Two new and four known polyphenolics obtained as new cell-cycle inhibitors from Rubus aleaefolius poir

Two new polyphenolics, rubuphenol (1) and sanguiin H-2 ethyl ester (2), were isolated together with ellagic acid (3), ethyl gallate (4), 1,2,3,4,6-penta-O-galloyl-g -D-glucopyranose (5) and 1,2,3,6-tetra-O-galloyl-g -D-glucopyranose (6) as new cell-cycle inhibitors from Rubus aleaefolius by bioassay-guided separation procedure and the structures of 1 and 2 were elucidated by spectroscopic method. Compounds 1 - 6 inhibited the cell cycle progression of tsFT210 cells at the G₀/G₁ phase with the MIC values of 14.6 w M (1), 22.1 w M (2), 10.3 w M (3), 7.8 w M (4), 7.9 w M (5) and 6.6 w M (6).     

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.     

A new triterpenoid from <Emphasis Type="Italic">Panax ginseng</Emphasis> exhibits cytotoxicity through p53 and the caspase signaling pathway in the HepG2 cell line

A new triterpenoid, 20(R),22(ξ),24(S)-dammar-25(26)-ene-3β,6α,12β,20,22,24-hexanol (1), and three known triterpenoids, β-D-glucopyranoside,(3β,12β)-12,20-dihydroxydammar-24-en-3-yl,6-acetate (2), 20(R)-ginsenoside Rg₃ (3), and 20(R)-ginsenoside Rh₂ (4), were isolated from the leaves of Panax ginseng. Their structures were determined by chemical analysis and spectral methods (IR, 1D and 2D NMR, HR-ESI-MS). Compounds 1–4 were exhibited various degrees of cytotoxicity in the human hepatoma cell line, HepG2. Compound 1 had the highest cytotoxic potency, with an IC₅₀ value of 20.1 μM, by stimulating p53-mediated cell cycle arrest at the G1 to S phase transition, leading to apoptosis via activation of the caspase signaling pathway.     

Four new C19-diterpenoid alkaloids from the roots of Aconitum ouvrardianum

Four new C₁₉-diterpenoid alkaloids, 3-dehydroxyl-lipoindaconitine (1), 8-dehydroxyl-bikhaconine (2), 19R-acetonyl-talatisamine (3), and 16-hydroxyl-vilmorisine (4), were isolated from the roots of Aconitum ouvrardianum. Their structures were elucidated by spectral analyses, including ESI-MS, HR-ESI-MS, IR, UV, 1D and 2D NMR.     

New dianthramide and cinnamic ester glucosides from the roots of Aconitum carmichaelii

Four new compounds N-salicyl-3-hydroxyanthranilic acid methyl ester (1), N-(2′-dehydroxysalicyl)-3-hydroxyanthranilic acid methyl ester (2), methyl-4-β-D-allopyranosyl-ferulate (3), and methyl-4-β-D-gulopyranosyl-cinnamate (4), along with six known compounds (5–10), were isolated from the roots of Aconitum carmichelii Debx. Their structures were elucidated on the basis of spectral data analysis, including 1D, 2D-NMR, and HR-ESI-MS. Compounds 1 and 2 showed the inhibition of nitric oxide (NO) production with IC₅₀ values of 9.13 and 19.94 μM, respectively.     

Anthraquinones from the Roots of <Emphasis Type="Italic">Knoxia valerianoides</Emphasis> inhibit the formation of advanced glycation end products and rat lens aldose reductase <Emphasis Type="Italic">in vitro</Emphasis>

Eight known compounds, lucidin (1), lucidin-ω-methyl ether (2), rubiadin (3), damnacanthol (4), 1,3,6-trihydroxy-2-methoxymethylanthraquinone (5), 3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (6), 1,3,6-trihydroxy-2-hydroxymethyl-9,10-anthraquinone 3-O-β-primeveroside (7), and vanillic acid (8), were isolated from EtOAc- and n-BuOH-soluble fractions of the roots of Knoxia valerianoides. The structures of 1–8 were identified by analysis of spectroscopic data as well as by comparison with published values. All the isolates were subjected to in vitro bioassays to evaluate advanced glycation end products (AGEs) formation and rat lens aldose reductase (RLAR) inhibitory activity. Compound 5 showed the most potent inhibitory activity (IC₅₀ = 52.72 μM) against AGEs formation. Compounds 1, 2, and 8 also showed potent inhibitory activity on AGEs formation with IC₅₀ values of 79.28, 62.79, and 93.93 μM, respectively, compared with positive control, aminoguanidine (IC₅₀ = 962 μM). While, compounds 1 and 5–7 showed strong inhibitory activity against RLAR with IC₅₀ values of 3.35, 3.04, 6.39, and 2.05 μM, respectively.     

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.     

Lecanorosides A and B,two new triterpene glycosides from the sea cucumber Actinopyga lecanora

Two new sulphated triterpene glycosides, lecanorosides A (1) and B (2), along with the known compounds holothurins A (3), A₁ (4), and B (5), were isolated from the sea cucumber Actinopyga lecanora. Their structures were deduced from extensive spectral analysis (NMR and MS) and chemical evidence. Glycosides 1 and 4 showed marginal in vitro cytotoxicity against two human tumour cell lines.     

New prenylated flavones from <Emphasis Type="Italic">Artocarpus champeden</Emphasis>, and their antimalarial activity in vitro

Two new prenylated flavones, artocarpones A and B (1 and 2), and seven known isoprenylated flavonoids, artonin A (3), cycloheterophyllin (4), artoindonesianin E (5), artoindonesianin R (6), heterophyllin (7), heteroflavanone C (8), and artoindonesianin A-2 (9), have been isolated from the stem bark of Artocarpus champeden. Their structures were determined by spectroscopic analysis. Among the compounds isolated, 8 had the most potent inhibitory activity against the growth of Plasmodium falciparum 3D7 clone, with an IC₅₀ value of 1 nmol L⁻¹.     

Melanogenesis inhibitory compounds from Saussureae Radix

Ten compounds were isolated from the EtOAc soluble part of the MeOH extract of Saussureae Radix, with their effects on melanin production also evaluated in B-16 mouse melanoma cell lines stimulated with 3-isobutyl-1-methylxanthine (IBMX), an elevator of cellular cAMP. The compounds were identified as aplotaxene (1), 1β-hydroxy arbusculin A (2), costunolide (3), dehydrocostuslactone (4), 11β,13-dihydrocostunolide (5), reynosin (6), heptadec-(9Z)-enoic acid (7), β-sitosterol (8), linoleic acid methyl ester (9) and betulinic acid methyl ester (10). Compounds 2, 9 and 10 were identified from Saussureae Radix for the first time. Furthermore, compounds 2, 3 and 6 showed potent inhibitory effects on the IBMX-induced melanogenesis, in dose-dependent manners, with IC₅₀ values of 11, 3 and 2.5 μg/mL, respectively. As a positive control, arbutin exhibited an IC₅₀ value of 29 μg/mL.     

Three new guaiane sesquiterpene lactones from rhizomes of Curcuma wenyujin

Three new guaiane sesquiterpene lactones (4S)-4-hydroxy-gweicurculactone (1), zedoalactone G (2), and (1R, 4R, 5S, 10S)-zedoalactone B (3), and three known guaiane sesquiterpene lactones, including zedoarolide B (4), zedoalactone B (5), and a new natural product (+)-zedoalactone A (6), were isolated from the rhizomes of Curcuma wenyujin Y.H. Chen et C. Ling. The structures were elucidated by spectroscopic methods including 1D and 2D NMR and HR-ESI-MS. The absolute configuration of 2 was determined via the calculated electronic circular dichroism (ECD), whereas the absolute configurations of 1 and 3 were determined via the ECD data of the [Rh₂(OCOCF₃)₄] complex and [Mo₂(OAc)₄] complex, respectively. The inhibitory effects of compounds 1–6 on nitric oxide production in lipopolysaccharide-activated macrophages were evaluated. All of them exhibited weak anti-inflammatory activity.     

Prenylated C6–C3 compounds from the fruits of Illicium simonsii

Two new prenylated C₆–C₃ compounds, 4-epi-illicinone E-12-shikimate (1) and 3-hydroxyillifunone B (2), together with five known prenylated C₆–C₃ compounds (3–7), were isolated from the fruits of Illicium simonsii. Their structures were elucidated on the basis of extensive spectroscopic methods, including 1D and 2D NMR, CD spectra, and ESI-MS analysis.     

Three new flavanoids from artificially induced dragon’s blood of Dracaena cambodiana

Three new flavanoids, (2R)-7,4′-dihydroxy-8-methylflavan (1), (2R)-7,4′-dihydroxy-6-methylflavan (2), and (3R)-7,3′,4′-trihydroxyhomoisoflavan (3), together with seven known compounds (4–10), were isolated from artificially induced dragon’s blood of Dracaena cambodiana, and their structures were determined based on HR-ESI-MS and extensive spectroscopic techniques (UV, IR, 1D-, and 2D-NMR). Compound 2 exhibited weak cytotoxicity against BEL-7402 cells line with the IC₅₀ value of 39.2 μM. In addition, compound 3 showed significant acetylcholinesterase (AChE) inhibitory activity.     

Urease inhibitory constituents from Daphne retusa

The bioassay-guided fractionation of Daphne retusa Hemsl. has led to the isolation of a new aryl tetrahydronaphthalene lignan derivative named as daphnretusic acid (1), along with six new source compounds such as 5,7-dihydroxyflavone (2), 7-hydroxyflavone (3), 6-methoxyflavone (4), (+) pinoresinol (5), (+) sesamin (6), and β-sitosterol-3-O-β-D-glucopyranoside (7). Their structures were elucidated by ¹H NMR, ¹³C NMR, 1D, 2D NMR, UV, IR, and EIMS analyses. All the fractions (n-hexane, CHCl₃, AcOEt, CH₃OH, and water) and pure compounds (1–7) were subjected to the assay of urease and α-chymotrypsin inhibitory activities. Chloroform and methanol soluble fractions showed moderate urease inhibition. Compound 2 exhibited significant urease inhibition with IC₅₀ value 60.4 ± 0.72 μM, whereas compounds 1 and 3–7 remained inactive during urease inhibition and α-chymotrypsin bioassays.     

Three new diterpenoid alkaloids from the roots of Aconitum duclouxii

Three new C₁₉-diterpenoid alkaloids, ducloudines C (1), D (2), and E (3), were isolated from the roots of Aconitum duclouxii. Their structures were established on the basis of extensive spectroscopic analyses. Ducloudine C (1) is the first aconitine-type C₁₉-diterpenoid alkaloid with a C = O group at C-3 and a C = C bond between C-1 and C-2. All compounds were tested for their biological activities against one pathogenic fungi and two pathogenic bacteria.     

Guanacastane-type diterpenoids from the insect-associated fungus Verticillium dahliae

Four new guanacastane-type diterpenoids, namely dahlianes A (1), B (2), C (3), and D (4), were isolated from cultures of Verticillium dahliae. Their structures were elucidated on the basis of extensive spectroscopic data analysis. Their absolute configurations were determined by a combination of Mo₂(OAc)₄-induced electronic circular dichroism experiment and Mosher ester method. In cytotoxicity evaluation against human tumor cell lines, compounds 2 and 3 exhibited significant cytotoxicities against MCF-7 cell lines with IC₅₀ values of 3.35 and 4.72 μM, respectively.     

Terpenoids and bisbibenzyls from Chinese liverworts Conocephalum conicum and Dumortiera hirsuta

Four new monoterpene esters, 2α,5β-dihydroxybornane-2-cinnamate (1), 2α,5β-dihydroxybornane-5-acetyl-2-cinnamate (2), 2α,5β-dihydroxybornane-2-p-hydroxycinnamate (3) and 2α,5β-dihydroxy-bornane-2-cis-p-hydroxycinnamate (4), together with a known compound 3,4-dimethoxystyrene (5) were isolated from Chinese liverwort Conocephalum conicum and six known compounds, 5,7-dihydroxycalamenene (6), 7-hydroxycalamenene (7), lunularin (8), riccardin C (9), marchantin C (10) and riccardin D (11) were isolated from Dumortiera hirsuta. Their structures were elucidated by extensive spectral analysis and chemical correlations. Compounds 1 and 8 showed moderate cytotoxicity against human HepG2 cells with IC₅₀ 4.5 μg/ml and 7.4 μg/ml, respectively, while compound 8 also showed antimicrobacterial activity against Pseudomonas aeruginosa with minimum inhibitory concentration at 64 μg/ml.     

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 abietane diterpenoid from Isodon inflexus

A new ent-abietane diterpenoid, 3α,6β-dihydroxy-7,17-dioxo-ent-abieta-15(16)-ene (1), and three known ent-kaurane diterpenids, kamebacetal A (2), kamebakaurin (3), and excisanin A (4), and a known triterpenoid, ursolic acid (5), were isolated from the aerial parts of Isodon inflexus. Their chemical structures were determined by extensive analysis of spectroscopic data including 1D-and 2D-NMR experiments. All isolates (1–5) were evaluated for their potential to inhibit LPS-induced nitric oxide production in RAW264.7 cells. Of these, compounds 1–4 inhibited the production of NO with IC₅₀ values ranging from 1.0 to 26.5 μM.     

Cytotoxic ent-kaurane diterpenoids from Isodon macrophyllus

Two new ent-kaurane diterpenoids, dayecrystals D–E (1–2), together with nine known compounds, isojaponin A (3), rabdosin A (4), lushanrubescensin J (5), wikstroemioidin B (6), maoyecrystal C (7), rabdosin B (8), isodonal (9), shikokianin (10), and effusanin A (11), were isolated from the leaves of Isodon macrophyllus. The structures of the new compounds were elucidated using 1D and 2D NMR spectroscopy. The ¹³C-NMR spectral data of compound 4 are reported for the first time. All of the compounds were tested for their cytotoxicities against DU145 and LoVo human tumor cells. Compounds 4, 10, and 11 showed inhibitory effects on DU145 cells with IC₅₀ values 5.90, 4.24, and 3.16 μM, and LoVo cells with IC₅₀ values 14.20, 17.55, and 3.02 μM, respectively.