海洋来源真菌Hypocrea virens菌丝体的化学成分研究

采用硅胶柱色谱、Sephadex LH-20凝胶柱色谱、开放ODS柱色谱以及HPLC等对海洋来源真菌Hypocreavirens的菌丝体进行化学成分分离,通过理化性质和波谱数据鉴定化合物的结构。从菌丝体的丙酮提取物中分离得到8个化合物,分别鉴定为1（10→6）Abeo-（22E,24R）-ergosta-5,7,9,22-tetraene-3α,11α-diol（Ⅰ）、24-甲烯基羊毛脂烷-8-烯-3β-醇（Ⅱ）、（22E,24R）-麦角甾-5,7,22-三烯-3β-醇（Ⅲ）、（22E,24R）-麦角甾-8,22-二烯-3β,5α,6β,7α-四醇（Ⅳ）、5α,9α-过氧-（22E,24R）-麦角甾-7,22-二烯-3β,6β-二醇（Ⅴ）、5α,8α-过氧-（22E,24R）-麦角甾-6,22-二烯-3β-醇（Ⅵ）、（22E,24R）-麦角甾-7,22-二烯-3β,5α,6β-三醇（Ⅶ）、3β,5α,9α-三羟基-（22E,24R）-麦角甾-7,22-二烯-6-酮（Ⅷ）,其中化合物Ⅰ、Ⅱ、Ⅳ、Ⅴ、Ⅷ均为首次从该属真菌中分离得到,化合物Ⅲ、Ⅵ、Ⅶ为首次从该种真菌中分离得到。     

A new ceramide from the basidiomycete Russula cyanoxantha

A new phytosphingosine-type ceramide (1) was isolated along with nine other compounds—5α,8α-epidioxy-(22E,24R)-ergosta-6,22-dien-3β-ol, 5α,8α-epidioxy-(24S)-ergosta-6-en-3β-ol, (24S)-ergosta-7-ene-3β,5α,6β-triol,(22E,24R)-ergosta-7, 22-dien-3β,5α,6β-triol, inosine, adenine, l-pyroglutamic acid, fumaric acid, and d-allitol from the ethanol and chloroform/methanol extract of the fruiting bodies of the basidiomycete Russula cyanoxanotha (Schaeff.) Fr. The structure of (1) was established as (2S,3S,4R,2′R)-2-(2′-hydroxytetracosanoylamino) octadecane-1,3,4-triol by means of spectroscopic and chemical methods.     

刺齿贯众化学成分的研究

从鳞毛蕨科植物刺齿贯众(Cyrtomium caryotideum)地上部分通过溶剂提取、硅胶柱层析、SephadexLH-20柱层析和MCI柱层析等方法分离得到4个化合物,经核磁共振氢谱、碳谱和质谱确定了它们的结构,分别为山奈酚-3-O-β-D-葡萄糖苷(1)、山奈酚-3-O-β-D-芸香糖苷(2)、大黄素(3),5α,8α-过氧-(22E,24R)-麦角甾-6,22-二烯-3β-醇(4)。化合物3和4为首次从本植物中分离得到。     

Sterols of scallop. III. Characterization of some C-24 epimeric sterols by high resolution (220 MHz) nuclear magnetic resonance spectroscopy

Alkyl sterols epimeric at C-24 isolated from the Atlantic scallop,Placopecten magellanicus, were analyzed by high resolution (220 MHz) nuclear magnetic resonance spectrometry, and their spectra compared with authentic samples. This technique was used to assign absolute stereochemistry in epimeric mixtures of 24 R and S 24-methylcholest-5-en-3β-ol, (22E)-24-methylcholesta-5,22-dien-3β-ol and 24-ethylcholest-5-en-3β-ol. It also allowed a semiquantitative estimate of the R/S isomers present in the mixture. M.S.R.L. Contribution Number 242.     

Inhibition of sterol biosynthesis in chlorella ellipsoidea by AY-99441

WhenChlorella ellipsoidea was grown in the presence of 4 ppm AY-9944, complete inhibition of Δ⁵-sterol biosynthesis was achieved. However total sterol production remained unaltered. As a result a number of sterols accumulated that appear to be intermediates in sterol biosynthesis. These sterols were described and identified as (24S)-5α-ergost-8(9)-en3β-ol, (24S)-5α-stigmast-8(9)-en-3β-ol, 4α-methyl-(24S)-5α-ergosta-8, 14-dien-3β-ol, 4α-methyl-(24S)-5α-stigmasta-8, 14-dien-3β-ol, 4α-methyl-(24S)-5α-ergost-8(9)-en-3β-ol and (24S)-4α-methyl-5α-stigmast-8(9)-en-3β-ol. The occurrence of these sterols inChlorella ellipsoidea is the first time they have been noted in biological material. The accumulation of these sterols in treated cultures indicates that AY-9944 is an extremely effective inhibitor of the Δ⁸→Δ⁷ isomerase and the Δ¹⁴ reductase of these plants. The occurrence of small amounts of other sterols in treated cultures has led to a proposed pathway for thebiosynthesis of sterols inChlorella ellipsoidea. Scientific Article No. A1775, Contribution No. 4565 of the Maryland Agricultural Experiment Station.     

Characterization and composition of sterols in the free and esterified sterol fractions ofAspergillus oryzae

Free and esterified sterol fractions were isolated fromAspergillus oryzae, and their components analyzed mainly by gas chromatography-mass spectrometry. Cholesterol, brassicasterol, episterol (5α-ergosta-7,24[28]-dien-3β-ol), 4α-methyl-5α-ergosta-8[9],24[28]-dien-3β-ol, lanosterol and 24-methylene-24-dihydrolanosterol were well characterized, whereas 5-dihydroergosterol, sitosterol and 24[28]-dehydroergosterol were tentatively characterized. The principal sterol of the free sterol fraction was brassicasterol, and that of the esterified sterol fraction was episterol. Ergosterol, which is reported to be widely distributed in the fungi kingdom, was not detected.     

龙眼核中的神经酰胺和脑苷脂的分离和鉴定

研究龙眼(Dimocarpus longan Lour.)果核的化学成分,采用硅胶柱色谱对龙眼果核石油醚提取物和体积分数95%乙醇提取物进行分离,并利用理化性质和光谱数据鉴定化合物的结构。从龙眼果核的提取物中分离得到一组混合神经酰胺(化合物1、2)和一组混合脑苷脂(化合物3～6),结构鉴定为Rel-(3S,4S,5S)-3-[(2'R)-2'-羟基二十二酰胺]-4-羟基-5-[(4″Z)-十四烷-4″-烯]-2,3,4,5-四氢呋喃(1)、Rel-(3S,4S,5S)-3-[(2'R)-2'-羟基二十四酰胺]-4-羟基-5-[(4″Z)-十四烷-4″-烯]-2,3,4,5-四氢呋喃(2)、1-O-(β-D-吡喃葡萄糖基)-(2S,3S,4R,8E)-2-(2'-羟基二十四酰胺)-8-十八烯-1,3,4-三醇(3)、1-O-(β-D-吡喃葡萄糖基)-(2S,3S,4R,8Z)-2-(2'-羟基二十四酰胺)-8-十八烯-1,3,4-三醇(4)、1-O-(β-D-吡喃葡萄糖基)-(2S,3S,4R,8E)-2-(2'-羟基二十二酰胺)-8-十八烯-1,3,4-三醇(5)、1-O-(β-D-吡喃葡萄糖基)-(2S,3S,4R,8Z)-2-(2'-羟基二十二酰胺)-8-十八烯-1,3,4-三醇(6)。     

耳叶紫菀化学成分及生物活性研究

首次对耳叶紫菀(Aster auriculatus Franch)全草的化学成分及生物活性进行研究,采用柱层析(CC)对植物中的提取物进行分离提纯,并利用现代波谱方法(1H-NMR,13C-NMR,MS等)分析鉴定,确定化合物的结构并对其生物活性进行筛选。从该植物的氯仿部分分离得到8个倍半萜类化合物,它们的结构分别鉴定为:Ilicic acid(1),(7R,10S)-selina-4,11(13)-dien-3-on-12-oic acid(2),2-oxo-isocostic acid(3),1β,5α-diangeloyloxy-eudesm-(15)-ene(4),1β,6α-dihydroxyeudesm-4(15)-ene(5),4(15)-eudesmene-1β,7α-diol(6),Furanoligularenone(7),(4αR,5S,8αR)-4α,5,6,7,8,8α-Hexahydro-8α-hydroxy-3,4α,5-trimethylnaphtho[2,3-b]furan-2(4H)-one(8)。并采用杯碟法对以上8个化合物进行生物活性筛选,通过观测各供试菌抑菌圈的半径,发现化合物2、化合物4对大肠杆菌(Escherichia coli)有较强的抑制作用,所有化合物均为首次从该植物中分离得到。     

Chiral Synthesis of (Z)-3-cis-6,7-cis-9, 10-Diepoxyhenicosenes, Sex Pheromone Components of the Satin Moth, Leucoma salicis

All four isomers of (Z)-3-cis-6,7-cis-9,10-diepoxyhenicosenes, 1-4, have been synthesized using D-xylose as the chirally pure starting material. D-Xylose was first converted to 2-deoxy-4,5-O-isopropylidene-3-t-butyldimethylsilyl-D-threopentose 11, via several steps of selective protection, dehydroxylation, and deprotection. Wittig coupling of 11 with nonyltriphenylphosphonium bromide followed by hydrogenation and acid catalyzed deprotection of hydroxyl groups yielded the chiral (2R,3R)-1,2,3-triol, 14, which was used as the precursor for the C-8 to C-21 unit of the (Z)-3-cis-6,7-cis-9,10-diepoxyhenicosenes. Selective tosylation of 14 followed by stereospecific cyclization yielded (2R,3R)-1,2-epoxytetradecan-3-ol, 16, which was then divergently converted to the t-butyldimethylsilyl ether 17 and tosylate 22, respectively. Establishment of the C-5 through C-7 unit of the target molecules was accomplished via regiospecific coupling of 17 with 1-t-butyldimethylsiloxy-2-propyne to form 18. Stepwise transformation of 18 via the formation of tosylate 19, desilylation, and stereospecific cyclization to form epoxy alcohol 20, followed by P2-Ni reduction yielded a key intermediate, allylic epoxy alcohol (Z)-2-(5S,6R)-cis-5,6-epoxyheptadecen-1-ol, 21. Similarly, the coupling of 22 with 1-t-butyldimethylsiloxy-2-propyne yielded 23, which was stereospecifically cyclized to form 24. Desilylation and P2-Ni reduction of 24 gave the antipodal intermediate, (Z)-2-(5R,6S)-cis-5,6-epoxyheptadecen-1-ol, 26. Asymmetric epoxidation of antipodes 21 and 26 with (L)- or (D)-diethyl tartrates resulted in the formation of diepoxy alcohols 27 and 29 from 21, and 33 and 31 from 26, respectively. Tosylation of these diepoxy alcohols followed by coupling with lithium dibutenyl cuprate yielded the four stereoisomers of (Z)-3-cis-6,7-cis-9,10-diepoxyhenicosenes, 1-4. Analysis of the retention characteristics of these materials revealed that one or both of the S*,R*,S*,R* stereoisomers comprise the major pheromone component(s) of Leucoma salicis.     

Dealkylation of 24-ethylsterols byTetrahymena pyriformis

WhenTetrahymena pyriformis was incubated with sitosterol ([24R]-24-ethylcholest-5-en-3β-ol]) or itstrans-Δ²²-derivative (stigmasterol), the C-24-dealkylated product, cholesta-5,7,trans-22-trien-3β-ol, was obtained in both cases. 24(S)-24-Ethylcholesta-5,7,trans-22-trien-3β-ol also was found to be a metabolite. When sitosterol was the substrate, 24(R)-24-ethylcholesta-5,7-dien-3β-ol was obtained as a third product. Identifications were made by mass spectroscopy, quantitative chromatography, labeling with¹⁴C, and by other means. The dealkylated product (cholestratrienol) represented 30% of the sterols isolable after incubation. The administration of sterols to this organism did not induce sterol biosynthesis, since 2-¹⁴C-mevalonate failed to yield radioactive sterol in the presence of added stigmasterol.     

思茅引种催吐萝芙木的化学成分研究

从加纳引种思茅的催吐萝芙木(Rauvolfia vomitoriaAfzel)根的乙醇提取物分别在pH=2和pH=9时,用氯仿萃取,从中得到了14个化合物,经波谱分析鉴定为:α-onocerin(1)、methyl 3,4,5-trimethoxycinnamate(2)、betulinic acid(3)、3β,22E,22S-stigmasta-5,22-dien-3-O-β-D-glucopyranoside(4)、loganic acid(5)、7,2′-O-diacetylloganic acid(6)、mitoridine(7)、10,11-dimethoxy-α-yohimbine(8)、isoreserpiline(9)、19-epiajmalicine(10)、10,11-dimethoxy-19-epiajmalicine(11)、reserpine(12)、poke-weed cerebroside(13)、β-sitoterol(14)。其中化合物1、2、3、4、6、13为首次从该属植物中分离得到。     

赤芝中脂溶性化合物的体外抗肿瘤活性

从赤芝中分离获得3个化合物:灵芝萜烯酮醇(Ⅰ)、麦角甾-7,22-二烯-3β-醇(Ⅱ)、过氧化麦角甾醇(Ⅲ)。化疗药物顺氯氨铂(DDP)作为阳性对照,用MTT(microculture tetrazolium)法和形态学方法评定了它们对人肝癌细胞株BEL-7402、人胃癌细胞株MGC-803的增殖抑制作用。Ⅰ、Ⅱ、Ⅲ、DDP对BEL-7402的半数抑制浓度IC50值分别为:20.15、5.05、24.35、7.67μmol/L;对MGC-803的IC50值分别为:6.32、10.09、9.88、3.52μmol/L。Ⅰ和Ⅱ分别与DDP以质量比1∶1混合处理BEL-7402细胞有正协同作用,效果明显优于单独使用DDP。化合物Ⅰ、Ⅱ、Ⅲ对HMEC人微血管内皮细胞的毒性很小,质量浓度6.25 mg/L的Ⅰ甚至能促其增殖,增长率为0.93%,Ⅱ、Ⅲ的抑制率仅为21.14%和2.86%。Ⅰ、Ⅱ、Ⅲ是极具潜力的抗肿瘤药物。     

New phospholipid fatty acids from the Caribbean spongeEctyoplasia ferox

The phospholipid fatty acids from the Caribbean spongeEctyoplasia ferox were studied. The novel fatty acids 25-methyl-5,9-heptacosadienoic (1) and 26-methyl-5,9-heptacosadienoic (2) were identified in 3.4 and 2.0% abundance, respectively, representing the longest set of Δ5,9iso andanteiso acids yet isolated from a marine sponge. The new acid 10,13-dimethyltetradecanoic (3), the unusual acid 15-methyl-11-hexadecenoic (4) and the also novel acid 9-methyl-11-hexadecenoic (5) were also identified inE. ferox. The principal sterols isolated fromE. ferox were 24-ethylcholest-5-en-3β-ol (46%) and 24(R)-methylcholesta-5,22-dien-3β-ol (14%).     

毛杜仲藤中神经酰胺类化合物的分离与结构鉴定

用硅胶,重结晶等手段进行分离纯化,根据化合物的理化性质和光谱数据鉴定结构,来研究毛杜仲藤的化学成分.结果分离得到一个神经酰胺类混合物(化合物1-4),即N-(2'-羟基二十一碳酰基)-1,3,4-三羟基-2-氨基-△8,9(E)-十八碳烯,N-(2'-羟基二十二碳酰基)-1,3,4-三羟基-2-氨基-△8,9(E)-十...     

Novel ceramides and a new glucoceramide from the roots of <Emphasis Type="Italic">Incarvillea arguta</Emphasis>

Novel ceramides, rel-(3S,4S,5S)-3-[(2R)-2-hydroxycosanoyl-hexacosanoylamino]-4-hydroxy-5-[(4Z)-tetradecane-4-ene]-2,3,4,5-tetrahydrofuran (1a-g), and a new glucoceramide, 1-O-β-d-glucopyranosyl-(2S,3S,4R,8E)-2-[(2R)-2-hydroxytetracosanoylamino]-1,3,4-octodecanetriol-8-ene (2) were isolated from the aqueous ethanolic extract of the roots of Incarvillea arguta, together with eight known compounds: β-sitosterol (3), oleanolic acid (4), ursolic acid (5), piperin (6), maslinic acid (7), β-sitosterol 6′-O-acyl-β-d-glucopyranoside (8), 8-epideoxyloganic acid (9), and plantarenaloside (10). Their structures were elucidated on the basis of spectral data including IR, MS, NMR [¹H NMR, ¹³C NMR (distortionless enhancement by polarization transfer), ¹H−¹H COSY, heteronuclear multiplequantum coherence, and heteronuclear multiple-bond coherence correlations]. The relative configurations were established by nuclear Overhauser effect spectroscopy experiments and by comparison of the NMR spectral data and coupling constants with those already reported in the literature.     

N-苄基吲哚类熊果酸衍生物的合成及抗肝癌活性

为开发高效低毒的抗肝癌天然产物衍生物,依据药物拼合原理设计并合成了一系列未见文献报道的熊果酸衍生物.将熊果酸与不同取代的N-苄基吲哚片段通过Claisen-Schmidt缩合反应得到目标化合物,其化学结构均经过核磁氢谱、核磁碳谱以及质谱的联合确证.采用噻唑蓝(MTT)法考察其体外抗肝癌活性,结果表明,2-{[1-(2-...     

酸枣粉中挥发性香气成分的提取与分析

采用同时蒸馏萃取法,对酸枣粉分别进行3、69、h的萃取,然后用气质联用仪对其挥发性成分进行分离鉴定,共鉴定出165种化合物,其中酸类33种、酯类24种、醛类20种、酮类19种、醇类22种、杂环类16种、烃类29种、酚类2种.含量较高(峰面积比大于1%)的化合物有月桂酸、棕榈酸、十四酸、正癸酸、顺式-11-十六烯酸、肉豆蔻油酸、辛酸、2-辛烯酸、壬酸、庚酸、乙酸、正己酸、糠醛、植酮、顺式-11-十四烯-1-醇等.通过考察和对比这些成分的香气特征,其中对酸枣粉香气起到关键作用的有酸类(乙酸、己酸、庚酸、辛酸、壬酸等)、酮类(1-辛烯-3-酮、1-羟基-2-丁酮、大马士酮等)、酯类(丁酸丁酯和己酸己酯)、醛类(己醛、壬醛、反-2-辛烯醛等)、酚类(丁香酚和4-乙烯基愈创木酚)、醇类(正己醇、苄醇、α-松油醇等)及杂环化合物(糠醛、5-甲基糠醛、2-乙酰基呋喃等).     

Potential allelochemicals fromPistia stratiotes L.

Among the substances isolated from ethyl ether extract ofPistia stratiotes L., linoleic acid,-linolenic acid, (12R,9Z,13E,15Z)-l2-hydroxy- 9,13,15-octadecatrienoicacid, (9S,10E,12Z,15Z)-9-hydroxy-10,12,15-octadecatrienoic acid, -asarone, and 24S-ethyl-4,22-cholestadiene-3,6-dione were found to inhibit the growth of some microalgae in solid medium. Toxicity of -asarone on the growth of sensitive algal strains in liquid medium is discussed.     

Semiochemistry of the Goldeneyed Lacewing Chrysopa oculata: Attraction of Males to a Male-Produced Pheromone

Gas chromatographic-electroantennographic detection (G3C-EAD) experiments showed that antennae of males and females of the goldeneyed lacewing, Chrysopa oculata Say (Co. = Chrysopa), consistently responded to four compounds extracted from the abdominal cuticle of males:nonanal, nonanol, nonanoic acid, and (1R*,2S*,5R*,8R*)-iridodial. These compounds were not detected from abdominal cuticle of females. Thoracic extracts of both sexes contained antennal-stimulatory 1-tridecene and EAD-inactive skatole. Chrysopa oculata adults were most sensitive to (1R,2S,5R,8R)-iridodial standard at an EAD-response threshold between 0.1 and 1 pg, which was 10-100 times lower than thresholds for nonanal and nonanoic acid, and up to 10,000 times lower than thresholds for other compounds tested. A similar EAD response pattern was also found in another Chrysopa sp. (Co. quadripunctata Burmeister). In field-trapping experiments, (1R,2S,5R,8R)-iridodial was the only male-specific compound that attracted Co. oculata males. Males also were weakly attracted to (1R,4aS,7S,7aR)-nepetalactol (an aphid sex pheromone component), probably due to the 5% (1R,2S,5R,8R)-iridodial present in the synthetic sample as an impurity. A herbivore-induced plant volatile, methyl salicylate, increased attraction of males to (1R,2S,5R,8R)-iridodial, whereas 1-tridecene was antagonistic. No females were caught in the entire study. Scanning electron micrographs revealed numerous male-specific, elliptical epidermal glands on the 3rd-8th abdominal sternites of Co. oculata, which are likely the pheromone glands. Another lacewing species, Chrysoperla rufilabris (Burmeister) (Cl. = Chrysoperla), did not produce male-specific volatiles or possess the type of gland presumed to produce pheromone in Co. oculata males, but (Z)-4-tridecene was identified as a major antennal-stimulatory compound from thoracic extracts of both sexes of Cl. rufilabris. Thus, (1R,2S,5R,8R)-iridodial (or its enantiomer) is now identified as a male-produced male aggregation pheromone for Co. oculata, the first pheromone identified for lacewings.