Gypsins A-D from Gypsophila arabica

Four new cyclopeptides, named gypsins A-D (1- 4), together with one known oleanane saponin, were isolated from the roots of Gypsophila arabica. The structures of cyclo(-Leu(1)-Pro(2)-Leu(3)-Trp(4)-Pro(5)-Gly(6)-) (1), cyclo(-Leu(1)-Pro(2)-Tyr(3)-Phe(4)-Pro(5)-Gly(6)-) (2), cyclo(-Ala(1)-Pro(2)-Tyr(3)-Leu(4)-Leu(5)-Pro (6)-Pro(7)-Ala(8)-) (3), and cyclo(-Leu(1)-Trp(2)-Pro(3)-Gly(4)-Gly(5)-Ser(6)-Ser(7)-) (4) were elucidated by 1D and 2D NMR spectroscopy including 1D-TOCSY, DQF-COSY, 2D-ROESY, HSQC, and HMBC experiments, as well as ESI tandem mass spectrometric fragmentation analysis and chemical evidence.     

Crotogossamide, a cyclic nonapeptide from the latex of Croton gossypifolius

A new cyclic nonapeptide, crotogossamide (1), was isolated from the latex of Croton gossypifolius. Its structure was elucidated by use of 1D and 2D NMR and MS and by hydrolysis followed by GC-MS analysis as cyclo(-Gly(1)-Ala(2)-Ser(3)-Gly(4)-Leu(5)-Asn(6)-Gly(7)-Ile(8)-Phe(9)-). This is the first report of a cyclic peptide from a Croton species. The known flavonoids kaempferol 3-O-rhamnopyranoside, quercitrin, and myricitrin were also isolated from the plant latex.     

Bioactive compounds from the aerial parts of Brachystemma calycinum and structural revision of an octacyclopeptide

Four new cyclic peptides, brachystemins F-I (1-4), and 11 known compounds were isolated from the aerial parts of Brachystemma calycinum. The absolute configurations of compounds 1-4 were assigned using Marfey's method. The structure of compound 5 was revised from cyclo(Pro1-Phe2-Leu3-Ala?-Thr?-Pro?-Ala?-Gly?) to cyclo(Pro1-Pro2-Ala3-Gly?-Leu?-Ala?-Thr?-Phe?) with QTOF/MS and X-ray diffraction analysis. The N-containing compounds were assessed for their inhibitory effects on the secretion of monocyte chemokine ligand 2 (CCL-2), interleukin 6 (IL-6), and collagen IV against high-glucose-stimulated mesangial cells. Compound 5 was evaluated for its effects on collagen I, reactive oxygen species (ROS), superoxide anion (O?(??)) production, and cell viability in mesangial cells, and on nitric oxide (NO) production in macrophage cells.     

dd-diketopiperazines: antibiotics active against Vibrio anguillarum isolated from marine bacteria associated with cultures of Pecten maximus

Bacterial strains CF-20 (CECT5719) and C-148 (CECT5718), isolated from cultures of larvae of molluscs, are shown to produce substances 1-5 with strong antibiotic activity against Vibrio anguillarum (MIC: 0.03-0.07 mug/mL) and identified as the dd-diketopiperazines cyclo(d)-Pro-(d)-Phe (1), cyclo(d)-Pro-(d)-Leu (2), cyclo(d)-Pro-(d)-Val (3), cyclo(d)-Pro-(d)-Ile (4), and cyclo-trans-4-OH-(d)-Pro-(d)-Phe (5). Comparison with other stereoisomers indicates that inhibition of V. anguillarum is associated with the presence of at least one d-amino acid in the diketopiperazine system. This is the first time a series of dd-diketopiperazines has been isolated from a single natural source and their inhibitory activity against V. anguillarum described.     

白僵蚕化学成分研究

目的研究白僵蚕Bombyx Batryticatus的化学成分。方法利用正相硅胶柱色谱、Sephadex LH20、反相硅胶柱色谱及反相制备液相色谱等手段进行分离纯化,并通过1H-、13C-NMR等波谱技术进行结构鉴定。结果从白僵蚕醋酸乙酯层中分离得到11个化合物,分别鉴定为环(D-脯-D-缬)二肽(1)、环(S-脯-R-亮)二肽(2)、环(D-脯-D-异亮)二肽(3)、环(D-脯-D-苯丙)二肽(4)、金色酰胺醇酯(5)、(+)-松脂醇(6)、异黑麦草内酯(7)、butyl-2-pyrrolidone-5-carboxylate(8)、(-)-杜仲树脂酚(9)、(-)-落叶松树脂醇(10)、4-羟基苯乙酸甲酯(11)。结论所有化合物均为首次从僵蚕中分离得到。     

金铁锁根中的3个环二肽

目的 :对金铁锁中的环肽成分进行系列研究。方法 :利用柱层析进行化合物的分离 ,用波谱法鉴定其结构。结果 :从其丙酮溶解部分分离得到 3个环二肽 ,其结构分别为环 (脯-缬 ) (1 )、环 (脯-丙 ) (2 )和环 (脯-脯 ) (3)。结论 :化合物 1和 2为新的天然产物 ,化合物 3为首次从金铁锁中得到。     

三种红树林内生真菌的环肽类次级代谢产物的研究

从三种红树林内生真菌Paecilomyces sp.(treel-7),4557,ZZF65中分到九个环肽类的次级代谢产物,分别是viscumamide(1),cyclo(Pro-Iso)(2),cyclo(Phe-Gly)(3),cyclo(Phe-Ana)(4),cyclo(Gly-Pro)(5),cyclo(Gly-Leu)(6),cyclo(Trp-Ana)(7),neoechinulin A(8),cyclo(Pro-Thr)(9)。其中化合物1,7,8,9是首次从海洋真菌中分离得到。     

Glaciapyrroles A, B, and C, pyrrolosesquiterpenes from a Streptomyces sp. isolated from an Alaskan marine sediment

A Streptomyces sp. (NPS008187) isolated from a marine sediment collected in Alaska was found to produce three new pyrrolosesquiterpenes, glyciapyrroles A (1), B (2), and C (3), along with the known diketopiperazines cyclo(leucyl-prolyl) (4), cyclo(isoleucyl-prolyl) (5), and cyclo(phenylalanyl-prolyl) (6). The structures of 1, 2, and 3 were established using spectroscopic methods.     

海洋放线菌Streptomyces sp.（#195-02）的代谢产物研究

从一株南海海洋链霉菌属放线菌195-02中分离得到8个化合物,利用波谱技术确定其结构分别为对羟基苯腈（1）、2-甲基-3-呋喃甲酸（2）、2-呋喃甲酸（3）、环（苯丙-苯丙）二肽（4）、环（亮-异亮）二肽（5）、烟酸（6）、吲哚-3-乙酸（7）和邻苯二甲酸二（2-乙基己基）酯（8）。化合物1、3、8为首次从链霉菌属中分离得到,化合物4～7为首次从海洋放线菌中分离得到。活性测试表明化合物4和5在浓度为50μg/ml时,对喉癌细胞hep2抑制率分别为51%和47%,对肝癌细胞hepG2抑制率分别为40%和31%。     

火木层孔菌液体培养物的化学成分研究

目的:研究针层孔属火木层孔菌Phellinus igniarius液体培养物的化学成分并对其在多种体外药理模型上进行随机活性筛选.方法:分别对发酵液及菌丝体的化学成分进行研究,采用硅胶柱色谱、Sephadex LH-20柱色谱以及反相HPLC柱色谱等分离方法进行分离纯化;运用光谱数据解析鉴定化合物结构;在细胞水平模型上,筛选化合物在肿瘤细胞毒、神经保护、肝保护、抗炎和抗HIV等方面的活性.结果:从发酵液和菌丝体2部分共分离鉴定了29个化合物,分别为3个倍半萜:3S,9R,10S-3-羟基-11,12-O-异丙基血苋烷烯(1),3S,9R,10S-3,11,12-三羟基血苋烷烯(2)和3S,4S,9R,10-11,12,14-三羟基血苋烷烯(3);3个甾体:24R-麦角甾-4,6,8(14),22-四烯-3-酮(4),豆甾-7,22-二烯-3β,5α,6α-三醇(5)和麦角甾5α,8α-过氧-6,22-二烯-3β-醇(6);14个环二肽:环(L-脯氨酸-L-缬氨酸)(7),环(L-亮氨酸-D-脯氨酸)(8),环(L-亮氨酸-L-脯氨酸)(9),环(异亮氨酸-脯氨酸)(10),环(甘氨酸-亮氨酸)(11),环(苯丙氨酸-丝氨酸)(12),环(丙氨酸-脯氨酸)(13),环(丙氨酸-苯丙氨酸)(14),环(4-羟基-脯氨酸-苯丙氨酸)(15),环(L-苯丙氨酸-D-脯氨酸)(16),环(D-苯丙氨酸-D-脯氨酸)(17),环(6-羟基-脯氨酸-苯丙氨酸)(18),环(谷氨酸氨-脯氨酸)(19)和环(天冬氨酸-亮氨酸)(20);9个其他类化合物:乙酰氨基苯丙氨酸(21)、腺苷(22)、苯乙二醇(23)、邻-羟基苯乙醇(24)、苯甲酸(25)、对-甲氧基苯甲酸(26)、间-甲氧基苯甲酸(27)、十六烷酸(28)和3-吡啶羧酸(29).化合物5和8在1×10-5mol·L-1时能够有效地抑制MPP+诱导的PC12-syn细胞损伤,相对保护率分别为90.3%和87.5%,与模型组比较有显著性差异(P<0.05).在1×10-5mol·L-1浓度下,化合物12和18可较好地保护DL-半乳糖胺诱导的WB-F344细胞损伤,细胞成活率分别为25%和24%(双环醇作为对照,细胞成活率为24%).结论:化合物1-29均为首次从针层孔属火木层孔菌液体培养物中分离鉴定;化合物5和S有神经细胞保护活性,化合物12和18具有肝细胞损伤保护活性,其他化合物在测试浓度下在以上筛选模型中未显示明确活性.     

Cyclic heptapeptides from the Jamaican sponge Stylissa caribica

Two new cyclic heptapeptides, stylisin 1(1) and stylisin 2 (2), were isolated and characterized from the Jamaican sponge Stylissa caribica, in addition to the cyclic heptapeptide phakellistatin 13 (3) and the known bromopyrrole alkaloids sceptrin (4), stevensine (5), and oroidin (6). The new structures were assigned on the basis of 1D and 2D NMR spectroscopic data, as well as chemical methods for the elucidation of the absolute configuration of amino acids. The peptides and alkaloids have been evaluated for their antimicrobial, antimalarial, anticancer, anti-HIV-1, anti-Mtb, and antiinflammatory activities.     

格木内生真菌烟曲霉的代谢产物

采用GPY培养基对格木内生真菌烟曲霉Aspergillus fumigatus菌株进行培养发酵,发酵产物经冻融处理后分离得到菌液与菌丝体.菌丝体经乙醇提取后,分别用乙酸乙酯和正丁醇萃取,根据肿瘤细胞毒活性筛选结果,选择菌体的乙酸乙酯萃取物进行化学成分研究.运用硅胶色谱柱、凝胶Sephadex LH-20柱色谱、反相柱色谱和制备HPLC等多种色谱技术,采用波谱学方法从中分离鉴定了5个二酮哌嗪化合物,其结构分别为cyclo-(R-Pro-R-Phe)(1),cyclo-( trans-4-OH-D-Pro-D-Phe)(2),cyclo-(R-Tyr-S-Ile)(3),cyclo- (R-Phe-S-Ile)(4),cyclo-(R-Val-S-Tyr) (5).     

瑞香狼毒细胞培养物的化学成分研究

采用常压与减压硅胶柱色谱、半制备HPLC、Sephadex LH-20等方法,从瑞香狼毒Stellera chamaejasme细胞培养物85％乙醇提取物的乙酸乙酯部分分离纯化得到了17个化合物,依据理化性质和各种波谱技术分别鉴定为:丁香脂素(1),杜仲树脂酚(2),松脂素(3),(1R,2S,5R,6S) -2-(4-hydroxyphenyl) -6-( 3-methoxy-4- hydroxyphenyl)-3,7-dioxabicyclo[3,3,0]octane(4),表松脂酚(5),caruilignan D(6),3-羰基愈创木烷-4-烯-11,12-二醇(7),落叶松脂素(8),tetrahydro-2-( 4-hydroxy-3-methoxyphenyl) -4-[ (4-hydroxyphenyl) methyl] -3-furanmethanol(9),5′-甲氧基落叶松脂醇(10),vladinol D( 11),环(L-脯氨酸-L-缬氨酸)(12),7′-羰基马台树脂醇(13),(+) -guayarol( 14),acutissimalignanB(15),异落叶松脂素(16)以及β-谷甾醇(17).其中化合物12为环二肽类化合物,7为倍半萜类化合物.除化合物7,12与17外,其余均为木脂素类化合物.17个化合物均首次从该植物组织培养物中获得.     

Mammea coumarins from the flowers of Mammea siamensis

Four new mammea coumarins, mammea E/BA cyclo D (1), mammea E/BC cyclo D (2), mammea E/BD cyclo D (3), and mammea E/AC cyclo D (4), were isolated from the flowers of Mammea siamensis, along with six known coumarins. Extensive 1D and 2D NMR experiments and other spectroscopic studies, as well as chemical transformations, were employed to determine the structures of 1-4.     

植物内生真菌Fusariums sp.LC-1次级代谢产物的研究

 目的 研究植物内生真菌Fusariums sp.LC-1发酵液的乙酸乙酯萃取物和菌丝体的丙酮提取物中的化学成分,以期得到有活性的先导化合物。方法 采用硅胶柱色谱、凝胶柱色谱、高效液相色谱等方法进行分离纯化,通过理化性质和波谱数据分析鉴定化合物的结构。结果 从植物内生真菌Fusariums sp.LC-1发酵液的乙酸乙酯萃取物和菌丝体的丙酮提取物中共分离得到17个化合物,分别鉴定为：环(甘-缬)二肽（1）、环(甘-异亮)二肽（2）、白僵菌素（3）、麦角甾醇（4）、3β,5α,6β,9α-tetrahydroxyergosta-7,22-diene（5）、fusaric acid（6）、dehydrofusaric acid（7）、对羟基苯甲酸（8）、环(羟脯-亮)二肽（9）、环(甘-脯)二肽（10）、环(丙-苯丙)二肽（11）、环(亮-丙)二肽（12）、环(亮-缬)二肽（13）、环(苯丙-甘)二肽（14）、环(亮-甘)二肽（15）、尿嘧啶（16）、胸腺嘧啶（17）。结论 其中,化合物1、2为首次从天然产物中分离得到,化合物5、9、12、13、14为首次从镰刀菌属中分离得到。     

冬虫夏草内生真菌Nigrospora oryzae的化学成分分离鉴定

目的:研究冬虫夏草内生菌Nigrospora oryzae的化学成分。方法:采用糙米对其进行扩大培养,利用柱色谱、制备色谱等手段进行分离纯化,并利用核磁共振(NMR),电喷雾质谱(ESI-MS)等手段对化合物进行结构鉴定。结果:分离得到15个化合物,分别为蜂蜜曲菌素(mellein,1),亚油酸(linoleic acid,2),2-(2-羟乙基)苯酚[2-(2-hydroxyethyl) phenol,3],(3R)-甲基亮氨酸甲酯[(3R)-mellein methyl ether,4],(3R,4S)-4-hydroxymellein(5),2-羟基苯甲醛(2-hydroxybenzaldehyde,6),3-苯丙-1,2-二醇(3-phenylpropane-1,2-diol,7),苯乙二醇(1-phenyl-1,2-ethanediol,8),恩镰包菌素B(enniatin B,9),(22E,24R)-麦角甾-7,22-二烯-3β,5α,9α-三醇-6-酮[(22E,24R)-ergost-7,22-dien-3β,5α,9α-riol-6-one,10],环-(S-脯氨酸-R-缬氨酸)[cyclo-(S-Pro-R-Val),11],4-hydroxy-8-O-methylmellein(12),环-(S-脯氨酸-S-苯丙氨酸)[cyclo-(S-Pro-S-Phe),13],环-(D-脯氨酸-L-异亮氨酸)[cyclo-(D-Pro-L-Ile),14],环-(D-脯氨酸-L-亮氨酸)[cyclo-(D-Pro-L-Leu),15]。结论:化合物1～15为首次从该真菌中分离得到。     

槐耳发酵液乙酸乙酯部位化学成分的研究

目的 探究槐耳Trames robiniophila Murrll.发酵液乙酸乙酯部位的化学成分.方法 槐耳发酵液乙酸乙酯部位采用硅胶、ODS、HPLC进行分离纯化,根据理化性质及波谱数据鉴定所得化合物的结构.结果 从中分离得到16个化合物,分别鉴定为尿嘧啶(1)、3,4-二羟基苯甲酸甲酯(2)、3,4-二羟基苯甲酸(...     

Serinocyclins A and B, cyclic heptapeptides from Metarhizium anisopliae

Two new cyclic heptapeptides, serinocyclins A (1) and B (2), were isolated from conidia of the entomopathogenic fungus Metarhizium anisopliae. Structures were elucidated by a combination of mass spectrometric, NMR, and X-ray diffraction techniques. Serinocyclin A (1) contains three serine units, a hydroxyproline (Hyp), a beta-alanine (beta-Ala), and two uncommon nonproteinogenic amino acids, 1-aminocyclopropane-1-carboxylic acid (Acc) and gamma-hydroxylysine (HyLys). The peptide sequence established for 1 by NMR is cyclo-(Acc-Hyp-Ser1-HyLys-beta-Ala-Ser2-Ser3). Serinocyclin B (2) has Lys in place of the HyLys unit found in 1. Chiral amino acid analysis indicated the presence in both compounds of one (2 S,4 R)-Hyp, two L-Ser, and one D-Ser residue. A Lys found in the hydrolyzate of 2 was established as D-configured. A crystal structure of 1 established the position of the D-Ser (Ser2) and the absolute configuration of the HyLys unit (2 R,4 S). The absence of methyl groups is unusual among fungal peptides and, along with the charged lysyl side chain and multiple hydroxyl groups, contributes to the polar nature of the compounds. Serinocyclin A produced a sublethal locomotory defect in mosquito larvae at an EC 50 of 59 ppm.     

Cycloleonuripeptides E and F, cyclic nonapeptides from Leonurus heterophyllus

Two new cyclic nonapeptides, cycloleonuripeptide E, cyclo (-Ala-Pro-Ile-Val-Ala-Ala-Phe-Thr-Pro-), and cycloleonuripeptide F, cyclo (-Gly-Tyr-Pro-Leu-Pro-Phe-Tyr-Pro-Pro-), have been isolated from the fruits of Leonurus heterophyllus, and their structures were elucidated by 2D NMR analysis and chemical degradation. Cycloleonuripeptides E (1) and F (2) showed moderate vasorelaxant effects on rat aorta.     

知母中的生物碱

目的:研究知母中的生物碱成分.方法:Sephdex LH-20,Rp-18及硅胶色谱柱分离纯化,根据理化性质和光谱数据鉴定结构.结果:分离鉴定了6个生物碱,分别为aurantiamide acetate(1)、环(酪-亮)二肽(2)、香豆酰基酪胺(3)、N-反式阿魏酰基酪胺(4)、N-顺式阿魏酰基酪胺(5)、烟酸(6).结论:化合物1～5为首次从百合科植物中分离得到,化合物1～6为首次从知母中分离得到.