胆木枝叶中一个新的吲哚生物碱类化合物

综合运用多种现代色谱学分离方法对黎药胆木中的化学成分进行了研究,从其枝叶的乙醇提取物中分离得到了4个吲哚生物碱类化合物,采用多种现代波谱技术确定了这些化合物的化学结构,分别鉴定为:nauclofficine(1)、naucleamide A(2)、naucleamide D(3)和latifoliamide A(4).其中化合物1为一个新生物碱,化合物2~4为首次从胆木中分离得到的化合物.化合物1~4的体外细胞毒活性评价结果表明,它们对5种肿瘤细胞株(HL-60、A549、SMMC-7721、MCF-7和SW480)均显示出了较为显著的体外生长抑制活性,细胞毒活性与抗肿瘤阳性对照药顺铂的活性相当.     

毛叶鹰爪花中一个新颖的裂环多氧取代环己烯类化合物

综合运用多种现代色谱学分离方法对毛叶鹰爪花中的化学成分进行了研究,从其枝叶的乙醇提取物中分离得到了3个裂环多氧取代环己烯类化合物,采用多种现代波谱技术确定了这些化合物的化学结构,分别鉴定为artapilosol A(1),microcarpin A(2)和uvarisubol B(3).其中化合物1为一个新化合物,化合物2和3为首次从鹰爪花属植物中分离得到的化合物.化合物1~3的体外细胞毒活性筛选结果表明它们对5种肿瘤细胞株(HL-60,A549,SMMC-7721,MCF-7和SW480)均显示出了较强的体外生长抑制活性,它们的细胞毒活性与抗肿瘤阳性对照药顺铂相当.     

内生真菌叶下珠生拟茎点霉的次级代谢产物研究（英文）

从广藿香内生真菌叶下珠生拟茎点霉(PhomopsisphyllanthicolaA658)中分离纯化得到6个聚酮类化合物,分别鉴定为dothioreloneO(1),2-[3,5-二羟基-2-(7-羟基辛酰基)苯基]乙酸(2),dothioreloneM(3),dothioreloneK(4),cytosporoneB(5),和cytosporoneC(6).其中化合物1为新化合物,化合物2为新天然产物,新化合物的结构进一步通过HR-ESIMS,1DNMR和2DNMR等光谱技术确定.此外,对分离所得的化合物进行了体外细胞毒测试,结果表明化合物3～5显示出不同程度的细胞毒活性.     

海洋异壁放线菌WH1-2216-6产生的多环含特特拉姆酸大环内酰胺

采用紫外跟踪分离和波谱鉴定的方法,从海洋异壁放线菌(Actinoalloteichus cyanogriseus WH1-2216-6)的发酵产物中分离鉴定了6个5,5,6-多环含特特拉姆酸大环内酰胺(PTMs)类天然产物:16-hydroxymaltophilin(1)、dihydromaltophilin(2)、4-deoxydihydromaltophilin(3)、maltophilin(4)、xanthobaccin C(5)和FI-2(6),其中1为新化合物.评价了化合物1~5对人正常肝细胞L-02及人癌细胞A549、MCF-7、Jurkat、BXPC-3、HCT-116、PANC-1和K562的细胞毒活性,结果表明:化合物1~5对上述人癌细胞具有细胞毒活性,其半数抑制浓度(IC50)为0.1~9.7μmol·L-1;新化合物1对L-02的毒性较低,但对Jurkat、HCT-116和BXPC-3的选择指数(SI)分别高达31.5、41.1和52.4.除化合物2和3对A549和MCF-7的肿瘤细胞毒活性外,其余的肿瘤细胞毒活性是首次报道.还测试了化合物1~6的抗烟曲霉活性,发现化合物2和4的活性较好,其最小抑菌浓度(MIC)分别为3.04和6.12μmol·L-1,这是首次发现5,5,6-PTMs类化合物具有抗烟曲霉活性.     

新的19-降海绵烷二萜的分离及结构确定

从海洋海绵Spongiazimoccaaubspeclesirregularia中分离到一种新的19-降海绵烷二萜(ZimoclactoneA,1)和胆甾-5,7-二烯-3β-醇,化合物1的化学结构和立体化学通过波谱方法和X射线单晶衍射分析确定,化合物1对P388肿瘤细胞具有中等程度的细胞毒活性.     

见血封喉乳汁中的化学成分研究

从海南产见血封喉[Antiaris toxicaria(Pers.)Lesch.]乳汁的乙醇提取物中分离得到6个化合物,经现代波谱技术,包括红外、一维、二维核磁共振谱和高分辨质谱,上述化合物的结构分别鉴定为:toxicarioside Ⅰ(1),毒毛旋花子苷元(2),杠柳苷元(3),(3β,5a,14P,17a)-3,14-二羟基孕甾-20-酮(4),α-生育酚(5)和3,4,5-三甲氧基苯酚(6),其中化合物1为新的强心苷,化合物4和5为首次从该植物中分离得到.经MTT法进行体外细胞毒活性测试,结果表明化合物1～3对慢性髓原白血病细胞(K562)、人胃癌细胞(SGC-7901)和人肝癌细胞(SMMC-7721)的增殖显示了抑制活性,其ICso值范围为0.001～12.3 μm01.L-1.     

异叶三宝木枝叶中一个新的Stemodane型二萜类化合物

综合运用硅胶柱色谱、反相硅胶柱色谱、Sephadex LH-20凝胶柱色谱以及制备型高效液相色谱等色谱分离技术对大戟科三宝木属植物异叶三宝木Trigonostemon heterophyllus枝叶中的化学成分进行了系统研究,从其枝叶的85%乙醇提取物中分离得到了8个二萜类化合物.采用多种波谱鉴定技术确定了这些化合物的化学结构.其中一个化合物为新的罕见的stemodane型二萜类化合物,七个化合物为首次从三宝木属植物中分离得到的化合物.所有化合物的体外细胞毒活性评价结果表明,它们对五种肿瘤细胞株(HL-60、A549、SMMC-7721、MCF-7和SW480)均显示出了较为显著的体外生长抑制活性,它们的细胞毒活性与抗肿瘤阳性对照药顺铂的活性相当.     

海洋珊瑚中抗肿瘤活性物质及其提取、分离方法

珊瑚主要生长在热带、亚热带海洋中，资源非常丰富且具有显著的生物多样性。研究表明，海洋珊瑚中含有许多结构多样、生理活性独特的次生代谢产物。本文概要地介绍了从珊瑚中发现的具有抗肿瘤活性的各种萜类和甾类化合物的来源、结构、抗肿瘤活性和提取、分离方法，同时展望了海洋药物的研究与开发前景。     

海洋放线菌Streptomyces sp. 124092中的细胞毒活性成分

对海洋放线菌Streptomyces sp.发酵液的提取物进行柱层析分离, 得到5个化合物. 经MS, NMR, 1H-1H COSY, HSQC和HMBC等数据鉴定, 其结构分别为3-氨基-丙酸对甲苯酯(1)、6-Amino-3-(4-hydroxybenzyl)-1,4-diazonane-2,5-dione(2)、正丁基-α-D-吡喃甘露糖苷(3)、大豆苷元(4)和1H-3-吲哚甲酸(5). 其中化合物1和2为新化合物, 细胞毒活性测试结果表明, 化合物1~4对人肝癌细胞(SMMC-7721)具有不同程度的生长抑制活性.     

毛姜花中的细胞毒活性二萜成分

从毛姜花(Hedychium villosum Wall.)中分离得到1个新二萜(1)和1个已知二萜(3). 新二萜命名为Villosumcoronarin, 该化合物在氯仿或甲醇溶液中发生异构化, 部分转化为其差向异构体1'; 其平面结构经质谱、红外光谱、氢谱、碳谱及无畸变极化转移增强技术(DEPT)、氢氢相关谱(¹H-¹H COSY)和异核多键相关谱(HMBC)等方法确证; 其相对构型由氢谱、ROESY及量化计算确证. 化合物3用琼斯试剂氧化后得到化合物4. 生物活性筛选结果表明, 化合物1对人白血病细胞株(HL-60)和肝癌细胞株(SMMC-7721)具有强的细胞毒活性, 其活性超过阳性对照顺铂(DDP). 化合物4对HL-60和SMMC-7721细胞具有显著的细胞毒活性.     

Separation of five diketopiperazines from the marine fungus Alternaria alternate HK‐25 by high‐speed counter‐current chromatography

High‐speed counter‐current chromatography was applied to the separation of five diketoperazines from the marine Alternaria alternate HK‐25 for the first time using one‐step elution method with a pair of two‐phase solvent systems composed of petroleum ether/ethyl acetate/methanol/water (5.5:11:5:7, v/v). Where 151.6 mg of crude sample yielded five diketoperazines, 12,13‐dihydroxy‐fumitremorgin C ( 1 ), gliotoxin ( 2 ), demethoxyfum itremorgin C ( 3 ), bisdethiobis(methylthio)gliotoxin ( 4 ), fumitremorgin C ( 5 ), and the purities of all compounds were above 94% as determined by high‐performance liquid chromatography. The structures of these compounds were identified by ¹H and ¹³C NMR spectroscopy. These results showed that high‐speed counter‐current chromatography can provide a feasible way for highly effective preparation of marine natural products, which ensured the supple of numerous samples for drug development.     

Disulphides in the volatile oil of Ferula behboudiana Rech. f. & Esfand

A study on the volatile oil of Ferula behboudiana by gas chromatography and gas chromatography-mass spectrometry showed the presence of 27 compounds. Two disulphide derivatives, 1-sec-butyl-2-[(E)-3-(methylthio) prop-1-enyl] disulphane (1) and 1-sec-butyl-2-[(Z)-3-(methylthio)prop-1-enyl] disulphane (2) (59.4%), were isolated from the oil by thin layer chromatography and their structures were elucidated by spectroscopic techniques. Glubolol (12.5%), α-pinene (8.8%), α-bisabolol (6.1%) and β-pinene (3.9%) were the other major compounds.     

Volatile sulphur compounds in wines related to yeast metabolism and nitrogen composition of grape musts

The influence of nitrogen compounds in grape musts on the content of sulphur compounds of wines was studied. Different vinifications were performed with the addition of methionine (20 mg l⁻¹) and/or cysteine (40 mg l⁻¹) to grape musts before alcoholic fermentation. Six grape musts, with different nitrogen composition, from cultivars of the ‘Vinhos Verdes’ Region, in Portugal, were used. Addition of methionine to grape musts enhanced the content of wines in 3-(methylthio)-1-propanol, acetic acid-3-(methylthio)propyl ester, 3-(methylthio)propionic acid and some unidentified sulphur compounds. Increase of cysteine concentration in musts led to the production of wines with high levels of hydrogen sulphide and cis-2-methyltetrahydro-thiophene-3-OL and also unidentified sulphur compounds; however, the content of 3-(methylthio)propionic acid in the wines decreased considerately with the addition of cysteine to grape musts. This work showed that cultivars from the Vinho Verde Region show different sulphur compound contents. Avesso wines, elaborated from grape musts with low amino acids level, presented the highest total sulphur compounds content. Wines from Azal branco and Alvarinho were characterised by high contents of 4-(methylthio)-1-butanol and 3-(methylthio)propionic acid, respectively. A high content of N-(3-(methylthio) propyl)-acetamide and dimethylsulphone characterise the Loureiro wines. In contrast, Trajadura wines, produced from a must rich in amino acids, presented a low total sulphur compounds content; however, these wines were also characterised by high concentrations of 4-(methylthio)-1-butanol, acetic acid-3-(methylthio)propyl ester and hydrogen sulphide.     

Cytotoxic compounds from the marine-derived fungus Aspergillus sp. recovered from the sediments of the Brazilian coast

A fungal strain of Aspergillus sp. (BRF 030) was isolated from the sediments collected in the northeast coast of Brazil, and the cytotoxic activity of its secondary metabolites was investigated against HCT-116 tumour cell line. The cytotoxicity-guided fractionation of the extracts from this fungus cultured in potato-dextrose-sea water for 14 days at room temperature yielded the hetero-spirocyclic γ-lactams pseurotin A (1), pseurotin D (2) and pseurotin FD-838 (7), the alkaloids fumitremorgin C (5), 12,13-dihydroxy fumitremorgin C (6), methylsulochrin (4) and bis(dethio)bis(methylthio)gliotoxin (3). Among them, fumitremorgin C (5) and 12,13-dihydroxy fumitremorgin C (6) were the most active. The cytotoxic activities of the extracts from Aspergillus sp. grown from 7 to 28 days were investigated, and they were associated with the kinetic production of the compounds. The most active extracts (14 and 21 days) were those with the highest relative concentrations of the compounds fumitremorgin C (5) and 12,13-dihydroxy fumitremorgin C (6).     

Methylthiofurane: Herstellung und Reaktionen

Preparation and Reactions of Methylthiofurans By lithiation of 3,4-dimethoxyfuran, 2-methylfuran and furan, followed by reaction with dimethyldisulfide, the methylthiofurans 2, 8 , and 10 have been prepared. Reaction of 8 with maleic anhydride has yielded 6-methyl-3-(methylthio)phthalic anhydride ( 9 ), a yellow substance with a strong greenish fluorescence, obviously formed by elimination of H₂O from an unstable cycloadduct. An analgous reaction of 2 resulted in an unexpected mixture from which the following yellow compounds were isolated: 3-hydroxy-4,5-dimethoxy-6-(methylthio)phthalic anhydride ( 3 ), 4-hydroxy-5-methoxy-3,6-bis(methylthio)phthalic anhydride ( 4 ), and bis(S-methyl) (2Z,4E,6Z)-2,3,6,7-tetramethoxy-4,5-bis(methylthio)-2,4,6-octatrienethioate ( 5 ). Compound 5 is also formed on standing of 2 at RT. Mild acid hydrolysis of 2 results in ring-opening accompanied by an intramolecular oxido-reduction to yield S-methyl(3Z)-3-methoxy-4-(methylthio)-2-oxo-3-butenethioate ( 6a ). The structures of compounds 5 and 6a have been determined by X-ray analysis.     

Synthesis,Crystal Structure and Biological Activity of 2-[(Pyridin-2-yl)methylthio]-1H-benzimidazole Derivatives

In order to discover the novel anti-tumor agents, a series of 2-[(pyridin-2-yl)methylthio]-1 H-benzimidazole derivatives were designed and synthesized, and the structures were characterized by IR, MS, and proton NMR. 2-[(3,4-Dimethoxypyridin-2-yl)methylthio]-1 Hbenzimidazole was investigated with X-ray crystallography, and the molecule is in orthorhombic system, space group P212121, with a = 9.1828(16), b = 11.625(2), c = 13.463(2) ?, Z = 4, R = 0.0231 and wR = 0.0596. The antitumor activities of target compounds were evaluated against human liver cancer cell line HepG2, and human liver normal cell line HL7702 using MTT assay. The target compounds have demonstrated weak or moderate anti-tumor activity against HepG2, while all the target compounds exhibit no cytotoxic effects on HL7702.     

Synthesis and [3+2] cycloaddition reaction of 3‐[(trimethylsilylmethylamino)(methylthio)‐methylene]heterocyclic compounds

3‐[(Trimethylsilylmethylamino)(methylthio)]methylene‐2‐coumaranone ( 4a ) and 1‐methyloxindole ( 4b ), readily prepared by reactions of the corresponding bis(methylthio)methylene heterocyclic compounds ( 2a, b ), with (trimethylsilylmethyl)amine (3), were found to be synthetic equivalents of heterocyclic alkylidene‐azomethine ylides. Reactions of 4a, b with reactive heterodipolarophiles such as aldehydes and ketones and reactive alkenes in the presence of cesium fluoride gave the 1,3‐dipolar cycloadducts, 3‐(2‐oxazoli‐dinylidene)‐oxindole and ‐coumaran‐2‐one derivatives ( 8a‐j, 9a‐h ), as well as pyrrolylidenecoumaran‐2‐one and oxindole derivatives ( 12‐15,17,18 ), via the 1,3‐elimination of (methylthio)trimethylsilane.     

Unique diketopiperazine dimers from the insect pathogenic fungus Verticillium hemipterigenum BCC 1449

[structure: see text]. Vertihemiptellides A (1) and B (2), unique diketopiperazine dimers, were isolated from the insect pathogenic fungus Verticillium hemipterigenum BCC 1449. Structures of these compounds were elucidated by NMR and mass spectral analysis, and the stereochemistry of 1 was determined by X-ray crystallography. The absolute stereochemistry of bisdethiodi(methylthio)-1-demethylhyalodendrin (3), previously isolated from the same fungus, was revised to the (3R,6R) configuration.     

Antifeedant activity of long-chain alcohols,and fungal and plant metabolites against pea aphid (Acyrthosiphon pisum) as potential biocontrol strategy

Aphids are noxious insect pests of major crops including cereals and legumes. Particularly, pea aphid (Acyrthosiphon pisum) causes significant yield and quality loses in pea. Crop protection is largely based on noxious chemical pesticides which have prompted a renewed interest in the discovery of natural products as alternatives to synthetic insecticides. In this study different classes of natural compounds were tested in dual choice bioassays to evaluate their feeding deterrence and mortality effect on pea aphid. High feeding deterrence was produced by some of the compounds, particularly1-hexadecanol, gliotoxin, cyclopaldic acid and seiridin. On the contrary, aphid mortality was low although significant for 1-heptadecanol, cytochalasin A, 1-nonadecanol and gliotoxin. Phytotoxicity assessment showed low or imperceptible plant damaged for cytochalasin A, seiridin and 1-nonadecanol. The results obtained showed the potential of seiridin to be used as an alternative to synthetic insecticides.     

2,7,12,17-四(甲硫基)-3,8,13,18-四(苯甲酰硫基)四氮杂卟啉及其Mg(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)配合物的合成与表征

硫杂酞菁、含硫取代基的四氮杂卟啉及其金属配合物由于具有优异的光、电及催化性能而日益受到重视.据此,我们以自制的1-甲硫基-2-苯甲酰硫基马来二腈(MBM)为原料,合成了2,7,12,17-四(甲硫基)-3,8,13,18-四(苯甲酸硫基)四氮杂卟啉H_2T(mbm)TAP及其Mg(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)配合物MT(mbm)TAP,经IR、UV-Vis和DTA等进行了表征.