Antioxidant caffeic acid derivatives from leaves of<Emphasis Type="Italic">parthenocissus tricuspidata</Emphasis>

Five caffeic acid derivatives; methyl ester of caffeoylglycolic acid (1), dimethyl ester of caffeoyltartaric acid (2), dimethyl ester of caffeoyltartronic acid (3), monomethyl ester of caffeoyltartronic acid (4), methyl ester of caffeic acid (5), and some other secondary metabolites including; quercetin, quercetin 3-O-beta-D-glucuronide methyl ester, kaempferol, 3,5,7,4'-O-tetramethylkaempferol, beta-sitosterol glucoside, 2alpha-hydroxyursolic acid and 2,24-dihydroxyursolic acid, have been isolated and characterized. All the isolated compounds were characterized with the help of NMR spectroscopy and mass spectrometry. Structure of compound 3 was also confirmed by a single X-ray crystallographic technique. Isolates were evaluated for antioxidant activities and most of the tested compounds were found to be potent in DPPH free radical scavenging (IC50 = 4.56-14.17 microg/mL) and superoxide anion scavenging (IC50 = 0.58-7.39 microg/mL) assays.     

Antioxidative constituents fromlycopus lucidus

Three phenolic compounds, rosmarinic acid (1), methyl rosmarinate (2), ethyl rosmarinate (3), and two flavonoids, luteolin (4), luteolin-7-O-beta-D-glucuronide methyl ester (5) were isolated from the aerial part of Lycopus lucidus (Labiatae). Their structures were determined by chemical and spectral analysis. Compounds 1-5 exhibited potent antioxidative activity on the NBT superoxide scavenging assay. The IC50 values for compounds 1-5 were 2.59, 1.42, 0.78, 2.83, and 3.05 microg/mL respectively. In addition, five compounds were isolated from this plant for the first time.     

A new lignan glycoside from the fruits of <Emphasis Type="Italic">Cornus kousa</Emphasis> Burg.

A new lignan glycoside, (7'S, 8'R)-dihydrodehydrodiconiferyl alcohol-4'-O-beta-D-xylopyranoside (1), named cornuskoside A, was isolated from the fruits of Cornus kousa. The structure of the compound was determined by spectroscopy, including FABMS, UV, IR, (1)H-and 13C-NMR, DEPT and 2D-NMR (COSY, HSQC, and HMBC). This new lignan glycoside, along with its aglycone, (7'S, 8'R)-dihydrodehydrodiconiferyl alcohol (3), and another lignan with a similar skeleton, (-)-balanophonin (2), which have been previously isolated from this plant, were evaluated for cytotoxicity in human cancer cell lines such as HeLa, MCF-7, SK-MEL-5, and SK-OV-3. Compounds 2 and 3 showed cytotoxicity against HeLa [IC50 = 29.1 microM (2), 45.5 microM (3)], MCF-7 [IC50 = 29.2 microM (2), 28.2 microM (3)], SK-MEL-5 [IC50 = 31.3 microM (2), 32.3 microM (3)], and SK-OV-3 [IC50 = 33.4 microM (2), 43.4 microM (3)] cell lines.     

Antiinflammatory constituents from the roots of smilax bockii warb.

From 70% ethanol extract of the roots of Smilax bockii warb., seven flavonoids, kaempferol (1), kaempferol-7-O-beta-D-glucopyranoside (2), quercetin (3), isorhamnetin (4), (+)-dihydro-kaempferol (5), engeletin (6), isoengeletin (7), and n-butyl-beta-D-fructopyranoside (8), caffeic acid n-butyl ester (9) were isolated and identified by means of chemical and spectroscopic. Compounds 2, 4, and 6-9 were isolated for the first time from the roots of S. bockii and compounds 2, 8, and 9 were firstly isolated from the genus Smilax. In addition, using the SEAP (Secreted alkaline phosphatase) assay system, we investigated the in vitro anti-inflammatory activity of the 70% ethanol extract of the roots of S. bockii, which showed moderate activity in inhibiting TNF-alpha-induced NF-kappaB activation with an IC50 value of 166.6 microg/mL.     

Cytotoxic constituents fromSolanum lyratum

Activity-guided fractionation of the ethanol extract of the whole plant from Solanum lyratum resulted in the isolation of a new pregnane derivative glycoside, 16-dehydropregnenolone 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosid uronic acid (2), as well as other six known compounds: 16-dehydropregnenolone (1), allopregenolone (3), protocatechuic acid (4), vanillic acid (5), caffeic acid (6), and scopoletin (7). The structures of the isolated compounds were elucidated on the basis of their spectral data and chemical evidences. Compounds 1, 3, 4 were isolated for the first time from this plant. Cytotoxic activities of the isolated compounds were evaluated. Compound 1 exhibited significant cytotoxic activity against A375-S2, HeLa, SGC-7901, and Bel-7402 with IC50 values of 13.1 +/- 0.9, 21.5 +/- 1.0, 40.2 +/- 0.7, and 49.8 +/- 1.2 microg/mL, respectively.     

卷柏中化学成分的分离与结构鉴定

目的研究中药卷柏(Selaginella tamariscina (Beauv.) Spring)水提物中的化学成分。方法用Sephadex LH-20及硅胶等色谱技术进行分离纯化,根据理化性质、光谱数据进行结构鉴定。结果得到9个化合物,分别鉴定为(2r,3s)-二氢-2-(3′,5′-二甲氧基-4′-羟基苯基)-3-羟甲基-7-甲氧基-5-乙酰基苯骈呋喃(1),3-羟基-苯丙酸-(2′-甲氧基-4′-羧基苯酚)酯(卷柏酯A,2),丁香脂素(3),1-(4′-羟基-3′-甲氧基苯基)丙三醇(4),阿魏酸(5),咖啡酸(6),香荚兰酸(7),丁香酸(8),7-羟基香豆素(9)。结论化合物1,2为新化合物,其余化合物均为首次从卷柏属植物中分离得到。     

Constituents from the fruiting bodies ofGanoderma applanatum and their aldose reductase inhibitory activity

Eight compounds were isolated from the fruiting bodies of Ganoderma applanatum, and were identified as 2-methoxyfatty acids (1), 5-dihydroergosterol (2), ergosterol peroxide (3) 3beta,7beta, 20,23xi-tetrahydroxy-11,15-dioxolanosta-8-en-26-oic acid (4), 7beta,20,23xi-trihydroxy-3,11,15-trioxolanosta-8-en-26-oic acid (5), cerevisterol (6), 7beta,23xi-dihydroxy-3,11,15-trioxolanosta-8,20E (22)-dien-26-oic acid (7), and 7beta-hydroxy-3,11,15,23-tetraoxolanosta-8,20E(22)-dien-26-oic acid methyl ester (8) by spectral analysis. All compounds were isolated for the first time from this fruiting bodies, and their effect on rat lens aldose reductase (RLAR) activity was tested. Among these eight compounds, ergosterol peroxide (3) was found to exhibit potent RLAR inhibition, its IC50 value being 15.4 microg/mL.     

Phytochemical constituents of Artemisia stolonifera

Repeated column chromatographic separation of the CH2Cl2 extract of Artemisia stolonifera (Asteraceae) led to the isolation of a triterpene (I), a sesquiterpene (II), two aromatic compounds (III and IV) and a benzoquinone (V). Their structures were determined by spectroscopic means to be simiarenol (I), (1S,7S)-1beta-hydroxygermacra-4(15),5,10(14)-triene (II), 3'-methoxy-4'-hydroxy-trans-cinnamaldehyde (III), vanillin (IV) and 2,6-dimethoxy-1,4-benzoquinone (V), respectively. Among these products, compound V showed significant cytotoxicity against five human tumor cell lines in vitro, A549 (non small cell lung adenocarcinoma), SK-OV-3 (ovarian), SK-MEL-2 (skin melanoma), XF498 (CNS) and HCT15 (colon) with ED50 values ranging from 1.33-4.22 microg/ml.     

A new ferulic acid ester and other constituents from Dracocephalum peregrinum

A new ferulic acid ester, 1′-methyl-2′-hydroxyethyl ferulate (1), together with methylcaffeate (2), 4-hydroxy cinnamic acid (3), ferulic acid (4), caffeic acid (5), diosmetin (6), luteolin (7), 5,3′,4′-trihydroxy-3,7-dimethoxyflavone (8), eriodictyol (9), kaempferol (10), quercetin (11), acacetin-7-O-glcopyranoside (12), 4-(β-glucopyranosyloxy) benzoic acid (13), luteolin-7-O-(6″-feruloyl) glucopyranoside (14), luteolin-7-O-glucopyranoside (15), kaempferide-3-O-rhamnopyranoside (16), quercitrin (17), kaempferol-3-O-glucopyranoside (18), prunasin (19), quercetin-7-O-glucopyranoside (20), quercetin-3-O-glucopyranoside (21), plantaginin (22), linarin (23), luteolin-7-O-rutinoside (24), and chlorogenic acid (25) were isolated from the aerial parts of Dacocephalum peregrinum. The structure of 1 was elucidated on the basis of spectroscopic and HR-ESI-MS analyses. In addition, compound 1 exhibited mild inhibitory effect on NO production in LPS-stimulated RAW264.7 cells.     

Total synthesis of a norneolignan from Ratanhia radix

The total synthesis of a norneolignan isolated from Ratanhia, 5-(3-hydroxypropyl)-2-(2-methoxy-4'-hydroxyphenyl)benzofuran (8), is described. The key steps contain the one-pot reaction for a 2-arylbenzofuran 6 from methyl 3-(4-hydroxyphenyl)propionate with 2-chloro-2-methylthio-(2'-methoxy-4'-acetoxy)acetophenone (5) in the presence of ZnCl2, and reductive desulfurization of the resulting product 6.     

Antioxidant constituents and a new triterpenoid glycoside from<Emphasis Type="Italic">Flos Lonicerae</Emphasis>

As a component of our continuing investigations into herb-derived antioxidant agents, we have evaluated the antioxidant effects of Flos Lonicerae (Lonicera japonica flowers), via 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, total reactive oxygen species (ROS), hydroxyl radical (*OH), and peroxynitrite (ONOO-) assays. Among the methanolic extract and the dichloromethane, ethyl acetate, n-butanol, and water fractions, the EtOAc fraction of Flos Lonicerae exhibited marked scavenging/inhibitory activities, as follows: IC50 values of 4.37, 27.58 +/- 0.71, 0.47 +/- 0.05, and 12.13 +/- 0.79 microg/mL in the DPPH, total ROS, ONOO-, and *OH assays, respectively. Via a bioactivity-guided fractionation approach, a new triterpenoid glycoside, oleanolic acid 28-O-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-xylopyranosyl(1-->6)]-beta-D-glucopyranosyl ester (12), along with eleven known compounds, including chrysoeriol (1), luteolin (2), 5-hydroxymethyl-2-furfural (3), caffeic acid (4), protocatechuic acid (5), chrysoeriol 7-O-beta-D-glucopyranoside (6), isorhamnetin 3-O-beta-D-glucopyranoside (7), kaempferol 3-O-beta-D-glucopyranoside (8), quercetin 3-O-beta-D-glucopyranoside (9), hederagenin 3-O-alpha-L-arabinopyranoside (10), and luteolin 7-O-beta-D-glucopyranoside (11), were isolated from the EtOAc fraction. The structures of isolated compounds 1-12 were elucidated via spectroscopic analyses. Compound 12 was isolated from a natural source for the first time. Compounds 2, 4, 5, 7, 9, and 11 evidenced marked scavenging activities, with IC50 values of 2.08-11.76 microM for DPPH radicals, and 1.47-6.98 microM for ONOO-.     

分蘖葱头中新黄酮苷的结构鉴定

目的　研究百合科植物分蘖葱头（Allium cepa L. var agrogatum Don）鳞茎的黄酮类化学成分。方法　利用Sephadex LH-20柱色谱进行分离纯化。从分蘖葱头中分离得到4个化合物,用IR,UV,MS,¹HNMR,¹³CNMR,¹H-¹H COSY,¹H-¹³C COSY和HMBC等光谱鉴定化合物。结果　经光谱鉴定化合物结构为：槲皮素3′-甲氧基-4′-O-β-D-葡吡喃糖苷(I)、山奈酚(II)、槲皮素4′-O-β-D-葡吡喃糖苷(III)和槲皮素3,4′-二-O-β-D-葡吡喃糖苷(IV)。结论　化合物I为新的黄酮苷类化合物,命名为分蘖葱头苷甲（Alliumoside A）; II,III和IV为首次从该植物中分得。     

Heterocyclic compounds from Chrysanthemum coronarium L. and their inhibitory activity on hACAT-1, hACAT-2, and LDL-oxidation

The aerial parts of Chrysanthemum coronarium L. were extracted with MeOH, and the concentrated extract was partitioned using EtOAc, n-BuOH, and H(2)O, successively. Repeated column chromatography of the EtOAc and n-BuOH fractions gave a new heterocycle, 5,5'-dibuthoxy-2,2'-bifuran (1) along with five known compounds: methyl trans-ferulate (2), prunasin (3), sambunigrin (4), pterolactam (5), and adenosine (6), which were identified by several spectroscopic methods including NMR and MS. This paper is the first report on the isolation of these compounds from C. coronarium L. The IC(50) values of compound 1 for human Acyl-CoA:cholesterol acyltransferase (hACAT)-1 and hACAT-2 were 0.16 mM and 0.19 mM, respectively. Compound 2 inhibited low-density lipoprotein (LDL) oxidation with an IC(50) value of 7.7 microM.     

Protoberberine alkaloids and their reversal activity of P-gp expressed multidrug resistance (MDR) from the rhizome ofCoptis japonica Makino

Six protoberberine alkaloids were isolated from the chloroform layer of the rhizome of Coptis japonica Makino (Ranunculaceae). The structures of the isolated compounds were determined to be 6-([1,3]dioxolo[4,5-g]isoquinoline-5-carbonyl)-2,3-dimethoxy-benzoic acid methyl ester (1), oxyberberine (2), 8-oxo-epiberberine (3), 8-oxocoptisine (4), berberine (5) and palmatine (6) by physicochemical and spectroscopic methods. The compound 3 (8-oxo-epiberberine) was first isolated from natural sources. The compounds were tested for cytotoxicity against five tumor cell lines in vitro by SRB method, and also tested for the MDR reversal activities. Compound 4 was of significant P-gp MDR inhibition activity with ED50 value 0.018 microg/mL in MES-SA/DX5 cell and 0.0005 microg/mL in HCT15 cell, respectively.     

Sesquiterpenes and other constituents from the aerial parts of Inula japonica

Three new sesquiterpenes, 1beta-hydroxy-8beta-acetoxycostic acid methyl ester, 1beta-hydroxy-8beta-acetoxyisocostic acid methyl ester and 1beta-hydroxy-4alpha,11alpha-eudesma-5-en-12,8beta-olide, along with fourteen known compounds were isolated from the aerial parts of Inula japonica. The structures of these new compounds were elucidated by spectroscopic methods (IR, EIMS, HRMS, 1D and 2D NMR). 1,6alpha-dihydroxy-4alphaH-1,10-secoeudesma-5(10),11(13)-dien-12,8beta-olide exhibited appreciable cytotoxic activity against cultured SMMC-7721 (human hepatoma cell) and HO-8910 (human ovarian carcinoma cell) with IC 50 values of 52.22 and 21.32 microg/mL, while 5alphaH-eudesma-4(15),11(13)-dien-12,8beta-olide showed remarkable cytotoxic activity against cultured SMMC-7721 and HO-8910 with IC 50 values of 6.21 and 5.28 microg/mL, respectively.     

A potent anti-complementary acylated sterol glucoside fromOrostachys japonicus

In order to isolate substances that inhibit the hemolytic activity of human serum against erythrocytes, we have evaluated whole plants of the Orostachys japonicus species with regard to its anti-complement activity, and have identified its active principles following activity-guided isolation. A methanol extract of the O. japonicus, as well as its n-hexane soluble fraction, exhibited significant anti-complement activity on the complement system, which was expressed as total hemolytic activity. A bioassay-guided chromatographic separation of the constituents resulted in the isolation of three known compounds 1-3 from the active n-hexane fraction. The structure of these compounds were analyzed, and they were identified as hydroxyhopanone (1), beta-sitosteryl-3-O-beta-D-glucopyranosyl-6'-O-palmitate (2), and beta-sitosteryl-3-O-beta-D-glucopyranoside (3), respectively. Of these compounds, compound 2 exhibited potent anti-complement activity (IC50= 1.0 +/- 0.1 microM) on the classical pathway of the complement, as compared to tiliroside (IC50= 76.5 +/- 1.1 microM), which was used as a positive control. However, compounds 1 and 3 exhibited no activity in this system.     

哥兰叶化学成分的研究

为研究哥兰叶(Celastrus gemmatus Loes.)中的化学成分，用Diaion HP-20，Toyopearl HW-40，silica gel等柱色谱方法，从其70%含水丙酮提取物中分离得到化合物，并根据理化性质和波谱数据鉴定其结构。共得到9个化合物，分别为左旋马尾松树脂醇-3a-O-β-D-吡喃葡糖苷(1)，ambrosidine(2)，异落叶松脂素-9-O-β-D-吡喃葡糖苷(3)，山柰酚-3-O-β-D-吡喃葡糖苷(紫云英苷)(4)，山柰酚-3-O-α-L-吡喃鼠李糖基-(1→6)-β-D-吡喃葡糖苷(5)，山柰酚-3-O-α-L-吡喃鼠李糖基-(1→2)-β-D-吡喃葡糖苷(6)，芹菜素-7-O-β-D-葡糖醛酸苷(7)，芹菜素-7-O-β-D-吡喃葡糖醛酸甲酯(8)，D-山梨醇(9)。化合物1为新化合物，其余化合物为首次从该属植物中分离得到。本文为首次报道该属植物中的木脂素类化合物。     

A novel isoflavonoid from Millettia puguensis

From the roots of Millettia puguensis (Leguminosae), a novel isoflavonoid (5), 2'-methoxy-4',5'-methylenedioxy-7,8-[2-(1-methylethenyl)furo]isoflavone, and four known compounds, i. e., lupeol (1), (-)-maackiain (2), 6,7-dimethoxy-3',4'-methylenedioxyisoflavone (3) and 7,2'-dimethoxy-4',5'-methylenedioxyisoflavone (4) were isolated and identified by 1H-, 13C-NMR and mass spectroscopy. All compounds were evaluated for their antiprotozoal and cytotoxic activities, but only a moderate antileishmanial activity was observed for compound 3 (IC50 = 32 microM against Leishmania infantum), and a moderate cytotoxicity for compound 2 (IC50 = 43 microM on MRC-5 cells).     

Total synthesis of a demethoxy-egonol fromStyrax obassia

The total synthesis of a demethoxy-egonol isolated from Styrax obassia, 5-(3-hydroxypropyl)-2-(3',4'-methylenedioxyphenyl)benzofuran (9), is described. The key steps involve the construction of a 2-arylbenzofuran skeleton 7 from methyl 3-(4-hydroxyphenyl)propionate with 2-chloro-2-methylthio-(3',4'-methylenedioxy)acetophenone (6) in the presence of ZnCl2 and successive desulfurization of the resulting product 7.