株特殊生境荒漠植物雾冰藜内生真菌Stagonospora sp.的次级代谢产物

本文通过对1株特殊生境荒漠植物雾冰藜内生真菌Stagonospora sp.的次级代谢产物进行研究,首次分离得到4个松萝酸结构类似物,包括1个新化合物stagonone（1）和3个已知化合物：松萝酸（2）,cercosporamide（3）和usnic acid amide（4）。通过高分辨质谱和NMR实验解析了新化合物1的平面结构,采用圆二色谱（CD）方法确定了其绝对构型;本文还报道了松萝酸（2）的单晶结构以及松萝酸（2）的CD谱,为确定该同类化合物的绝对构型提供了支持;活性试验结果证实化合物1-4具有选择性抗肿瘤细胞活性。基于化合物1-4的结构特征,推测了其可能的生物合成途径。     

地衣内生真菌 Pestalotiopsis sp.次生代谢产物

拟盘多毛孢属 Pestalotiopsis真菌由于能够产生大量结构新颖活性显著的次生代谢产物,特别是从中发现抗肿瘤药物紫杉醇,成为近年来研究的热点。本研究通过对1株地衣内生真菌 Pestalotiopsis sp.的固体培养基次生代谢产物的UPLC-Q-TOF-MS分析,发现该菌株能够产生分子量比较特殊的两个色谱峰。通过进一步的菌株大量发酵,结合硅胶柱色谱,高效液相色谱等技术跟踪分离,得到了2个单体化合物。采用核磁共振波谱技术、质谱技术等方法确定这2个单体化 合物平面结构,分别为已知torrenyanic acid衍生物（1）和新化合物pestalotiopsin（2）。比对化合物的CD谱及考虑生源关系,确定了新化合物（2）的绝对构型。化合物1和2的体外抑制人白血病细胞K562实验显示二者均具有抗肿瘤活性,IC₅₀值分别为25.2和32.1µmol/L。     

何首乌中新的二苯乙烯甙

用反相层析法从何首乌（Polygonum multiflorum Thunb.)根茎的水提物只发得2个新的二苯乙烯甙（1,2）及9个已知化合物：没食子酸（3）,2,6－二羟基－苯甲酸（4）,吲哚－3－（L－）α氨基－α－羟基－丙酸）甲酯（5）1,2－二羟基丙烷－1－（4－羟基－苯基）（6）,大黄素（7）,大黄素－8－β－D－葡萄糖甙（8）,（＋）－lyoniresinol-3α－O－β－D－葡萄糖甙（9）,2,3,4、,5－四羟基反式二苯乙烯－2－O－β－D－吡喃葡萄糖甙（10）和2,3,4',5－四羟基反式二苯乙烯－2,3,－二－O－β－D－吡喃葡萄糖甙（11）。亲化合物结构通过理化性质与波谱分析特别是2D NMR得以确定。化合物2表现出很强的DNA裂解活性,化合物1,2与10具有很强的抗脂质过氧化活性。     

一株特殊生境荒漠药用植物沙蓬内生真菌Rhinocladiella similis中苯甲酸大环内酯化合物

从一株特殊生境荒漠药用植物沙蓬的内生真菌Rhinocladiella similis中分离得到4个苯甲酸大环内酯化合物,包括2个新化合物rhinoclactones E（2）和F（1）、2个已知化合物8,9-dihyrogreensporone D（3）和8,9-dihydrogreensporone A（4）。基于高分辨质谱与核磁共振谱数据以及相关文献比对,确定了新化合物与已知化合物的结构。化合物1和2是一对立体异构体,在大环内酯环中并有一个呋喃环,这种环系统在自然界比较稀少。化合物1-4对3株肿瘤细胞株和植物病原真菌没有抑制活性。本结果进一步丰富了该真菌的化学成分研究,暗示特殊生境荒漠植物内生真菌具有产生结构新颖的次级代谢产物的潜力,是发现新活性天然产物的一个新的重要宝库;此外,根据化合物的结构特征与生物活性结果,本文还探讨了这些化合物潜在的生态学功能。     

荷叶离褶伞子实体化学成分

本文对祁连山野生荷叶离褶伞Lyophyllum decastes子实体的化学成分和生物活性进行研究。采用硅胶色谱、高效液相色谱等多种方法进行分离纯化得到8个化合物,通过MS、NMR和电子圆二色谱 （ECD）等方法确定了化学结构,其中有4个为聚炔类化合物。化合物1作为天然产物系首次报道,其相绝对构型是通过比较ECD的方法确定。对所得聚炔类化合物应用细胞模型进行抗氧化活性（CAA）指标检测,化合物1-4均呈现一定抗氧化活性,其中化合物1的抗氧化活性最强,其EC₅₀为(24.73±6.12)μmol/L。聚炔类化合物1-4为荷叶离褶伞首次报道成分,可作为祁连山野生荷叶离褶伞HPLC-DAD化学表征参考化合物。     

四棱草中的一个新环八肽

从四棱草（Schnabalia oligophylla Hand.-Mazz.）全草的甲醇提取物中分离得到一个新的环八肽,命名为四棱草环肽（1）。用波谱方法鉴定了1的结构,并以通过HPLC手性柱分析指定了除脯氨酸和甘氮酸外的氨基酸的绝对构型。活性实验显示,四棱草环肽（1）对T／B淋巴细胞有免疫抑制作用,另外,从该植物中还分离鉴定了7个已知化合物。     

灯盏花中的糖苷

从灯盏花（Erigeron breviscapus (Vant.) Hand.-Mazz.) 全株的乙醇提取物的正丁醇部分分得10个化合物,通过波谱方法鉴定为erigeside I(1)、γ－吡喃酮－3－O－β－D－[6′－（4″－羟基－3″,5″－二甲氧基苯甲酰）-]-吡喃葡萄糖苷（erigeside D,2)、erigeside A(3)、erigeside B(4)、erigeside Ⅱ(5)、7-O-β-D-吡喃葡萄糖－6－甲氧基香豆素（6）、icariside B2(7)、blumenol C葡萄糖苷（8）、（＋）－丁香树酯醇O－β－D－吡喃葡萄糖苷（9）和野黄芩苷甲酯（10）。用X射线单晶衍射方法确定了化合物7的绝对构型。2是一个新化合物,7、8和9首次从该属植物分离得到,6首次从该种植物分离得到。     

北五味子的水溶性化学成分

从北五味子（Schisandra chinensis）果实的水溶性部位得到8个已知化合物,经波谱分析确定其结构分别为：原儿茶酸（protocatechuic acid 1）,奎尼酸（quinic acid）,柠檬酸单甲酯（2－methyl citrate,3),5－羟甲基－2－糠醛（5-hydroxymethyl-2-furancarboxaldehyde 4),4-(3′－甲氮基－4′－羟基－苯基）－2－丁酮－4′-O-β-D0吡喃葡萄糖甙(zingerone glucoside 5),2－异丙基－5－甲基－1,4－苯二酚1－O－β－D－吡喃葡萄糖甙（thymoquinol 2-glu-coside 6),2－甲基－5－异丙基－1,4－苯二酚1－O－β－D－吡喃葡萄糖甙（thymoquinol 5-glu-coside 7)和胡萝卜甙（daucosterol 8）。     

金针菇固体发酵菌丝体次级代谢产物分离鉴定

采用硅胶柱色谱、ODS柱色谱、Sephadex LH-20柱色谱、HPLC等分离方法对金针菇大米发酵乙酸乙酯提取物进行分离,根据理化性质和波谱数据鉴定化合物结构：鉴定了4个倍半萜,包括1个新的桉叶烷型倍半萜,3个侧柏烷型倍半萜,分别是flamvelutpenol A(1),aquaticol(2),enokipodin C(3),limacellone(4)。并通过与Rh2(OCOCF3)4络合的方法确定了新化合物flamvelutpenol A(1)和limacellone(4)的绝对构型。其中化合物3具有较好的抗菌活性,对耐甲氧西林金黄色葡萄球菌和枯草芽孢杆菌的MIC值分别为12.5mg/L,25mg/L。且化合物1－4均是首次从该种真菌中分离得到。     

多蕊商陆的化学成分

从多蕊商陆（Phytolacca polyandra)根的乙醇提取物中分到一个新的环二肽,两个已知的环二肽的混合物以及两个甾体化合物。根据化学和光谱数据,它们的化学结构分别确定为：环（脯氨酸－酪氨酸）（1）,环（丙氨酸－亮氨酸）（2）,环（丙氨酸－异亮氨酸）（3）,α－菠甾醇（4）和α－菠甾醇吡喃葡萄糖苷（5）。在商陆科植物中,环肽成分是首次被发现。     

常绿臭椿的酚类成分研究

从常绿臭椿(AilanthusfordiiNooteboom)枝条乙醇提取物的乙酸乙酯萃取部分分离得到了5个酚类成分和胡萝卜苷。经波谱分析确定其结构分别为:槲皮苷(1),杨梅苷(2),阿福豆苷(3),( )-没食子儿茶素(4),3-氯-4-羟基-苯甲酸(5),胡萝卜苷(6)。其中化合物1-5为首次从该属植物中分离得到。     

Isolation of iridoid and secoiridoid glycosides and comparative study on Radix gentianae and related adulterants by HPLC analysis

HPLC profile guided study led to the isolation of an acylated secoiridoid glycoside, named gentiotrifloroside (1), together with six known compounds, i.e., loganic acid (2), 6-O-beta-d-glucopyranosylgentiopicroside (3), swertiamarin (4), gentiopicroside (5), sweroside (6) and 2 -(o,m-dihydroxybenzyl)-sweroside (7) from Gentiana triflora and Gentiana rigescens. The structure of 1 was deduced from one- and two-dimensional NMR spectroscopic experiments. Compounds 1-7 were used successfully as chemical markers for the comparison of the four species of Gentiana used as Radix gentianae. Additionally, differentiation of Gentiana species mentioned and those used as adulterants was evaluated. The close similarity of chemical composition among the four genuine Gentiana species explain their popular usage as R. gentianae in Chinese medicine. We have also shown that the variation of chemical composition in R. gentianae and related adulterants agree well with their botanical phylogeny.     

Two novel C29-5beta-sterols from the stems of Opuntia dillenii

Two novel C29-5beta-sterols, opuntisterol [(24R)-24-ethyl-5beta-cholest-9-ene-6beta,12alpha-diol] (1) and opuntisteroside [(24R)-24-ethyl-6beta-[(beta-d-glucopyranosyl)oxy]-5beta-cholest-9-ene-12alpha-ol] (2), together with nine known compounds, beta-sitosterol (3), taraxerol (4), friedelin (5), methyl linoleate (6), 7-oxositosterol (7), 6beta-hydroxystigmast-4-ene-3-one (8), daucosterol (9), methyl eucomate (10) and eucomic acid (11), were isolated from the stems of Opuntia dillenii collected in Guizhou Province, China. Their structures were elucidated mainly by spectroscopic analysis. The absolute configuration of 1 were deduced from comparative 1H NMR data of the (S)- and (R)-methoxyphenyl acetate derivatives. Compounds 6-8, 10 and 11 were isolated from O. dillenii for the first time.     

裸花紫珠的化学成分

从裸花紫珠(Callicarpa nudiflora Hook.ex Arn.)地上部分的乙醇提取物中分离得到了7个化合物,经波谱分析确定其结构分别为:木犀草苷(1),木犀草素-3'-O-β-D-吡喃葡萄糖苷(2),木犀草素-4'-O-β-D-吡喃葡萄糖苷(3),2α,3α,19α-三羟基-乌索-12-烯-28-酸(4),乌索酸(5),2α-羟基-乌索酸(6)和齐墩果酸(7)。其中化合物2-7为首次从该植物中分离得到。     

Seco C-nucleoside analogs of the 1,2,4-triazole

The seco C-nucleosides 3-(1,2,3,4,5-penta-O-acetyl-D-gluco- and D-galacto-pentitol-1-yl)-1H-1,2,4-triazoles (6 and 7) were obtained in one pot by deamination and dethiolation of 4-amino-3-(D-gluco- and D-galacto-pentitol-1-yl)-5-mercapto-1,2,4-triazoles (1 and 2), respectively, using sodium nitrite in orthophosphoric acid and subsequent acetylation. The structures were confirmed by using 1H, 13C and 2D NMR spectra, DQFCOSY, HMQC and HMBC experiments. The favored conformational structures were deduced from the vicinal coupling constants of the protons.     

Chemical constituents of Malagasy liverworts: cyclomyltaylanoids from Bazzania madagassa

Five cyclomyltaylanoids (2-6), together with 1R,5R-diacetoxycyclomyltaylan-10-one (1), (+)-globulol, and ent-4beta,10alpha-dihydroxyaromadendrane have been isolated from the diethyl ether fraction of the Malagasy liverwort, Bazzania madagassa. The structure of 1 was confirmed by X-ray analysis, while those of the compounds were established on the basis of one- and two-dimensional NMR spectroscopic evidence, and comparison with data reported in the literature. The chemosystematics of B. madagassa are discussed.     

Microbial transformation of spirolaxine, a bioactive undecaketide fungal metabolite from the basidiomycete Sporotrichum laxum

Incubation of (+)-spirolaxine (= (3R)-5-hydroxy-7-methoxy-3-{5-[(2R,5R,7R)-2-methyl-1,6-dioxaspiro[4.5]dec-7-yl]pentyl}-2-benzofuran-1(3H)-one; 1a) with Bacillus megaterium afforded two new mono- and one new dihydroxylated metabolite(s), all OH groups being introduced on the non-activated six-membered ring. In contrast, exposure of 1a to Cunninghamella echinulata gave rise to hydroxylation on the five-membered ring of the parent structure. The structures and absolute configurations of the new products 1b-e were deduced on the basis of MS and NMR data. The metabolite 1b was investigated, in comparison to 1a, for its cytotoxicity (sulforhodamin-B test) and for its antiproliferative activity towards bovine microvascular endothelial cells (BMEC).     

Five biflavonoids from Calycopteris floribunda (Combretaceae)

The structures of five biflavonoids, 6"-demethoxyneocalycopterone (1), calyflorenone C (2), 6"-epi-calyflorenone B (3), 6"-epi-calyflorenone C (4) and calyflorenone D (5) from the green parts of Calycopteris floribunda were established by NMR and MS. Their NMR and chiroptical properties (CD, [alpha]20D ) were compared with those of the known C. f. biflavonoids 6-11. Compound 1 represents a calycopterone derivative, 2-5 have a calyflorenone skeleton. With regard to one chiral center (C-6"), 4 and 3 are the respective epimers of 2 and 11.     

关于岩芋属二个种的模式化问题

岩芋属Remusatia(Araceae)是一个特征鲜明的属,共含三种,即R.vivipara(Lo-dd.)Schott,R．hookeriana Schott,R．ornata(Schott)H．Li et Q．F．Guo。Go－natanthus(?)ornatus Schott中的(?)这类植物转入Remusatia属,其名应为秀丽岩芋Remusatia ornata(Schott)H．Li et Q．F．Guo．Gonatanthus ornatus 的模式标本是Hooker f．s．n．采自印度喀西山,现只有Schott绘制的模式图照片; Schlagintweit n．313,亦采自喀西山,是Krause(1920）补充描述本种的重要凭证标本,现只有遗图。R．hooke－riana Schott(1857）的模式标本Hooker f．s．n．产锡金,Krause(1920）发表的图和描述的大部分可作为该种的凭证,是一个不同于R.ornata的好种。Rao et Verma(1968）描述的 Gonatanthus ornatus应是Remusatia hookeriana.     

Novel synthesis of seco type of acyclo C-nucleosides of 1,2,4-triazole and 1,2,4-triazol

The seco C-nucleosides 3-(1,2,3,4,5-penta-O-acetyl-D-gluco- and D-galacto-pentitol-1-yl)-1H-1,2,4-triazoles (8 and 9) were obtained in a one pot by deamination and dethiolation of 4-amino-3-(D-gluco- and D-galacto-pentitol-1-yl)-5-mercapto-1,2,4-triazoles (1 and 2), respectively, using sodium nitrite in orthophosphoric acid and subsequent acetylation. Condensation of 1, 2, and 4-amino-3-(D-glycero-D-gulo-hexitol-1-yl)-5-mercapto-1,2,4-triazole (12) with phenacylbromide (11) afforded the corresponding 3-(D-gluco-, D-galactopentitol-1-yl) and 3-(D-glycero-D-gulo-hexitol-1-yl)-6-phenyl-7H-1,2,4-triazolo[3,4-b][1,3,4] thiadiazines (15, 16, and 17). Acetylation of 15-17 gave the penta- and hexa-O-acetyl derivatives 18-20, respectively. The structures were confirmed by using 1H, 13C, and 2D NMR spectra, DQFCOSY, HMQC, and HMBC experiments. The favored conformational structures were deduced from the vicinal coupling constants of the protons.