MPTP and a potent mitochondrial toxin. The corresponding 5-membered analogue, 1-methyl-3-phenyl-3-pyrroline, is also a selective MAO-B substrate. Unlike MPTP, the MAO-B-catalyzed oxidation of 1-methyl-3-phenyl-3-pyrroline is a 2-electron process that leads to the neutral 1-methyl-3-phenylpyrrole. MPP(+) is thought to exert its toxic effects only after accumulating in the mitochondria, a process driven by the transmembrane electrochemical gradient. Since this energy-dependent accumulation of MPP(+) relies upon its permanent charge, 1-methyl-3-phenyl-3-pyrrolines and their pyrrolyl oxidation products should not be neurotoxic. We have tested this hypothesis by examining the neurotoxic potential of 1-methyl-3-phenyl-3-pyrroline and 1-methyl-3-(4-chlorophenyl)-3-pyrroline in the C57BL/6 mouse model. These pyrrolines did not deplete striatal dopamine while analogous treatment with MPTP resulted in 65-73% depletion. Kinetic studies revealed that both 1-methyl-3-phenyl-3-pyrroline and its pyrrolyl oxidation product were present in the brain in relatively high concentrations. Unlike MPP(+), however, 1-methyl-3-phenylpyrrole was cleared from the brain quickly. These results suggest that the brain MAO-B-catalyzed oxidation of xenobiotic amines is not, in itself, sufficient to account for the neurodegenerative properties of a compound like MPTP. The rapid clearance of 1-methyl-3-phenylpyrroles from the brain may contribute to their lack of neurotoxicity.     

除臭大蒜口服液的GC／MS分析

应用GC/MS联用技术,对除臭大蒜口服液进行了检测,定性鉴定了25种含硫有机化合物。二烯丙基硫醚、甲基烯丙基三硫醚、3-乙烯基-1,2-二硫杂-5-环己烯、2-乙烯基-1,3-二硫杂-5-环己烯和二烯丙基三硫醚是主要组分;二烯丙基四硫醚、烯丙基四硫化氢、2-和3-(2’,3’-二硫杂-5’-己烯基)-3,4-二氢-2H-噻喃、2-(2’-[3’,4’-二氢-2H噻喃基])-1,3-二硫杂-5-环己烯和3-(2’-[3’,4’-二氢-2H-噻喃基])-1,2-二硫杂-5-环己烯是次要组分。最后4种次要组分在大蒜油和大蒜口服液中的鉴定在国内尚属首次。