Glycosides from Roots of Cyathula officinalis Kuan

Abstract: To search for new and bioactive compounds from traditional Chinese medicines, a new glycoside, 3-O-[α- L -rhamnopyranosyl-(1→3)-( n -butyl-β- D -glucopyranosiduronate)]-28-O-β- D -glucopyranosyloleanolic acid ( 1 ), was isolated from the roots of Cyathula officinalis Kuan, along with 3-O-(methyl-β- D -glucopyranosiduronate)-28-O-β- D -glucopyranosyl oleanolic acid ( 2 ), 3-O-β- D -glucopyranosyl oleanolic acid ( 3 ), 3-O-β- D -glucuronopyranosyl oleanolic acid ( 4 ), 3-O-[β- L -rhamnopyranosyl-(1→3)-(β- D -glucuronopyranosyl)] oleanolic acid ( 5 ), 3-O-(β- D -glucuronopyranosyl)-28-O-β- D -glucopyranosyl oleanolic acid ( 6 ), 28-O-β- D -glucuronopyranosyl-(1→4)-β- D -glucopyranosyl hederagenin ( 7 ), 3-O-[β- L -rhamnopyranosyl-(1→3)-β- D -glucuronopyranosyl]-28-O-β- D -glucopyranosyl oleanolic acid ( 8 ), and 3-O-[β- D -glucopyranosyl-(1→2)-α- L -rhamnopyranosyl-(1→3)-β- D -glucuronopyranosyl]-28-O-β- D -glucopyranosyl oleanolic acid ( 9 ). The structures of these compounds were determined based on spectral and chemical evidence. The 50 per cent growth-inhibiting (GI₅₀) of compounds 1 and 5 against MDA-MB-231 (a human breast cancer cell line) was 3.44 × 10^-4 and 4.66 × 10^-4 mol/L, respectively.
(Managing editor: Wei WANG)     

A novel function of the MA-3 domains in transformation and translation suppressor Pdcd4 is essential for its binding to eukaryotic translation initiation factor 4A

An alpha-helical MA-3 domain appears in several translation initiation factors, including human eukaryotic translation initiation factor 4G (eIF4G) and DAP-5/NAT1/p97, as well as in the tumor suppressor Pdcd4. The function of the MA-3 domain is, however, unknown. C-terminal eIF4G (eIG4Gc) contains an MA-3 domain that is located within the eIF4A-binding region, suggesting a role for eIF4A binding. Interestingly, C-terminal DAP-5/NAT1/p97 contains an MA-3 domain, but it does not bind to eIF4A. Mutation of amino acid residues conserved between Pdcd4 and eIF4Gc but not in DAP-5/NAT1/p97 to the amino acid residues found in the DAP-5/NAT1/p97 indicates that some of these amino acid residues within the MA-3 domain are critical for eIF4A-binding activity. Six Pdcd4 mutants (Pdcd4(E249K), Pdcd4(D253A), Pdcd4(D414K), Pdcd4(D418A), Pdcd4(E249K,D414K), and Pdcd4(D253A,D418A)) lost >90% eIF4A-binding activity. Mutation of the corresponding amino acid residues in the eIF4Gc also produced similar results, as seen for Pdcd4. These results demonstrate that the MA-3 domain is important for eIF4A binding and explain the ability of Pdcd4 or eIF4Gc but not DAP-5/NAT1/p97 to bind to eIF4A. Competition experiments indicate that Pdcd4 prevents ca. 60 to 70% of eIF4A binding to eIF4Gc at a Pdcd4/eIF4A ratio of 1:1, but mutants Pdcd4(D253A) and Pdcd4(D253A,D418A) do not. Translation of stem-loop structured mRNA is susceptible to inhibition by wild-type Pdcd4 but not by Pdcd4(D253A), Pdcd4(D418A), or Pdcd4(D235A,D418A). Together, these results indicate that not only binding to eIF4A but also prevention of eIF4A binding to the MA-3 domain of eIF4Gc contributes to the mechanism by which Pdcd4 inhibits translation.     

Acylated iridoid glucosides from Veronica anagallis-aquatica

Three new (1-3) and four known iridoid glucosides (4-7) as well as a known phenylethanoid glycoside (8) were isolated from the aerial parts of Veronica anagallis-aquatica and their structures were determined as 6'-O-benzoyl-8-epiloganic acid named aquaticoside A (1), 6'-O-p-hydroxybenzoyl-8-epiloganic acid named aquaticoside B (2), 6'-O-benzoyl-gardoside named aquaticoside C (3), veronicoside (4), catalposide (5), verproside (6), verminoside (7) and martynoside (8) on the basis of 1D and 2D NMR spectral analysis.     

Chemical constituents from Celastrus aculeatus Merr.

Phytochemical investigation of Celastrus aculeatus Merr. led to the isolation of nine compounds. Their structures were identified to be dulcitol (1), β-sitosterol (2), n-tritriacontane (3), nimbidiol (4), pristimerin (5), p-hydroxybenzoic acid (7), vanillic acid (8), 3, 5-dimethoxy-4-hydroxybenzoic acid (9) and a new compound named pristimerol (6) on the basis of mass and NMR spectra. This is the first report of phenolic acids (compounds 7–9) from C. aculeatus Merr. We present the HR-MS, 1D NMR (¹H, ¹³C NMR, DEPT) and 2D NMR (HMBC) data of the new compound (6).     

A sugar ester and an iridoid glycoside from Scrophularia ningpoensis

From cytotoxic extracts of the roots of Scrophularia ningpoensis Hemsl. (Scrophulariaceae) a new sugar ester, ningposide D (3-O-acetyl-2-O-p-methoxycinnamoyl-alpha(beta)-L-rhamnopyranose) (1) and a new iridoid glycoside, scrophuloside B4 (6-O-(2'-O-acetyl-3'-O-cinnamoyl-4'-O-p-methoxycinnamoyl-alpha-L-rhamnopyranosyl) catalpol) (2) along with known compounds: oleanonic acid (3), ursolonic acid (4), cinnamic acid (5), 3-hydroxy-4-methoxy benzoic acid (6), 5-(hydroxymethyl)-2-furfural (7) and beta-sitosterol (8) were isolated. The structures of the new compounds were elucidated by spectral data (1, 2D NMR, EI, HRESI-MS and MS/MS). Oleanonic acid (3) and ursolonic acid (4) were found to be cytotoxic against a series of human cancer cell lines with IC50=4.6, 15.5 microM on MCF7; 4.2, 14.5 microM on K562; 14.8, 44.4 microM on Bowes; 24.9, 43.6 microM on T24S; 61.3, 151.5 microM on A549, respectively. Beta-sitosterol (8) inhibited Bowes cells growth at IC50=36.5 microM. Scrophuloside B4 (2) showed activity on K562 and Bowes cells at IC50=44.6, 90.2 microM, respectively.     

Cytotoxic triterpenes from the twigs of Celtis philippinensis

Two triterpene esters, 3beta-trans-sinapoyloxylup-20(29)-en-28-ol (1) and 3beta-trans-feruloyloxy-16 beta-hydroxylup-20(29)-ene (2), were isolated as cytotoxic constituents from the chloroform-soluble extract of the twigs of Celtis philippinensis, along with five known triterpenes, 3beta-O-(E)-feruloylbetulin (3), 3beta-O-(E)-coumaroylbetulin (4), betulin (5), 20-epibryonolic acid (6), and ursolic acid (7). The structures of 1 and 2 were assigned from their 1D and 2D NMR spectroscopic data. All isolates were evaluated for cytotoxicity against several human cancer cell lines.     

龙眼果肉化学成分的研究

从龙眼(Dimocarpus longan Lour.)果肉的乙醇提取物中分离出9个化合物,分别鉴定为:二十四碳酸(1)、7,8-二甲基咯嗪(2)、(2S,3S,4R,10E)-2-[(2'R)-2'-羟基二十四碳酰胺]-10-十八碳烯-1,3,4-三醇(3)、尿嘧啶(4)、丁二酸(5)、腺苷(6)、甘露醇(7)、β-谷甾醇(8)和β-胡萝卜苷(9),其中化合物1～3、5和7为首次从龙眼果肉中分离得到.     

Free radical scavengers from the medicinal mushroom Inonotus xeranticus and their proposed biogenesis

New free radical scavengers, inoscavin D (1) and methylinoscavin D (2), were isolated from the methanolic extract of the fruiting bodies of Inonotus xeranticus (Hymenochaetaceae), along with the known compounds phelligridin D (3), 3,4-dihydroxybenzaldehyde (4), and 3,4-dihydroxybenzoic acid (5). Their structures were established by various spectroscopic analyses. Compounds 1 and 3 were proposed to be biosynthesized from the oxidative coupling of the precursor hispidin with 3,4-dihydroxybenzaldehyde and 3,4-dihydroxybenzoic acid, respectively. These compounds exhibited significant scavenging activity against the ABTS radical cation, and compounds 2 and 4 displayed moderate superoxide radical scavenging activity.     

Formation of leukotrienes E3, E4 and E5 in rat basophilic leukemia cells

Rat basophilic leukemia (RBL-1) cells incubated with ionophore A23187 and 5,8,11-eicosatrienoic acid produced three slow-reacting substances identified as leukotrienes C3, D3 and E3 by spectroscopic, chromatographic and enzymatic methods. 5,8,11,14,17-Eicosapentaenoic acid was similarly converted by RBL-1 cells to leukotrienes C5, D5. and E5. Leukotrienes C4, D4 and E4 were also formed in these experiments from endogenous arachidonic acid. Time-course studies, incubations with 3H-labeled leukotriene C3 and effects of acivicin [L-(alpha S, 5S)-alpha-amino-3-chloro-4,5-dihydro-5-isoxazoleacetic acid; a gamma-glutamyl transpeptidase inhibitor] indicated that leukotrienes C and D are intermediates in the formation of leukotrienes E. L-Cysteine enhanced the conversion of leukotriene C3 to leukotriene D3 and inhibited further degradation of leukotriene D3 to leukotriene E3.     

Studies on the Constituents of Aristolochia versicolar S. M. Hwang

Twenty-four constituents were isolated from the root of Aristolochia versicolar S. M. Hwang (collected from Guangxi province, China). Ten of them (two novel sesquiterpene lacrones and eight known compounds) were reported recently. This paper deals with the other eight compounds. From the petroleum ether extraction a sesquiterpene lactone, C15H20O2, mp. 94–95℃ [α]D36 –49˚ (C=1.8, EtOH), confirmed to be isoaristolactone, was obtained from plants for the first time. On the basis of spectral analysis (UV, IR, 1HNMR, 13CNMR, MS) and chemical reactions its structure was determined as B2. From the petroleum enter unsoluble sec- tion 6-methoxyaristolic acid methyl ester (D1), aristolic acid (D3), 6-methoxyaristolic acid (ari- stolinic acid) (D4f), 6-methoxyaristolochic acid methyl ester (D4y), aristolochic acid A(D5), β-sitosterol-D-glucoside (D10) and allantoin (C2) were isolated and identified. Dx, Ds, and Ds show ed antifertility activity in mice.     

Terpenoid and phenolic metabolites from the fungus xylaria sp. associated with termite nests

Three new sesquiterpene acids, xylaric acids A-C (1-3, resp.), and a new tetralone (=3,4-dihydronaphthalen-1(2H)-one) derivative, 4, along with nine known compounds, xylaric acid D (5), hydroheptelidic acid (6), gliocladic acid (7), chlorine heptelidic acid (8), trichoderonic acid A (9), 16-(α-D-mannopyranosyloxy)isopimar-7-en-19-oic acid (10), 16-(α-D-glucopyranosyloxy)isopimar-7-en-19-oic acid (11), 5-carboxymellein (12), and naphthalen-1,8-diol 1-O-α-D-glucopyranoside (13) have been isolated from the solid culture of the ascomycete fungus Xylaria sp. associated with termite nest. The structures of these compounds were elucidated primarily by NMR experiments. The absolute configurations of compounds 1-3 and 5-9 were determined by combination of X-ray data and CD spectral analysis. The absolute configuration of 4 was assigned by Snatzke's method. Compounds 8 and 11 showed slight cytotoxicities against two cell lines A549 and SGC7901.     

Stereocontrolled dopamine receptor binding and subtype selectivity of clebopride analogues synthesized from aspartic acid

Employing the achiral 4-aminopiperidine derivative clebopride as a lead compound, chiral analogues were developed displaying dopamine receptor binding profiles that proved to be strongly dependent on the stereochemistry. Compared to the D1 receptor, the test compounds showed high selectivity for the D2-like subtypes including D2(long), D2(short), D3 and D4. The highest D4 and D3 affinities were observed for the cis-3-amino-4-methylpyrrolidines 3e and the enantiomer ent3e resulting in K(i) values of 0.23 and 1.8 nM, respectively. The benzamides of type 3 and 5 were synthesized in enantiopure form starting from (S)-aspartic acid and its unnatural optical antipode.     

Phenylpropanoid glucosides from leaves of Coussarea hydrangeifolia (Rubiaceae)

Phenylpropanoid glycosides, 1'-O-benzyl-alpha-L-rhamnopyranosyl-(1'-->6')-beta-D-glucopyranoside (1) and alpha-L-xylopyranosyl-(4'-->2')-(3-O-beta-D-glucopyranosyl)-1'-O-E-caffeoyl-beta-D-glucopyranoside (2), together with the known derivatives, 1,6-di-O-caffeoyl-beta-D-glucopyranoside (3), 1-O-(E)-caffeoyl-beta-D-glucopyranoside (4) and 1-O-(E)-feruloyl-beta-D-glucopyranoside (5), were isolated from leaves of Coussarea hydrangeifolia. Their structures were determined by IR, HRESIMS, and 1D and 2D NMR experiments, and their antioxidant activities, evaluated by assaying the free radical scavenging capacity using the DPPH (1,1-diphenyl-2-picrylhydrazyl) radical as substrate. The antioxidant activities of 3 and 4 (IC50 values of 15.0 and 19.2 microM, respectively) were comparable to that of the standard positive control caffeic acid, whilst 2 and 5 were only weakly active and 1 was inactive.     

Cytotoxic bromoindole derivatives and terpenes from the Philippine marine sponge Smenospongia sp

A detailed chemical analysis of a Philippine marine sponge Smenospongia sp. has been performed. This study yielded four new metabolites, 5-bromo-L-tryptophan (1), 5-bromoabrine (2), 5,6-dibromoabrine (3) and 5-bromoindole-3-acetic acid (4). The pyrroloiminoquinone alkaloid, makaluvamine O (5) as well as 5,6-dibromotryptamine (6), aureol (7) and furospinulosin 1 (8) were also isolated. Although 1 and 4 have been synthesized previously, this is the first report on the isolation of these compounds from a natural source. The furanosesterterpene furospinulosin 1 (8) was obtained for the first time from the genus Smenospongia. The structures of all compounds were established by spectroscopic methods (UV, IR, 1D and 2D NMR, MS, [alpha]D). The cytotoxic potential of 1-8 was evaluated in a panel of isogenic HCT-116 human colon tumor cell lines.     

Chemical constituents of leaves and stem bark of Plumeria obtusa

The continued studies on the constituents of the fresh leaves and stem bark of Plumeria obtusa Linn. have led to the isolation and characterization of four new triterpenoids, dammara-12,20(22)Z-dien-3-one (1), dammara-12,20(22)Z-dien-3beta-ol (2), olean-12-en-3beta,27-diol (3), and 27-hydroxyolean-12-en-3-one (4) and 12 known compounds, which included eight triterpenoids; dammara-3beta,20(S),25-triol (5), urs-12-en-3beta-hydroxy-27-Z-feruloyloxy-28-oic acid (6), 3beta-hydroxyolean-12-en-28-oic acid (7), 3beta,27-dihydroxylupan-29-ene (8), 3beta-hydroxylupan-29-en-28-oic acid (9), 3beta-hydroxyursan-12-en-28-oic acid (11), 3beta-hydroxy-27-p-coumaroyloxy-olea-12-en-28-oic acid (12) and urs-12-en-3-one (15); an iridoid 1alpha-plumieride (10); a cardenolide 3alpha,14beta-dihydroxy-17beta-card-20(22)-enolide (13); a fatty acid ester methyl n-octadecanoate (14) and a steroid 3beta-hydroxy-delta5-stigmastane (16). The new constituents were characterized through spectroscopic studies including 1D (1H and 31C NMR) and 2D (COSY-45, NOESY, J-resolved, HMQC and HMBC) NMR and chemical transformations. This is the first report on the isolation of dammarane triterpenoids from P. obtusa. Compounds 5 and 6 are hitherto unreported from P. obtusa. The known compounds were identified by comparison of their spectral data with those reported in the literature.     

Antioxidant C-glycosyl flavones from the leaves of Sasa kurilensis var. gigantea

C-glycosyl flavones, kurilensin A (1) and B (2), together with two known compounds, tricin-4'-O-beta-d-glucopyranoside (3) and tricin-5-O-beta-d-glucopyranoside (4), were isolated from hot-water extracts of the leaves of Sasa kurilensis. The structure of the compounds was determined by spectroscopic analyses including 1D, 2D NMR and MS. The absolute configuration of sugar moieties in 1 and 2 was determined by chiral HPLC analyses of the benzoyl derivatives of acid hydrolysis. Compounds 1 and 2 exhibited higher radical scavenging activity than ascorbic acid in the 1,1-diphenyl-2-pycrylhydrazyl (DPPH) assay system.     

Six New Constituents from the Fruit of Hypericum patulum and Their Anti-Inflammatory Activity

Four new xanthone glucosides, 3-hydroxy-2-methoxyxanthone-4-O-β-D-glucopyranoside ( 1 ), 4,8-dihydroxy-2-methoxyxanthone-3-O-β-D-glucopyranoside ( 2 ), 2-methoxyxanthone-5-O-β-D-glucopyranoside ( 3 ), 4-hydroxy-2-methoxyxanthone-3-O-β-D-glucopyranoside ( 4 ), a new phenolic acid, 4,4′-dihydroxy-3,3′-imino-di-benzoic acid monomethyl ester ( 5 ), and a new isoquinoline, methyl 6-hydroxy-1-oxo-1,2,3,4-tetrahydroisoquinoline-4-carboxylate ( 6 ) were isolated from the fruit of Hypericum patulum. The structural elucidation of the isolated compounds was primarily based on HR-ESI-MS, UV, IR, 1D and 2D NMR. All compounds were evaluated for their inhibitory effect against LPS-induced NO production in RAW 264.7 cells. Compound 2 , 3 exhibited moderate inhibitory activity against NO production.     

草果果实中的酚性成分

从草果( Amomum tsao-ko) 果实的甲醇提取物中分离得到了9 个酚性化合物, 其中一个为新的糖基被酰化的酚性配糖体。用1D, 2D NMR 和MS 等现代波谱学方法鉴定为2-甲氧基-1 , 4-二苯酚-1-O - [6- O -(3-甲氧基-4-羟基苯甲酰基) ]-β-D-吡喃葡萄糖苷(1) 。8 个已知化合物分别为3′, 5′-二-C-β-D-吡喃葡萄糖基根皮素( 2)、芦丁(3) 、槲皮素-3- O-β-D-吡喃葡萄糖苷(4 ) 、邻苯三酚( 5 )、邻苯二酚( 6) 、对羟基苯甲酸( 7)、原儿茶酸(8) 和香草酸(9) 。化合物2 , 3 , 5 , 7～9 均为首次从草果果实中分离得到。     

Evaluation of immunostimulatory and growth promoting effect of seed fractions of Achyranthes aspera in common carp Cyprinus carpio and identification of active constituents

Immunostimulatory and growth promoting properties of Achyranthes aspera seeds were studied with larvae of common carp Cyprinus carpio. Four experimental diets were prepared using raw (D1) and alcohol (D2), petroleum ether (D3) and 50% aqueous alcohol (D4) extracts of A. aspera seeds. Diet without seed served as control (D5). Fish were fed with test/control diet for 30 days and then immunized with 10 μl of c-RBC. Blood samples were collected 7 days after immunization. Survival (93 ± 3%) of fish was significantly (P < 0.05) higher in D1 diet fed group compared to others. Highest specific growth rate was found in fish fed with diet D2. Significantly (P < 0.05) higher levels of serum protein and albumin were found in D1 and D3 compared to others. Highest serum globulin level was found in D1, which was followed by D3, D2, D4 and D5. Hemagglutination titer level was 5-18 folds higher in diet D3 fed fish compared to others. SGOT and SGPT levels were significantly (P < 0.05) higher in control group compared to the treated groups. Myeloperoxidase activity was significantly (P < 0.05) higher in D1 (2.513 ± 0.27 λ 450 nm) and D3 (2.38 ± 0.07 λ 450 nm) diets fed groups compared to others. The best performance of fish was found in raw A. aspera seeds incorporated diet fed group and the active constituents were identified as ecdysterone and two essential fatty acids linolenic acid and oleic acid.     

Circularly polarized emission studies on Tb3+ and Eu3+ complexes with potentially terdentate amino acids in aqueous solution.

Circularly polarized emission (CPE) and total emission (TE) spectra are reported for Eu3+ and Tb3+ complexes of L-aspartic acid (L-asp), L-serine (L-ser), L-threonine (L-thr) and L-histidine (L-his) in D2O solution under various pH conditions. Variations in TE and CPE intensities and in CPE splittings and sign patterns as functions of solution pH are correlated with lanthanide ion/ligand binding characteristics and with structural changes in the coordination environment of the metal ion. In the Eu3+/amino acid systems, the emission bands associated with the 5D0 leads to 7F1 and 7F2 Eu3+ transitions are monitored, and in the Tb3+/amino acid systems the 5D4 leads to 7F5 Tb3+ emission is examined.