Polyphenolic compounds from the leaves of Koelreuteria paniculata Laxm

From the fresh leaves of Koelreuteria paniculata Laxm (Sapindaceae), four new compounds, named ethyl p-trigallate (1), 3"-O-galloyl-4'-O-galloyl-4-O-galloyl-gallic acid (2), ethyl p-heptagallate (3) and 3"-galloylquercitrin (4), together with 12 known compounds namely catechin (5), galloylepicatechin (6), isorhamnetin (7), kaempferol-3-O-arabinopyranoside (8), quercetin-3'-O- g -D-arabinopyranoside (9), quercitrin (10), methyl p-digallate (11), methyl m-digallate (12), p-digalloyl acid (13), m-digalloyl acid (14), hyperin (15) and kaempferol-3-O- f -L-rhamnoside (16) were isolated by extensive column chromatographic separation. Their structures were elucidated on the basis of chemical and spectroscopic methods. Compound 9 was not reported previously with pyranoside of arabinose at C-3'. Compounds 4 and 9 possessed the activity for PTK inhibition.     

Antifungal Diterpenoids and Flavonoids from Ballota inaequidens.

ABSTRACT

Two diterpenoids (hispanolone 1, ballonigrine 2) and six flavonoids (5-hydroxy-3,7,4′-trimethoxyflavone 3, retusin 4, 5-hydroxy-7,4′-dimethoxyflavone 5, pachypodol 6, 5-hydroxy-3,6,7,4′-tetramethoxyflavone 7, 5-hydroxy-7,3′,4′-trimethoxyflavone 8) have been isolated from the aerial parts of Ballota inaequidens. Hub.-Mor. & Patzak. Among them, 7 has not been reported previously in the genus Ballota.. The antibacterial and antifungal activities of 1–4, 6, and 8 were tested against Bacillus subtilis., Staphylococcus aureus., Escherichia coli., Pseudomonas aeruginosa., Candida albicans., and Candida crusei..     

Carbamate derivatives of felbamate as potential anticonvulsant agents

Several monocarbamate compounds derived from felbamate were synthesized and 11 target compounds (1, 4, and 6–14) were initially evaluated in mice MES and PTZ models in our laboratory. Carbamate compounds with varying substituents on the oxygen (1–4) gave anticonvulsant activity with a wide range of ED₅₀ in MES test from <20 mg/kg (2) to >300 mg/kg (4) and compounds with different groups on the nitrogen (5–14) also were quite active in the range of 15 mg/kg (14) to 170.5 mg/kg (6). This suggested that the spatial limitation in the MES model seemed flexible especially on the nitrogen end. All tested compounds showed some activity against mice scPTZ test, but none had the ED₅₀ value <50 mg/kg. Ten selected compounds (1 and 6–14) for subsequent pharmacological evaluation in NIH all gave positive mice MES activity except 8 and 9, which were unexpectedly active in rats after further evaluations. Among the compounds, 1, 8, and 9 advanced to the quantitative study and 1 and 9 provided the highest PI values, 15 and 21, respectively, in the rat oral MES test.     

Chemical constituents of Euonymus fortunei

A new flavonol glycoside, kaempferol-3-O-β-d-(2-O-E-p-coumaroyl)-glucopyranosyl-7-O-α-l-rhamnopyranoside (1), along with eleven known compounds including five flavonol glycosides (2–6), one phenolic glycoside (7), two megastigmane glycosides (8 and 9), two triterpenoids (10 and 11) and one alditol (12), was isolated from the aerial parts of Euonymus fortunei. Their structures were determined on the basis of spectroscopic analysis and chemical evidence. Compounds 2–4, 7, 8, and 10–12 were evaluated their antimicrobial activities against Ureaplasma urealyticumin vitro, but all tested compounds have no useful activities against Ureaplasma urealyticum.     

Uptake of Ozone in Human Lungs and Its Relationship to Local Physiological Response

To investigate whether intersubject variations in the dose of inhaled ozone (O₃) cause corresponding variations in the physiological response, 28 female and 32 male nonsmokers participated in a 1-h continuous inhalation of clean air or 0.25 ppm O₃ while exercising on a cycle ergometer at a constant ventilation rate of 30 L/min. The exposure protocols included continuous monitoring of respiratory flow rate and O₃ concentration from which O₃ uptake (OZU) and fractional uptake efficiency (UE) were computed. Pre-to-post changes in forced expired volume in 1 s (%ΔFEV₁), peripheral cross section for carbon dioxide diffusion (%Δ A_P), and Fowler dead space volume (V_D) were also measured for each exposure. Individual values of UE ranged from.70 to.98 among all the subjects, with significant differences (p < .05) existing between men and women. These intersubject differences were inversely correlated with breathing frequency and directly correlated with tidal volume. The mean ± SD values of %Δ FEV₁, %Δ A_P, and %Δ V_D were all significantly more negative in the O₃ exposure session (?13.31 ± 13.40, ?8.14 ± 7.62, and ?4.20 ± 5.12, respectively) than in the air exposure session (?0.06 ± 4.56, 0.22 ± 10.82, and ?0.70 ± 6.88, respectively). Finally, our results showed that neither %ΔFEV₁ nor %Δ V_D was correlated OZU, whereas there was a significant relationship (ρ = ?0.325, p = .0257) between %Δ A_P and OZU. We conclude that the overall uptake of O₃ is a weak predictor of intersubject variations in distal airspace response, but is not a predictor of intersubject variations in conducting airway responses.     

Synthesis and antimicrobial activities of N-chloroacetyl-2,6-diarylpiperidin-4-ones

An array of new N-chloroacetyl-2,6-diarylpiperidin-4-ones has been synthesised and their antibacterial activity against Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, and Salmonella typhi, and antifungal activity against Cryptococcus neoformans, Candida albicans, Rhizopus sp., Aspergillus flavus, and Aspergillus niger examined. Compounds 14 against P. aeruginosa, 15 against S. typhi, 16 against S. aureus, and 19 against B. subtilis showed marked antibacterial activity. Similarly, compounds 15 and 19 against A. niger and 19 against A. flavus exerted significant antifungal activities.     

Antiviral phenolics from Antenoron filiforme var. neofiliforme

Abstract

Two new phenolics, 1,3-di-O-p-coumaroyl-2′,6′-di-O-acetylsucrose (1) and quercetin 3-O-β-D-apiofuranoyl-(1→2)-α-L-rhamnopyranoside (2), along with nine known compounds (3–11), were isolated from the whole plants of Antenoron filiforme var. neofiliforme. Their chemical structures were characterized on the basis of various spectroscopic techniques. This is the first report of the isolation of phenylpropanoid sucrose (1, 3–4) from the genus Antenoron. The bioassay results showed that compound 11 exhibited antiviral activity against the Coxsackie virus B3 (CVB3).     

New flavonoids with 2BS cell proliferation promoting effect from the seeds of <Emphasis Type="Italic">Trigonella foenum</Emphasis>-<Emphasis Type="Italic">graecum</Emphasis> L.

Ten flavonoids were isolated from the ethyl acetate-soluble fraction of the ethanolic extract of the seeds of Trigonella foenum-graecum and their structures were elucidated on the basis of spectroscopic methods to be 5,7,3′-trihydroxy-5′-methoxylisoflavone (1), biochanin A (2), formononetin (3), irilone (4), tricin (5), daidzein (6), calycosin (7), orientin-2″-O-p-trans-coumarate (8), vitexin-2″-O-p-trans-coumarate (9), and tricin-7-O-β-d-glucopyranoside (10). Compounds 1 and 8 are new flavonoids, and 8 and 9 strongly promoted 2BS cell proliferation induced by H₂O₂.     

Stilbenes and oligostilbenes from leaf and stem of <Emphasis Type="Italic">Vitis amurensis</Emphasis> and their cytotoxic activity

Chromatographic separation of the EtOAc fraction from the leaf and stem of Vitis amurensis led to the isolation of six oligostilbenoids (i.e., r-2-viniferin (1), trans-amurensin B (2), trans-ɛ-viniferin (3), gnetin H (4), amurensin G (5), (+)-ampelopsin A (8)) and four stilbenoids (i.e., trans-resveratrol (6), (+)-ampelopsin F (7), piceatannol (9), and trans-piceid (10)). The structures have been identified on the basis of spectroscopic evidence and physicochemical properties. The isolates were investigated for cytotoxic activity against three cancer cell lines in vitro using the MTT assay method. Amurensin G (5) and trans-resveratrol (6) showed significant cytotoxic activity against L1210, K562 and HTC116 cancer cell lines with IC₅₀ values ranging from 15.7 ± 2.1 to 30.9 ± 1.8 μM. (+)-Ampelopsin A (8) and trans-piceid (10) exhibited considerable cytotoxic activity against L1210 (IC₅₀ values of 30.6 ± 4.1 and 28.7 ± 2.81 μM, respectively) and K562 (IC₅₀ values of 38.6 ± 0.82 and 24.6 ± 0.76 μM, respectively). Gnetin H (4) showed only weak cytotoxic activity against L1210 with an IC₅₀ value of 40.1 ± 4.23 μM. On the other hand, r-2-viniverin (1), trans-amurensin B (2), trans-ɛ-viniferin (3), (+)-ampelopsin F (7), and piceatannol (9) exhibited no activity on three cancer cell lines.     

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.     

Cholinesterase and BACE1 inhibitory diterpenoids from <Emphasis Type="Italic">Aralia cordata</Emphasis>

Fourteen diterpenes were isolated from the n-hexane fraction of the roots of Aralia cordata (syn. = A. continentalis). Through spectroscopy, the chemical structures were determined as: ent-pimara-8(14),15-diene-19-oic acid (1); ent-kaur-16-en-19-oic-acid (2); 18-nor-ent-pimara-8(14),15-diene-4β-ol (3); 18-nor-ent-kaur-16-ene-4β-ol (4); ent-pimara-8(14),15-diene-19-ol (5); 7α-hydroxy-ent-pimara-8(14),15-diene-19-oic acid (6); 7β-hydroxy-ent-pimara-8(14),15-diene-19-oic acid (7); ent-pimar-15-en-8α,19-diol (8); 7-oxo-ent-pimara-8(14),15-diene-19-oic acid (9); 16α-hydroxy-17-isovaleroyloxy-ent-kauran-19-oic acid (10); 17-hydroxy-ent-kaur-15-en-19-oic acid (11); 15α,16α-epoxy-17-hydroxy-ent-kauran-19-oic acid (12); 16α,17-dihydroxy-ent-kauran-19-oic acid (13); and 16α-methoxy-17-hydroxy-ent-kauran-19-oic acid (14). Compounds 4, 5, 8, 12, and 14 were first isolated from this plant. The anti-Alzheimer and antioxidant effects of ent-pimarane-type diterpenes 1, 3, 5, 8, and 9, as well as ent-kaurane-type diterpenes 2, 4, and 10∼13, were evaluated via β-site amyloid precursor protein cleaving enzyme 1 (BACE1), acetylcholinesterase (AChE), butyrylcholinesterase (BChE), peroxynitrite (ONOO⁻), and nitric oxide (NO·) assays. Of the compounds tested, 8 exerted the most effective BChE inhibition with an IC₅₀ value of 7.58 μM, followed by 3, 13, 11, 2, and 10. Compounds 9∼11 exhibited good BACE1 inhibitory activities with IC₅₀ values of 18.58∼24.10 μM. However, 11 showed marginal AChE inhibitory effect, and all compounds tested showed no scavenging activities on ONOO⁻ and NO· at a concentration of 100 μM.     

Investigation of 6-O-methyl-scutellarein metabolites in rats by ultra-flow liquid chromatography/quadrupole-time-of-flight mass spectrometry

Context Scutellarin (1) has been widely used in China to treat acute cerebral infarction and paralysis induced by cerebrovascular diseases. However, scutellarin (1) has unstable metabolic characteristics.

Objective The metabolic profile of 6-O-scutellarein was studied to determine its metabolic stability in vivo.

Materials and methods In this study, a method of UFLC/Q-TOF MS was used to study the 6-O-methyl-scutellarein metabolites in rat plasma, urine, bile and faeces after oral administration of 6-O-methyl-scutellarein (3). One hour after oral administration of 6-O-methyl-scutellarein (3) (34?mg/kg), approximately 1?mL blood samples were collected in EP tubes from all groups. Bile, urine and faeces samples were collected from eight SD rats during 0–24?h after oral administration. The mass defect filtering, dynamic background subtraction and information dependent acquisition techniques were also used to identify the 6-O-methyl-scutellarein metabolites.

Results The parent compound 6-O-methyl-scutellarein (3) was found in rat urine, plasma, bile and faeces. The glucuronide conjugate of 6-O-methyl-scutellarein (M1, M2), diglucuronide conjugate of 6-O-methyl-scutellarein (M3), sulphate conjugate of 6-O-methyl-scutellarein (M4), glucuronide and sulphate conjugate of 6-O-methyl-scutellarein (M5), methylated conjugate of 6-O-methyl-scutellarein (M6) were detected in rat urine. M1, M2 and M3 were detected in rat bile. M1 was found in rat plasma and M7 was detected in faeces.

Discussion and conclusion Because the parent compound 6-O-methyl-scutellarein (3) was found in rat urine, plasma, bile and faeces, we speculate that 6-O-methyl-scutellarein (3) had good metabolic stability in vivo. This warrants further study to develop it as a promising candidate for the treatment of ischemic cerebrovascular disease.     

Secoiridoid glycosides from the leaves of <Emphasis Type="Italic">Hydrangea macrophylla</Emphasis> subsp. <Emphasis Type="Italic">serrata</Emphasis>

Seven secoiridoid glycosides, secologanin dimethyl acetal (1), n-butyl vogeloside (2), n-butyl epi-vogeloside (3), (7R)-n-butyl morroniside (4), hydrangenoside A (5), hydrangenoside C (6), and hydrangenoside A dimethyl acetal (7), have been isolated from the leaves of Hydrangea macrophylla subsp. serrata (Thunb.) Makino (Saxifragaceae). The structures were elucidated on the basis of spectral data.     

Microbial deglycosylation and ketonization of ginsenosides Rg1 and Rb1 by Fusarium oxysporum

Two major ginsenosides, ginsenoside-Rg₁ (1) and ginsenoside-Rb₁ (2), were transformed by the fungus Fusarium oxysporum f. sp. Lycopersici (Z-001). 1 was converted into five metabolites, ginsenoside-F₁ (3), 6α,12β-dihydroxydammar-3-one-20(S)-O-β-d-glucopyranoside (4), 3a-oxa-3a-homo-6α,12β-dihydroxydammar-3-one-20(S)-O-β-d-glucopyranoside (5), 20(S)-protopanaxatriol (6), and 3-oxo-20(S)-protopanaxatriol (7). 2 was converted into four metabolites, ginsenoside-Rd (8), ginsenoside-F₂ (9), compound K (10), and 12β-hydroxydammar-3-one-20(S)-O-β-d-glucopyranoside (11). The structures of these metabolites were determined by the analysis of extensive spectroscopic data. Among them, 4 and 5 were two new compounds. Deglycosylation and ketonization at C-3 were recognized as the characteristic reactions of this strain.     

Microbial transformation of deoxyandrographolide by Fusarium graminearum AS 3.4598

Biotransformation of deoxyandrographolide (1) by Fusarium graminearum AS 3.4598 was investigated in this paper. And five transformed products of 1 by F. graminearum AS 3.4598 were obtained. Their chemical structures were characterized as 3-oxo-8α,17β-epoxy-14-deoxyandrographolide (2), 3-oxo-14-deoxyandrographolide (3), 3-oxo-17,19-dihydroxyl-8,13-ent-labdadien-15,16-olide (4), 1β-hydroxyl-14-deoxyandrographolide (5), and 7β-hydroxyl-14-deoxyandrographolide (6) by spectral methods including 2D NMR. Among them, products 2, 4, and 5 are new.     

Irritant and co-carcinogenic diterpene esters from the latex of Euphorbia cauducifolia L.

Ten (1–10) irritant and mild co-carcinogenic diterpene esters were isolated from the latex of Euphorbia cauducifolia L. using bioassay-guided countercurrent distribution and other chromatographic techniques. The isolated compounds were characterized on the basis of spectroscopic results and mass measurements. As an outcome, the ingenane-type esters were established with the following structures: 3-O-angeloyl-17-O-palmatoylingenol (1), 3-O-palmatoyl-5-O-angeloylingenol (2), 5-O-angeloyl-17-O-palmatoylingenol (3), 3-O-angeloyl-5-O-palmatoylingenol (4), 17-O-(2Z,4E,6Z)-2,4,6-tetradecatrienoyl-20-O-palmatoylingenol (5), 5-O-angeloyl-17-O-benzoylingenol (6), 5-O-angeloyl-17,20-diacetoxyingenol (7), 3-O-angeloyl-17-O-benzoyl-20-acetoxyingenol (8), 3-acetoxy-5-O-angeloyl-17-O-benzoylingenol (9), and 5-O-angeloyl-3,17,20-triacetoxyingenol (10). Their biological screening revealed that they are moderate irritants, and low to moderate tumor promoters compared to TPA, but hardly showed any solitary carcinogenic activity. The isolated esters represent new compounds and were not reported before from any source.     

Iridoid glucoside, (3<Emphasis Type="Italic">R</Emphasis>)-oct-1-en-3-ol glycosides,and phenylethanoid from the aerial parts of <Emphasis Type="Italic">Caryopteris incana</Emphasis>

Eleven compounds of interest were isolated from the aerial parts of Caryopteris incana, specifically a new acyl derivative (3) of 8-O-acetylharpagide, two new (3R)-oct-1-en-3-ol glycosides (5, 6), and 6-O-caffeoylphlinoside A (11) along with seven known compounds, 8-O-acetylharpagide (1), 6′-O-p-coumaroyl-8-O-acetylharpagide (2), (3R)-oct-1-en-3-ol (matsutake alcohol) O-α-l-arabinopyranosyl-(1″ → 6′)-O-β-d-glucopyranoside (4), apigenin 7-O-neohesperidinoside (7), 6′-O-caffeoylarbutin (8), and two phenylethanoids, leucosceptoside A (9) and phlinoside A (10). This paper deals with structural elucidation of the new compounds.     

Manoalide derivatives from a sponge,Luffariella sp.

A new derivative of manoalide, 24-n-propyl-O-manoalide (1) together with manoalide (4) and four known derivatives (2, 3, 5, 6) were isolated from the methanolic extract of a sponge. Their structures were elucidated on the basis of spectroscopic method. All the compounds showed significant cytotoxicity against HCT-116 cell line by MTS assay. Secomanoalide indicated antifungal activity on fungal lines Candida glabrata, Candida krusei and Candida albicans by in vitro antibiotic assay.     

Antifungal Flavonoids from Ballota glandulosissima

Abstract

The flavonoids kumatakenin (1), pachypodol (2), 5-hydroxy-7,3′,4′-trimethoxyflavone (3), velutin (4), salvigenin (5), retusin (6) and corymbosin (7) have been isolated from the aerial parts of Ballota glandulosissima Hub.-Mor & Patzak. Among them, 2–4 and 7 have not been reported previously in the genus Ballota. The antibacterial and antifungal activities of 1–4 and 6 were tested against Bacillus subtilis, Staphylococcus aureus, Staphylococcus faecalis, Echerichia coli, Pseudomonas aeruginosa, Candida albicans, Candida krusei and Candida galabrata.     

Three new eudesmanoids from the Formosan soft coral Nephthea erecta

Chemical investigations on the organic extract of the Formosan soft coral Nephthea erecta led to the isolation of two new eudesmanoids, (4R*,5S*,6Z,10R*)-8-oxo-eudesm-6-en-5α,11-diol (1) and (6E,10R )-4,5-dioxo-11-methoxy-eudesm-6-ene (2), together with one new tri-nor-eudesmane sesquiterpenoid, (4S*,5E,10R*)-7-oxo-tri-nor-eudesm-5-en-4β-ol (3). The structures of metabolites 1–3 were elucidated through extensive spectroscopic analyses and by comparison with those reported in the literature. The anti-inflammatory activity using RAW 264.7 macrophages and their cytotoxicity against selected cancer cells of 1–3 were evaluated in vitro.