猴头菌子实体化学成分研究

利用柱色谱技术从猴头菌(Hercium erinaceus)干燥子实体的甲醇提取物中分离得到11个化合物,经波谱技术分别鉴定为:D-赤藓糖醇(1)、D-阿拉伯糖醇(2)、1-O-β-D-吡哺葡萄糖基-(2S,4E,8E,2'R)-2-N-(2'-羟基十六烷酰)-9-甲基-4,8-sphingadienine(3)、3β-羟基-麦角甾-5,7,22-三烯(4)、3β-羟基-5α,8α-过氧化麦角甾-6,22-二烯(5)、硬脂酸(6)、油酸(7)、hericenone F(8)、hericenone C (9)、hericenone E(10)和hericene A(11).研究结果表明,hericenones型酚类物质在猴头菌子实体中含量丰富,化合物3是从猴头菌子实体中首次分离得到的脑酰胺类物质.     

Chemical constituents of Hericium erinaceum associated with the inhibitory activity against cellular senescence in human umbilical vascular endothelial cells

Abstract

Hericium erinaceum is an edible and medicinal mushroom widely used in Korea, Japan, and China. On the search for biologically active compounds supporting the medicinal usage, the MeOH extract of the fruiting bodies of H. erinaceum was investigated for its chemical constituents. Six compounds were isolated and identified as hericenone D (1), (22E,24R)-5α,8α-epidioxyergosta-6,22-dien-3β-ol (2), erinacerin B (3), hericenone E (4), hericenone F (5) and isohericerin (6) by comparing their spectroscopic data with previously reported values. The inhibitory effects on adriamycin-induced cellular senescence in human dermal fibroblasts (HDFs) and human umbilical vein endothelial cells (HUVECs) of the isolates (1–6) were studied. Among the isolated compounds, ergosterol peroxide (2) reduced senescence associated β-galactosidase (SA-β-gal) activity increased in HUVECs treated with adriamycin. According to experimental data obtained, the active compound may inspire the development of a new pharmacologically useful substance to be used in the treatment and prevention of age-related diseases.     

Diosgenin glucuronides from Solanum lyratum and their cytotoxicity against tumor cell lines

Bioassay-directed fractionation of the cytotoxicity active fraction of the whole plant from Solanum lyratum led to the isolation of a new steroidal saponin, diosgenin 3-O-beta-D-glucopyranosiduronic acid methyl ester (2), as well as four known compounds, diosgenin (1), diosgenin 3-O-beta-D-glucopyranosiduronic acid (3), diosgenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosiduronic acid (4), diosgenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucuroniduronic acid methyl ester (5). The structures of the isolated compounds were elucidated on the basis of their spectral data and chemical evidences. Compound 1 was isolated for the first time from this plant, and compound 3 was isolated as a new natural product. Cytotoxic activities of the isolated compounds were evaluated and the cytotoxicities of compounds 2-5 reported for the first time.     

Cycloartane type triterpenoids from the rhizomes of Polygonum bistorta

Two new compounds, 24(E)-ethylidenecycloartanone (1) and 24(E)-ethylidenecycloartan-3alpha-ol (2) were isolated from the rhizomes of Polygonum bistorta, together with seven known compounds viz., cycloartane-3,24-dione (3), 24-methylenecycloartanone (4), gamma-sitosterol (5), beta-sitosterol (6), beta-sitosterone (7), friedelin (8) and 3beta-friedelinol (9). All the cycloartane type triterpenoids, compounds 7 and 8 are reported for the first time from this plant. A combination of 1D and 2D NMR spectroscopy and MS were mainly used to elucidate the structures of the new compounds 1 and 2.     

Synthesis and biological activity of acetyl-protected hydroxybenzyl diethyl phosphates (EHBP) as potential chemotherapeutic agents

Several acetyl-protected hydroxybenzyl diethyl phosphates (EHBPs) that are capable of forming quinone methide intermediates were synthesized and their cell growth inhibitory properties were evaluated in four different human cancer cell lines. Compounds 1, 1a, and 1b, corresponding to (4-acetyloxybenzyl diethylphosphate), (3-methyl-4-acetyloxybenzyl diethylphosphate), and (3-chloro-4-acetyloxybenzyl diethylphosphate), were significantly more potent than compounds 2 and 3, (2-acetyloxybenzyl diethylphosphate) and (3-acetyloxybenzyl diethylphosphate), respectively. Using HT-29 human colon cancer cells, compounds 1 and 3 increased apoptosis, inhibited proliferation, and caused a G(2)/M block in the cell cycle. Our data suggest that these compounds merit further investigation as potential anti-cancer agents.     

Metabolism of Lignin Model Compounds of the Arylglycerol-beta-Aryl Ether Type by Pseudomonas acidovorans D(3)

A natural bacterial isolate that we have classified as Pseudomonas acidovorans grows on the lignin model compounds 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (compound 1) and 1-(4-hydroxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)propane-1,3-diol (compound 1'), as well as on the corresponding 1-oxo compounds (2 and 2') as sole sources of carbon and energy. Metabolic intermediates present in cultures growing on compound 1 included compound 2, 2-methoxyphenol (guaiacol [compound 3]), beta-hydroxypro-pioveratrone (compound 4), acetoveratrone (compound 5), and veratric acid (compound 6). Also identified were compounds 1', 2', beta-hydroxypropiovanillone (compound 4'), and acetovanillone (compound 5'), indicating that 4-O demethylation also occurs. The phenolic intermediates were the same as those found in cultures growing on compound 1'. Compounds 2 and 2' were in part also reduced to compounds 1 and 1', respectively. Compound 3 was shown to be derived from the 2-methoxyphenoxy moiety. A suggested degradation scheme is as follows: compound 1-->2-->(3 + 4)-->5-->6 (and similarly for 1'). In this scheme, the key reaction is cleavage of the ether linkage between C-2 (C(beta)) of the phenylpropane moiety and the 2-methoxyphenoxy moiety in compounds 2 and 2' (i.e., beta-aryl ether cleavage). On the basis of compounds identified, viz., 3 and 4 (4'), cleavage appears formally to be reductive. Because this is unlikely, the initial cleavage products probably were not detected. The implications of these results for the enzyme(s) responsible are discussed.     

Prenylated flavonoids of the leaves of Macaranga conifera with inhibitory activity against cyclooxygenase-2

Two prenylated flavonoid derivatives, 5-hydroxy-4'-methoxy-2",2"-dimethylpyrano-(7,8:6",5")flavanone (1) and 5,4'-dihydroxy-[2"-(1-hydroxy-1-methylethyl)dihydrofurano]-(7,8:5",4")flavanone (2), were isolated from an ethyl acetate-soluble extract of the leaves of Macaranga conifera using an in vitro activity-guided fractionation procedure based on the inhibition of cyclooxygenase-2. Also obtained were eight known compounds, 5,7-dihydroxy-4'-methoxy-8-(3-methylbut-2-enyl)flavanone (3), lonchocarpol A (4), sophoraflavanone B (5), 5,7-dihydroxy-4'-methoxy-8-(2-hydroxy-3-methylbut-3-enyl)flavanone (6), tomentosanol D (7), lupinifolinol (8), isolicoflavonol (9), and 20-epibryonolic acid (10). The structures of compounds 1 and 2 were determined using spectroscopic methods. All isolates were tested for their inhibitory effects against both cyclooxygenases-1 and -2, and selected compounds were evaluated in a mouse mammary organ culture assay.     

鞭打绣球中的一个新单萜苷

从鞭打绣球(Hemiphragma heterophyllum Wall.)全草中分离到1个新单萜苷和7个已知化合物.通过波谱数据分析,新单萜苷的结构鉴定为(4S)-α-萜烯醇-8-O-β-D-比喃木糖-(1→6)-β-D-比喃葡萄糖苷,已知化合物分别鉴定为globularin(2)、(2S 3S,4R,9E)-1,3,4-trihydroxy-2-[(2'R)-hydroxy-tetracosanoylamino]-9-octadecene(3)、β-香树素(4)、齐墩果酸(5)、肉桂酸(6)、β-谷甾醇(7)和胡萝卜甙(8).除化合物2外,其余化合物均为首次从鞭打绣球中分离得到.     

New Withanolides from Nicandra physaloides (Solanaceae)

Two new withanolides, named nicandrenone methyl ether (1), 26S nicandrenone methyl ether (2), together with ten known compounds were isolated from the whole plants of Nicandra physaloides (Solanaceae). Their chemical structures were deduced on the basis of spectroscopic analysis. Ten known compounds were identified as nicandrenone (3), Nic-7 (4), nicaphysalin E (5), pinosylvin monomethyl ether (6), 2S-pinocembrin (7), (1S, 2R)-1, 2-bis (4-hydroxy-3-methoxyphenyl)-1, 3-propanediol (8), vanillin (9), indole-3-carboxylic acid (10), vanillic acid (11) and drummondol (12).     

小茴香根的化学成分研究

从小茴香(Foeniculum vulgare Mill.)根的乙醇提取物中分离得到了5个化合物,通过MS和NMR等方法鉴定为:莳萝脑(1),亚油酸蔗糖苷(2),镰叶芹二醇(3),β-谷甾醇(4),豆甾醇-β-D-吡喃葡萄糖苷(5),其中化合物2和3首次从该种植物中分离得到。     

Cyclooxygenase-2 enzyme inhibitory triterpenoids from Picrorhiza kurroa seeds

A bioassay guided phytochemical study of the ethyl acetate extract of the seeds of Picrorhiza kurroa afforded a new triterpenoid, 2alpha, 3beta, 19beta, 23-tetrahydroxyolean-12-en-28-O-beta-D-glucoside (1), along with five known triterpenoids, 2alpha, 3beta, 19beta, 23-tetrahydroxyolean-12-en-28-oic acid (2), 2alpha, 3beta, 23-trihydroxyolean-12-en-28-O-beta-d-glucoside (3), 2alpha, 3beta, 23-trihydroxyolean-12-en-28-oic acid (4), 2alpha, 3beta, 19beta, trihydroxyolean-12-en-28-oic acid (5), and 2alpha, 3beta, 6beta, 23-tetrahydroxyolean-12-en-28-oic acid (6). Their structures were established by extensive NMR spectral studies. The acetyl derivatives, compounds 7 and 8, were prepared from compounds 1 and 2, respectively, to aid in their structure elucidation. The inhibition of cyclooxygenase-2 (COX-2) enzyme by compounds 1--6 at 100 microg/mL was 38.3%, 39%, 37%, 49.6%, 25%, and 45.0%, respectively. However, compounds 1--6, at 100 microg/mL, did not inhibit cyclooxygenase-1 (COX-1) enzyme. Compound 1 is a novel triterpenoid and compounds 1--6 are isolated for the first time from the seeds of P. kurroa.     

Minor phenolics from Crinum bulbispermum bulbs

From the bulbs of Crinum bulbispermum Milne, four new minor compounds were isolated viz. 4-hydroxy-2',4'-dimethoxydihydrochalcone (1), 4,5-methylenedioxy-4'-hydroxy-2-aldehyde[1,1'-biphenyl] (4), hippacine (6), and 4'-hydroxy-7-methoxyflavan-3-ol (7). In addition, four known compounds were isolated and identified as 2(S),3',4'-dihydroxy-7-methoxy flavan (2), isolarrien (3), isoliquiritigenin (5) and liquiritigenin (8). The structures of the isolated compounds were established by spectral evidence.     

Chemical constituents of rice (Oryza sativa) hulls and their herbicidal activity against duckweed (Lemna paucicostata Hegelm 381)

Four new compounds, stigmastanol-3beta-p-glyceroxydihydrocoumaroate (1), stigmastanol-3beta-p-butanoxydihydrocoumaroate (2), lanast-7,9(11)-dien-3alpha,15alpha-diol-3alpha-D-glucofuranoside (3) and 1-phenyl-2-hydroxy-3,7-dimethyl-11-aldehydic-tetradecane-2-beta-D-glucopyranoside (4), along with several known compounds were isolated from the methanol extract of hulls of Oryza sativa. The new structures were established by one- and two-dimensional NMR and in combination with IR, EI/MS, FAB/MS and HR-FAB/ MS. Compound (3) strongly inhibited the growth of duckweed (Lemna paucicostata Hegelm 381), whilst compounds (2) and (4) exhibited weak inhibition.     

Human ACAT inhibitory effects of shikonin derivatives from Lithospermum erythrorhizon

Three naphthoquinones were isolated by bioassay-guided fractionation from the CHCl(3) extracts of roots of Lithospermum erythrorhizon. They were identified as acetylshikonin (1), isobutyrylshikonin (2), and beta-hydroxyisovalerylshikonin (3) on the basis of their spectroscopic analyses. The compounds 1-3 were tested for their inhibitory activities against human ACAT-1 (hACAT-1) or human ACAT-2 (hACAT-2). Compound 2 preferentially inhibited hACAT-2 (IC(50)=57.5microM) than hACAT-1 (32% at 120microM), whereas compounds 1 and 3 showed weak inhibitory activities in both hACAT-1 and -2. To develop more potent hACAT inhibitor, shikonin derivatives (5-11) were synthesized by semi-synthesis of shikonin (4), which was prepared by hydrolysis of 1-3. Among them, compounds 5 and 7 exhibited the strong inhibitory activities against hACAT-1 and -2. Furthermore, we demonstrated that compound 7 behaved as a potent ACAT inhibitor in not only in vitro assay system but also cell-based assay system.     

Studies on the Chemical Constituents of the Leaves of WTBX]Pseudotaxus chienii (Cheng) Cheng

Fourteen compounds were isolated from the leaves of Pseudotaxus chienii (Cheng) Cheng which is uniquely indigenous to China, and their structures were identified mainly by spectrum analyses. Among them, 13 known compounds were determined as: 2-guaiacylpropane-1, 3-diol (1), vanillic acid (2), 3-methoxy-4-hydroxy cinnamic acid (3). 3. 5-dimethoxy-phenol (4), taxicatin (5), 5-oxymaltol (6), quercetin-3-rhamnoside (7), (±)-catechin (8), ecdysterone (9), β-sitosterol (10), D-glucose (11), (±)-10-nonacosanol (12) and octacosanoic acid (13). All these compounds butβ-sitosterol were isolated from this plant for the first time. Compounds 1 and 6 have never been reported in plant kingdom. Another compound was tentatively established as a new compound, named pseudotaxlactone (14).     

民族药四数九里香的化学成分及其细胞毒活性研究

为了阐明民族药四数九里香Murraya tetramera Huang的药效物质基础,课题组使用色谱技术从其醇提取物中分离得14个化合物;运用~1H NMR、¹³C NMR波谱方法和文献数据对比鉴定为正24烷酸(1)、9,13,17,21-tetramethyl-5-docosenoic acid(2)、3-O-β-D-吡喃葡萄糖基-山奈酚甙(3)、补骨脂素(4)、紫苏醛(5)、槲皮素(6)、methyl salicylate glucoside(7)、(9S,10R,11E,13R,15Z)-9,10,13-trihydroxyoctadeca-11,15-dienoic Acid(8)、2-isopropyl-5-methylphenol(9)、β-胡萝卜甘(10)、7-羟基香豆素(11)、七叶内酯(12)、β-谷甾醇醋酸酯(13)、山奈酚(14)。除了化合物4、6外,其他化合物为首次从该植物中分离得到。同时,研究各化合物对5株肿瘤细胞的体外生长抑制作用。与阳性对照组比较,结果表明:化合物3、4、5、6、7、8、10、11、12、13、14对白血病HL60显现良好的细胞毒活性;化合物1～14对肺腺癌A549的的细胞毒活性低于阳性对照组;化合物6、13、14对肝癌SMMC7721显现良好的细胞毒活性;化合物1、2、3、6、7、9、11、12对乳腺癌MCF7显现良好的细胞毒活性;化合物1～14对结肠癌SW480的细胞毒活性低于阳性对照组。     

Xanthones with quinone reductase-inducing activity from the fruits of Garcinia mangostana (Mangosteen)

Bioactivity-guided fractionation of a dichloromethane-soluble extract of Garcinia mangostana fruits has led to the isolation and identification of five compounds, including two xanthones, 1,2-dihydro-1,8,10-trihydroxy-2-(2-hydroxypropan-2-yl)-9-(3-methylbut-2-enyl)furo[3,2-a]xanthen-11-one (1) and 6-deoxy-7-demethylmangostanin (2), along with three known compounds, 1,3,7-trihydroxy-2,8-di-(3-methylbut-2-enyl)xanthone (3), mangostanin (4), and alpha-mangostin (5). The structures of compounds 1 and 2 were determined from analysis of their spectroscopic data. All isolated compounds in the present study together with eleven other compounds previously isolated from the pericarp of mangosteen, were tested in an in vitro quinone reductase-induction assay using murine hepatoma cells (Hepa 1c1c7) and an in vitro hydroxyl radical antioxidant assay. Of these, compounds 1-4 induced quinone reductase (concentration to double enzyme induction, 0.68-2.2microg/mL) in Hepa 1c1c7 cells and gamma-mangostin (6) exhibited hydroxyl radical-scavenging activity (IC50, 0.20microg/mL).     

茎花葱臭木化学成分的研究

从茎花葱臭木种子中分离得到5个化合物,经理化与波谱分析鉴定为β-谷甾醇(1)、没食子酸乙酯(2)、胡萝卜苷(3)、1-O-β-D-吡喃葡萄糖基-(2S,3S,4R,8Z)-2-N-(2 ′-羟基二十四烷酰氨基)十八二氧鞘氨-8-烯(4)和2,3,2″,3″-四氢穗花杉双黄酮(5).这5个化合物均首次从该植物中分离得到.其中化合物5进行细胞毒活性测试,没有显示抑制活性.     

Further constituents from Caralluma negevensis

Two new megastigmane glycosides (1 and 2) and two new flavone glycosides (3 and 4) were isolated from the methanol extract of the whole plant of Caralluma negevensis Zohary (Asclepiadaceae). The structures of the isolated compounds were characterized as (9R)-2beta,9-dihydroxymegastigma-4,7-dien-3-one-9-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (1), 2beta,9-dihydroxymegastigma-4-en-3-one 9-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (2), luteolin 3'-O-beta-D-glucopyranoside-4'-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (3), and luteolin 3',4'-di-O-beta-D-glucopyranoside (4). The structures of the isolated compounds were established on the basis of spectral evidence and chemical transformation.     

Triterpenoid saponins from Pteleopsis suberosa stem bark

Thirteen oleanane saponins (1-13), four of which were new compounds (1-4), were isolated from Pteleopsis suberosa Engl. et Diels stem bark (Combretaceae). Their structures were determined by 1D and 2D NMR spectroscopy and ESI-MS spectrometry. The compounds were identified as 2alpha,3beta,19alpha,23,24-pentahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (1), 2alpha,3beta,19beta,23,24-pentahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha,23-tetrahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (3), and 2alpha,3beta,6beta,19alpha,24-pentahydroxy-11-oxo-olean-12- en-28-oic acid 28-O-beta-D-glucopyranosyl ester (4). The presence of alpha,beta-unsaturated carbonyl function was not common in the oleanane class and the aglycons of these compounds were not found previously in the literature. Moreover, the isolated compounds were tested against Helicobacter pylori standard and vacA, and cagA clinical virulence genotypes. Results showed that compound 6 has an anti-H. pylori activity against three metronidazole-resistant strains (Ci 1 cagA, Ci 2 vacA, and Ci 3).