Anti-HBV active flavone glucosides from Euphorbia humifusa Willd.

Thirteen flavone glucosides from the herb of Euphorbia humifusa were isolated and elucidated. Among them, five compounds including apigenin-7-O-β-d-glucopyranoside (2), apigenin-7-O-(6′′-O-galloyl)-β-d-glucopyranoside (3), luteolin-7-O-β-d-glucopyranoside (7), luteolin-7-O-(6′′-O-trans-feruloyl)-β-d-glucopyranoside (8) and luteolin-7-O-(6′′-O-coumaroyl)-β-d-glucopyranoside (9) showed anti-HBV activity in vitro. The structure–activity relationship showed that the parent structure was closely relevant to the anti-HBV activity of these compounds (agigenin > luteolin > quercetin). It was found that the number of glucoside in the structure may significantly influence their activities (flavone monoglucoside > flavone diglucoside) and cytotoxicity (flavone > flavone monoglucoside > flavone diglucoside). In addition, the substitution of acyl group on glucoside may be important to keep the anti-HBV activities of these compounds (galloyl > feruloyl > coumaroyl).     

Protection against neurodegenerative diseases of Iris pseudopumila extracts and their constituents

The present study describes for the first time the in vitro properties of Iris pseudopumila flowers and rhizomes extracts and their constituents. The methanolic extract of rhizomes showed significant anti-inflammatory activity through inhibition of NO production in the murine monocytic macrophage cell line RAW 264.7. Among the isolated compounds, those which most effectively inhibited LPS-induced NO production were irisolidone and 7-methyl-tectorigenin-4′-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside], with IC₅₀ values of 23.6 μM and 29.4 μM respectively. Isoorientin and isovitexin exhibited the most promising activity against AChE with IC₅₀ of 26.8 μM and 36.4 μM, respectively. The same compounds exhibited also the higher activity against BChE.     

Cerebroside and ceramide from the pollen of Brassica napus L.

The new cerebroside 1-O-(β-d-glucopyranosyl)-(2 S, 3 S, 4R, 8E)-2-[(2′R)-2′-hydroxytetracosenoilamino]-8-octadecene-1,3,4-triol (1) and ceramide (2 S, 3 S, 4R, 8E)-2-[(2′R)-2′-hydroxytetracosenoilamino]-8-octadecene-1,3,4-triol (2) were isolated from the ethyl acetate extract of the pollen of Brassica napus L. The structures of 1 and 2 were elucidated on the basis of chemical and spectroscopic method. Two new compounds were evaluated for activity in vitro assays for the cytotoxic activities against human tongue squamous carcinoma cell line (Tca8113).     

Two new steroidal saponins from Selaginella uncinata (Desv.) Spring and their protective effect against anoxia

Four steroidal saponins were isolated from the anti-anoxic fraction of the 60% EtOH extract of Selaginella uncinata, including two new compounds, (3β, 7β, 12β, 25R)-spirost-5-ene-3, 7, 12-triol-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-[α-L-rhamnopyranosyl-(1 → 4)]-O-β-d-glucopyranoside (1), (2α, 3β, 12β, 25R)-spirost-5-ene-2, 3, 12-triol-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-[α-L-rhamnopyranosyl-(1 → 4)]-O-β-d-glucopyranoside (2) and two known compounds, (3β, 12β, 25R)-spirost-5-ene-3,12-diol-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-[α-L-rhamnopyranosyl-(1 → 4)]-O-β-d-glucopyranoside, (3), (1α, 3β, 25R)-spirost-5-ene-2-diol-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-[α-L-rhamnopyranosyl(1 → 4)]-O-β-d-glucopyranoside (4). The four compounds showed potent protective effect against anoxia in the anoxic PC12 cells assay, among which compounds 1 and 2 were the most active. To our knowledge, this is the first study to report the steroidal saponins in the plant S. uncinata and demonstrate their protective effect against anoxia in PC12 cell assay.     

The phenylpropanoids of Aster flaccidus

Aster flaccidus bge has been used as traditional medicine in northwestern China. Two new phenylpropanoids (1–2) including one lignan: (7′R, 8S)-9′-lariciresinol-(α-methyl)-butanoate (1), 5,9-dimethoxyl-7-(α-methyl)-butanoxyl-phenyl-2E-propenol-(α-methyl)-butanoate (2) isolated from the chloroform extract of the root of Aster flaccidus bge were identified by means of extensive spectroscopic studies: 1D and 2D NMR spectra as well as HRMS analysis. They have not obvious anti-HIV-1 therapeutic activity (TI = 1.0–1.1) compared with AZT (TI = 55,556) as the result of the determination of their in vitro anti-HIV-1 activity while compound 2 displays strong antitumor activity against BEL 7402 (human liver carcinoma) with cisplatin as a positive control and the effect increases with the measuring-time going on (24 h, IC₅₀: 106.67 ± 8.47 µM — 72 h, IC₅₀: 50.51 ± 6.11 µM).     

Polyprenylated isoflavanone and isoflavonoids from Ormosia henryi and their cytotoxicity and anti-oxidation activity

A rare naturally-occurring polyprenylated isoflavanone, designated ormosinol (1), and a new isoflavonoid glycoside, named ormosinoside (2), along with 21 known compounds were isolated from the root bark of Ormosia henryi Prain. The structures of compounds 1 and 2 were determined as 5,7,2′,4′-tetrahydroxyl-6,8,5′-tri-(γ,γ-dimethylallyl)isoflavanone and isoprunetin-7-O-β-d-xylopyranosyl-(1 → 6)-β-d-glucopyranoside on the basis of a combination of 1D-, 2D-NMR and mass spectroscopic measurements. Compound 1 showed significant anti-oxidation activity against DPPH radicals (IC₅₀ 28.5 μM) and cancer cell line (A549, LAC, and HepG2) growth inhibitory activity with IC₅₀ ranging from 4.25 to 7.09 μM, while compound 2 found to be inactive to both testing systems.     

A new dilactone from the seeds of Gaultheria yunnanensis

Gaultheriadiolide (1), a new compound, together with the known dauosterol (2), ginkgetin (3), myricetin (4), 6-ethyl-5-hydroxy-2,7-dimethoxy-1,4-naphthoquinone (5), ursolic acid (6), methyl salicylate 2-O-β-d-xylosyl(1→6)β-d-glucopyranoside (7), and methyl salicylate 2-O-β-d-glucopyranoside (8) were isolated from Gaultheria yunnanensis. The structure was elucidated on the basic of spectral analysis, especially 1D and 2D NMR. Primary bioassays showed that compound 1 had medium cytotoxic activity against HEp-2 and HepG2 Cells, with IC₅₀ of 23.337 μM and 29.4497 μM, respectively.     

A new fungitoxic metabolite from Spiraea alpina Pall.

The fungitoxic metabolites of Spiraea alpina Pall. were identified using inhibition of Rhizoctonia solani, Gibberella zeae, Pyricularia oryzea and Exserohilum turcicum as an end-point. The major fungitoxic constituent of S. alpina was a new diacylated sugar, structurally elucidated as 6-O-(3′,4′-dihydroxy-2′-methylenbutyryl)-1-O-trans-cinnamoyl-β-D-glucopyranose. This compound could inhibit at 0.1 mg/ml Rhizoctonia solani and Exserohilum turcicum, 87.6% and 63.2%, respectively.     

Cytotoxic triterpene saponins from the leaves of Aralia elata

Phytochemical investigation of the leaves of Aralia elata has led to the isolation of four new compounds, 3-O-β-D-glucopyranosyl (1→3)-β-D-glucopyranosyl (1→3)-β-D-glucopyranosyl oleanolic acid (1), 3-O-[β-D-glucopyranosyl (1→3)-β-D-glucopyranosyl (1→3)]-[β-D-glucopyranosyl (1→2)]-β-d-glucopyranosyl hederagenin 28-O-β-D-glucopyranoside (2), 3-O-{[β-D-glucopyranosyl (1→2)]-[β-d-glucopyranosyl (1→3)-β-d-glucopyranosyl (1→3)]-β-D-glucopyranosyl} oleanolic acid 28-O-β-D-glucopyranosyl ester (3) and 3-O-[β-D-glucopyranosyl (1→2)]-[β-D-glucopyranosyl (1→3)]-β-d-glucopyranosyl caulophyllogenin (4) and two known compounds, 3-O-[β-D-glucopyranosyl (1→3)-α-l-arabinopyranosyl]-echinocystic acid (5) and 3-O-α-L-arabinopyranosyl echinocystic acid (6). The structural determination was accomplished with spectroscopic analysis, in particular (13)C-NMR, 2D-NMR and HR-ESI-MS techniques. Compounds 1-6 were tested for their inhibition of the growth of HL60, A549 and DU145 cancer cells. Compound 1 showed significant cytotoxic activity against HL60 and A549 cancer cells with IC(50) values of 6.99μM and 7.93μM respectively. In addition, compounds 5 and 6 showed significant cytotoxic activity against HL60 cancer cells with IC(50) values of 5.75μM and 7.51μM, respectively.     

Iridoid, phenylethanoid and flavonoid glycosides from Sideritis trojana

From the MeOH extract of Sideritis trojana, a new iridoid glycoside, 10-O-(E)-feruloylmelittoside (1) was obtained in addition to four known iridoid glycosides [melittoside (2), 10-O-(E)-p-coumaroylmelittoside (3), stachysosides E (4) and G (5)]. Moreover, five phenylethanoid glycosides [verbascoside (6), isoacteoside (7), lamalboside (8), leonoside A (9), isolavandulifolioside (10), three flavone glycosides (isoscutellarein 7-O-[6'-O-acetyl-β-allopyranosyl-(1→2)]-β-glucopyranoside (11), 4'-O-methyisoscutellarein 7-O-[6'-O-acetyl-β-allopyranosyl-(1→2)]-β-glucopyranoside (12), 3'-hydroxy-4'-O-methyisoscutellarein 7-O-[6'-O-acetyl-β-allopyranosyl-(1→2)]-β-glucopyranoside (13) and a benzylalcohol derivative (di-O-methylcrenatin) were obtained and identified. The structures were elucidated on the basis of NMR and HRMS data. All compounds were tested for their antioxidant activity by in vitro TEAC assay and some of them exhibited moderate activity (0.97-1.44 mM) when compared with the reference compound (quercetin 1.86 mM). Glycosides 6-13, the most active compounds in the TEAC assay, were also tested by flow cytometry to evaluate their ability to affect the levels of reactive oxygen species (ROS) in human prostate cancer cells (PC3).     

Homoisoflavanones from Ledebouria floribunda

The bulbs of Ledebouria floribunda (Baker) Jessop have yielded two novel compounds, 7-O-[α-rhamnopyranosyl-(1→6)-β-glucopiranosyl]-5-hydroxy-3-(4-methoxybenzyl)-chroman-4-one (1) and 7-O-[α-rhamnopyranosyl-(1→6)-β-glucopiranosyl]-5-hydroxy-3-(4′-hydroxybenzyl)-chroman-4-one (2) along with five other known compounds, 5,7-dihydroxy-3-(4′-methoxybenzyl)-chroman-4-one or 3,9-dihidroeucomin (3), 5,7-dihidroxy-6-methoxy-3-(4′-methoxybenzyl)-chroman-4-one (4), 5,7-dihidroxy 3-(4′-hydroxybenzyl)-chroman-4-one or 4,4′-demethyl-3,9-dihydropuctatin (5), 5,7-dihidroxy-3-(4′-hydroxybenzyl)-6-methoxy-chroman-4-one or 3,9-dihydroeucomnalin (6) and 7-hydroxy-3-(4′-hydroxybenzyl)-5-methoxy-chroman-4-one (7). Their structures were elucidated by spectra analysis. The seven homoisoflavanones were found to be antioxidant against DPPH radical and β-carotene/linoleic acid system.     

New flavane gallates isolated from the leaves of Plicosepalus curviflorus and their hypoglycemic activity

Two new flavane gallates were isolated from the leaves of Plicosepalus curviflorus. The structure of the new compounds was established as 2S,3R-3,3′,4′,5,7-pentahydroxyflavane-5-O-gallate (1) and 2S,3R-3,3′,4′,5,5′,7-hexahydroxyflavane-4′,5-di-O-gallate (2), respectively. In addition, seven known compounds (−)-catechin (3), quercetin (4), lupeol (5), β-sitosterol (6), pomolic acid (7), β-sitosterol 3-O-β-d-glucopyranoside (8) and 4-methoxycinnamic acid (9) were reported for the first time from the genus Plicosepalus. Compounds 1, 2 and 3 were investigated for their hypoglycemic activity and showed significant hypoglycemic activity in Swiss Albino mice.     

Solanum incanum and S. heteracanthum as sources of biologically active steroid glycosides: confirmation of their synonymy

A new spirostanol saponin (1), along with four known saponins, dioscin (2), protodioscin (3), methyl-protodioscin (4), and indioside D (5), and one known steroid glycoalkaloid solamargine (6) were isolated from the two synonymous species, Solanum incanum and S. heteracanthum. The structure of the new saponin was established as (23S,25R)-spirost-5-en-3β,23-diol 3-O-{β-D-xylopyranosyl-(1→2)-O-α-L-rhamnopyranosyl-(1→4)-[O-α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside}, by using a combination of 1D and 2D NMR techniques including (1)H, (13)C, COSY, TOCSY, NOESY, HSQC and HMBC experiments and by mass spectrometry. The compounds 1, 3, 4 and 5 were evaluated for cytotoxicity against five cancer cell lines and for antioxidant and cytoprotective activity.     

Three new triterpenoid saponins from root of Gardenia jasminoides Ellis

Three new compounds (Gardeniside A–C), 11α,12α-epoxy-3β-[(O-β-D-glucuronopyranoside-6′-O-methly ester)oxy]olean-28,13-olide (1), siaresinolic acid 3-O-β-D-glucuronopyranoside-6′-O-methly ester (2), and 3-O-β-D- glucuronopyranoside-6′-O-methly ester-siaresinolic acid-28-O-β-D- glucopyranoside (3), with seven known compounds oleanolic acid 3-O-β-D- glucuronopyranoside-6′-O-methly ester (4), oleanolic acid 3-O-β-D- glucuropyranoside (5), hederagenin 3-O-β-D- glucuronopyranoside-6′-O- methly ester (6), chikusetsusaponin IVa methyl ester (7), chikusetsusaponin (8), chikusetsusaponin IVa butyl ester (9), siaresinolic acid 28-o-β-d-glucopyranosyl ester (10) were isolated from the root of Gardenia jasminoides Ellis. Six compounds (1, 4–7, and 9) showed cytotoxic activities against HeLa, A549, MCF-7 and A354-S2 cell lines.     

Benzyl-β-resorcylates from Cassia obtusifolia

The seed of Cassia obtusifolia Linn have yielded three new compounds, 2-benzyl-4,6-dihydroxy benzoic acid (1), 2-benzyl-4,6-dihydroxy benzoic acid-6-O-β-d-glucopyranoside (2) and 2-benzyl-4,6-dihydroxy benzoic acid-4-O-β-d-glucopyranoside (3). Their structures were determined by spectroscopic methods, including ¹D- and ²D NMR spectroscopy, HR-ESI-MS, as well as by comparison of their spectral data with those of related compounds.     

Five new triterpenoidal saponins from the roots of Ilex cornuta and their protective effects against H2O2-induced cardiomyocytes injury

Five new ursane-type triterpenoidal saponins (1–5), together with five known ones (6–10), were isolated from the EtOH extract of the roots of Ilex cornuta. The structures of saponins 1–5 were elucidated as 19α-hydroxyurs-12-en-28-oic acid 3β-O-β-D-glucuronopyranoside (1), 19α-hydroxyurs-12-en-28-oic acid 3β-O-β-D-glucuronopyranoside-6-O-ethyl ester (2), 19α-hydroxyurs-12-en-28-oic acid 3β-O-α-L-arabinopyranosyl-(1 → 2)-β-D-glucuronopyranoside (3), 3β-O-[α-L-arabinopyranosyl-(1 → 2)-β-D-glucuronopyranosyl]-19α-hydroxyurs-12-en-28-oic acid 28-O-β-D-glucopyranosyl ester (4) and 3β-O-[α-L-arabinopyranosyl-(1 → 2)-β-D-glucuronopyranoside-6-O-methyl ester]-19α-hydroxyurs-12-en-28-oic acid 28-O-β-D-glucopyranosyl ester (5), on the basis of spectroscopic analyses (IR, ESI-MS, HR-ESI-MS, 1D and 2D NMR) and chemical reactions. Protective effects of compounds 1–10 against H₂O₂-induced H9c2 cardiomyocyte injury were tested. Compounds 1–5, 7, and 10 showed cell-protective effects. Among them compound 5 exhibited the highest activity. No significant DPPH radical scavenging activity was observed for compounds 1–10.     

Mushroom tyrosinase inhibitors from Aloe barbadensis Miller

Two new chromones, 5-((S)-2′-oxo-4′-hydroxypentyl)-2-(β-glucopyranosyl-oxy-methyl)chromone (1) and 5-((S)-2′-oxo-4′-hydroxypentyl)-2-methoxychromone (2), together with four known analogues, 8-C-glucosyl-7-O-methyl-(S)-aloesol (3), isoaloeresin D (4), 8-C-glucosyl-(R)-aloesol (5), and aloesin (6) were isolated from the aqueous extract of Aloe barbadensis Miller. Their structures were determined on the basis of spectroscopic evidences (1-D and 2-D NMR, HRMS, UV, and IR data), chemical methods and the literature data. The Mosher's method was applied to establish the absolute configuration of compounds 1 and 2. The inhibitory effects of these chromones on the activity of mushroom tyrosinase were examined, and compound 6 was identified as a noncompetitive tyrosinase inhibitor with an IC₅₀ value of 108.62 μg·mL^− 1.     

Chemical constituents from endophytic fungus Fusarium oxysporum

A new oxysporidinone analogue (1) and a new 3-hydroxyl-2-piperidinone derivative (2), along with the known compounds (−)-4,6′-anhydrooxysporidinone (3), (+)-fusarinolic acid (4), gibepyrone D (5), beauvercin (6),cerevisterol (7), fusaruside (8), and (2S,2′R,3R,3′E,4E,8E)-1-O-D-glucopyranosyl-2-N-(2′-hydroxy-3′-octadecenoyl)-3-hydroxy-9-methyl-4,8-sphingadienine (9) were isolated from Fusarium oxysporum. Compounds 1-9 were evaluated for cytotoxicity using the MTT method against cancer cell lines, PC-3, PANC-1, and A549. Beauvericin showed cytotoxicity against PC-3, PANC-1, and A549 with IC₅₀ value of 49.5 ± 3.8, 47.2 ± 2.9, and 10.4 ± 1.6 μM, respectively. Beauvericin also exhibited anti-bacterial activity towards methicillin-resistant Staphylococcus aureus (MIC = 3.125 μg/mL) and Bacillus subtilis (MIC = 3.125 μg/mL).     

Dammarane-type glycosides and long chain sesquiterpene glycosides from Gynostemma yixingense

A new dammarane-type glycoside and a new long chain sesquiterpene glycoside, along with nine known compounds 20(S)-ginsenoside Rh1 (3), 20(R)-ginsenoside Rh1 (4), ginsenoside F1 (5), amarantholidoside IV (6), ginsenoside Rc (7), 20(S)-ginsenoside Rg2 (8), 20(R)-ginsenoside Rg2 (9), ginsenoside Rd (10) and gypenoside XLVI (11) were isolated from Gynostemma yixingense. The structures of the new compounds were determined on the basis of spectroscopic analysis, including 1D-, 2D-NMR and ESI-MS techniques as well as by comparison of the spectral data with those of related compounds as 2α,3β,20(S)-trihydroxydammar-24-ene-3-O-[β-d-glucopyranosyl((1 → 2)-β-d-glucopyranosyl]-20-O-[β-d-xylopyranosyl((1 → 6)-β-d-glucopyranoside] (1) (2E,6E)-10-β-d-glucopyranosyl-1,10,11-trihydroxy-3,7,11-trimethyldodeca-2,6-diene (2).     

Phenolic glycosides from Dodecadenia grandiflora and their glucose-6-phosphatase inhibitory activity

Phytochemical investigation of Dodecadenia grandiflora leaves led to the isolation and identification of three phenolic glycosides, designated 1-[(4′-O-(E)-p-coumaroyl)-β-d-glucopyranosyl]-oxy-2-phenol (1), 1-[(6′-O-(E)-p-coumaroyl)-β-d-glucopyranosyl]-oxy-2-phenol (2) and 1-[O-β-d-glucopyranosyl(1→2)-β-d-glucopyranosyl]-oxy-2-phenol (3), along with nine known compounds. Compounds 1, 2, 5 and 9 exhibited significant glucose-6-phosphatase inhibitory activity (63.7, 66.9, 82.9 and 85.4%) with IC₅₀ values of 88.5, 81.0, 51 and 50 μM respectively. On the basis of biological results, a structure–activity relationship has been discussed.