New clerodane diterpenoids from Casearia sylvestris

Two new clerodane diterpenoids 2β-methoxy-cleroda-3,13-dien-18-carboxy-15,16-olide (1) and 15ξ-methoxy-cleroda-3,12-dien-18-carboxy-15,16-olide (2) and one new nitrogen-containing clerodane diterpenoid 15-oxo-echinophyllin A (3), along with six known compounds, namely, echinophyllin A, (−)-patagonic acid, tyrosol, oplopanone, 4-hydroxy-4-methyl-2-[(1R)-1-(1-methylethyl)-4-oxopentyl]-2-cyclohexen-1-one and 1β,6α-dihydroxy-eudesman-4(15)-ene were isolated from the leaves of Casearia sylvestris. Their structures were determined by extensive NMR techniques.     

Abietane-type and labdane-type diterpenoids from the cones of Chamaecyparis obtusa

A novel compound, 8(17),12E,14-labdatrien-19-al (trans-communal), was isolated from ethyl acetate extract of young cones of hinoki (Chamaecyparis obtusa Endl.). The chemical structure of the compound was determined mainly with various nuclear magnetic resonance spectral techniques. Its stereochemistry was determined by derivation to a known compound,trans-communol. In addition to this compound, four known compounds — ferruginol, chamaecydin, 12-hydroxy-6,7-seco-abieta-8,l 1,13-triene-6,7-dial, and frans-communic acid — were isolated. All isolated compounds were subjected to an antifeedant bioassay against the pest insectSpodoptera litura. Results of the bioassay showed that chamaecydin and 12-hydroxy-6,7-seco-abieta-8,11,13-triene-6,7-dial had antifeedant activity.Part of this report was presented at 45th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1995     

Two new chalcone glycosides from the stems of Entada phaseoloides

Two new chalcone glycosides 4′-O-(6″-O-galloyl-β-d-glucopyranosyl)-2′,4-dihydroxychalcone (1) and 4′-O-(6″-O-galloyl-β-d-glucopyranosyl)-2′-hydroxy-4-methoxychalcone (2) together with one known chalcone glycoside 4′-O-β-d-glucopyranosyl-2′-hydroxy-4-methoxychalcone (3) were isolated from the stems of Entada phaseoloides. The structures of the new compounds were elucidated on the basis of extensive spectroscopic analysis, including HSQC, HMBC, ¹H–¹H COSY, and chemical evidences. This is the first report of chalcone-type compounds isolated from the genus Entada.     

Dihydroroseoside, a new cyclohexanone glucoside, from the leaves of shirakamba (Betula platyphylla Sukatchev var.japonica Hara)

A new cyclohexanone glucoside (II) and a known cyclohexenone glucoside roseoside [I, (6S, 9S)-6-hydroxy-6-(9--D-glucopyranosyloxy-trans-7-butenyl)-1,5,5-trimethyl-1-cyclohexenone] were isolated from an ethanol extract of shirakamba (Betula platyphylla Sukatchev var.japonica Hara) leaves. The structure ofII was determined to be (6S, 9R)-6-hydroxy-6-(9-O--D-glucopyranosyloxy-trans-7-butenyl)-1, 5,5-trimethyl-1-cyclohexanone by¹H-NMR and¹³C-NMR spectroscopic analyses. It was named dihydroroseoside.     

Sesquiterpenoids from Trichoderma atroviride, an endophytic fungus in Cephalotaxus fortunei

Two new sesquiterpenoids, identified as (rel 1S, 3R, 4R, 7R)-3-[5-hydroxy-4-methylpent-3-enyl]-1, 3, 7-trimethyl-2-oxabicyclo [2, 2, 1] heptane (1) and (rel 1S, 3R, 4R, 7R)-3-[3, 4-dihydroxy-4-methylpentyl]-1, 3, 7-trimethyl-2-oxabicyclo [2, 2, 1] heptane (2), were isolated from cultures of Trichoderma atroviride (strain no. S361), an endophytic fungal strain residing in the bark of Cephalotaxus fortunei. The structures of compounds 1 and 2 were elucidated by detailed spectroscopic analyses on the basis of NMR, IR, and MS data. Both compounds 1 and 2 were potent inhibitors on NO production in LPS-stimulated RAW264.7 cells, with IC₅₀ values of 15.3 and 9.1 μM, respectively.     

Isolation of new flavan-3-ol and lignan glucoside from Loropetalum chinense and their antimicrobial activities

Phytochemical and antimicrobial activity study on the ethanol extract of the leaves and stems of Loropetalum chinense led to the isolation of a new flavan-3-ol compounds, 8-[1-(3,4-dihydroxyphenyl)-3-methoxy-3-oxopropyl]-catechin (loropetaliside A) (1) and a new lignan glucoside, 1-(5-hydroxy-3-methoxyphenyl)-2-(2-β-glucopyranosyl-4-hydroxy-5-(1-(E)propen-3-ol)-phenyl)-propane-3-ol (loropetaliside B) (3) and several known compounds manglieside D (2), quercetin (4), kaempferol-3-O-D-glucopyranoside (5), quercetin-3-O-β-L-rhamnoside (6) and tiliroside (7). Their structures were elucidated on the basis of extensive spectroscopic analysis.     

Multihydroxylation of ursolic acid by Pestalotiopsis microspora isolated from the medicinal plant Huperzia serrata

The structural modification of ursolic acid by an endophytic fungus Pestalotiopsis microspora, isolated from medicinal plant Huperzia serrata was reported for the first time. The structure diversity was very important for the SAR study of ursolic acid and its derivatives. Incubation of ursolic acid 1 with P. microspora afforded four metabolites: 3-oxo-15α, 30-dihydroxy-urs-12-en-28-oic acid (2), 3β, 15α-dihydroxy-urs-12-en-28-oic acid (3), 3β, 15α, 30- trihydroxy-urs-12-en-28-oic acid (4) and 3,4-seco-ursan-4,30-dihydroxy-12-en-3,28-dioic acid (5). All products were new compounds and their structures elucidation was mainly based on the spectroscopic data.     

Two new flavonoids from Retama raetam

Two new flavones were isolated from the aerial parts of Retama raetam subsp. raetam. Their structures were established as luteolin 4′-O-neohesperidoside (1) and 5,4′-dihydroxy-(3″,4″-dihydro-3″,4″-dihydroxy)-2″,2″-dimethylpyrano-(5″,6″:7,8)-flavone (2) by means of spectroscopic methods. Also present was ephedroidin (4′,5,7-trihydroxy-8-(2-hydroxy-3-butenyl)-flavone).     

A new biphenyl and antimicrobial activity of extracts and compounds from Clusia burlemarxii

Phytochemical investigation on Clusia burlemarxii (Clusiaceae) led to isolation and identification of nine compounds. Were isolated from leaves 3-O-α-L- rhamnopyranosylquercetin, 3-O-α-L-rhamnopyranosylkaempferol, 4-hydroxy-5,5-dimethyldihydrofuran-2-one, 2Z-δ-tocotrienoloic acid and friedelin and were isolated from trunk betulinic acid, protocatechuic acid, lyoniresinol, and a new biphenyl 2,2-dimethyl-3,5-dihydroxy-7-(4-hydroxyphenyl)chromane. The structures were determined by ¹H, ¹³C-NMR, DEPT, HMBC, HMQC, HRESIMS. The Minimal Inhibitory Concentration against Streptococcus mutans, Staphylococcus aureus, Bacillus subtilis, Micrococcus luteus, Escherichia coli, Salmonella choleraesuis, Pseudomonas aeruginosa, Aspergillus niger and Cladosporium cladosporioides was also determined. Extracts and compounds showed significant activity against tested Gram-positive bacteria, none activity against tested Gram-negative bacteria and fungi.     

Organic acid exudation from the roots of Cunninghamia lanceolata and Pinus massoniana seedlings under low phosphorus stress

Organic acid exudation from the roots of Chinese fir (Cunninghamia lanceolata) and Masson pine (Pinus massoniana) seedlings under low phosphorus stress was studied using the solution culture method. The results revealed that organic acid exudation from the roots of Chinese fir and Masson pine seedlings under low phosphorus stress increased. Compared with P₃ (KH₂PO₄, 0.5 mmol/L), the average organic acid exudation from the root of Masson pine seedlings under P₀ (KH₂PO₄, 0 mmol/L), P₁ (KH₂PO₄, 0.03 mmol/L) and P₂ (KH₂PO₄, 0.09 mmol/L) increased by 328.6%, 267.9% and 126.4% respectively. Masson pine from Zhejiang Province in China had the highest organic acid exudation. Under low phosphorus stress, the increase in organic acid exudation from the different provinces of Chinese fir and Masson pine varied. Masson pine from Zhejiang Province mainly increased oxalic acid, tartaric acid, citric acid and malic acid exudation, that from Guangxi Province mainly increased oxalic acid and tartaric acid exudation, and that from Guizhou Province, China mainly increased oxalic acid, tartaric acid and malic acid exudation. Chinese fir mainly increased oxalic acid and tartaric acid exudation. __________ Translated from Journal of Nanjing Forestry University, 2007, 31(2): 9–12 [译自: 南京林业大学学报]     

Proanthocyanidins and a phloroglucinol derivative from Rumex acetosa L.

From the ethyl acetate soluble fraction of an acetone–water extract of the aerial parts of Rumex acetosa L. (Polygonaceae), a variety of monomeric flavan-3-ols (catechin, epicatechin, epicatechin-3-O-gallate), A- and B-type procyanidins and propelargonidins (15 dimers, 7 trimers, 2 tetramers) were isolated with 5 so far unknown natural products. Dimers: procyanidin B1, B2, B3, B4, B5, B7, A2, epiafzelechin-(4β→8)-epicatechin, epiafzelechin-(4β→8)-epicatechin-3-O-gallate (new natural product), epiafzelechin-(4β→6)-epicatechin-3-O-gallate (new natural product), epiafzelechin-3-O-gallate-(4β→8)-epicatechin-3-O-gallate, B2-3′-O-gallate, B2-3,3′-di-O-gallate, B5-3′-O-gallate, and B5-3,3′-di-O-gallate. Trimers: procyanidin C1, epiafzelechin-(4β→8)-epicatechin-(4β→8)-epicatechin (new natural product), epicatechin-(4β→8)-epicatechin-(4β→8)-catechin, cinnamtannin B1, cinnamtannin B1-3-O-gallate (new natural product), tentatively epicatechin-(2β→7, 4β→8)-epiafzelechin-(4α→8)-epicatechin (new natural product), and epicatechin-3-O-gallate-(4β→8)-epicatechin-3-O-gallate-(4β→8)-epicatechin-3-O-gallate.Tetramers: procyanidin D1 and parameritannin A1. All compounds were elucidated by ESI-MS, CD spectra, 1D- and 2D-NMR experiments as free phenols or peracetylated derivatives and, in part, after partial acid-catalysed degradation with phloroglucinol.A more abundant proanthocyanidin polymer was also isolated, purified and its chemical composition studied by ¹³C NMR.In addition a so far unknown phloroglucinolglycoside (1-O-β-d-(2,4-dihydroxy-6-methoxyphenyl)-6-O-(4-hydroxy-3,5-dimethoxybenzoyl)-glucopyranoside) was isolated.     

Chemical constituents from Gmelina arborea bark and their antioxidant activity

Gmelina arborea Roxb. is a fast-growing species and is known to have been used in traditional Indian medicine. Chemical constituents from the bark have not been reported, although some chemical constituents from part of this plant (heartwood, leaf, and root) are known. In this study, the bark meal was successively extracted with acetone and methanol. Fractionation of the acetone extract with n-hexane, diethyl ether, and ethyl acetate and subsequent chromatographic separation of the fractions led to the isolation of four compounds. The diethyl ether-soluble fraction yielded tyrosol [2-(4-hydroxyphenyl)ethanol] (1); (+)-balanophonin (2), an 8-5′ neolignan, with opposite optical rotation to known (−)-balanophonin; and gmelinol (3), a known lignan. The ethyl acetate-soluble fraction afforded a new phenylethanoid glycoside to the best of our knowledge, which was identified as (−)-p-hydroxyphenylethyl[5′″-O-(3,4-dimethoxycinnamoyl)-β-d-apiofuranosyl(1′" → 6′)]-β-d-glucopyranoside (4). From the methanol extract, two known compounds, 2,6-dimethoxy-p-benzoquinone (5) and 3,4,5-trimethoxyphenol (6), were isolated and identified. The 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay of the identifi ed compounds indicated that 3,4,5-trimethoxyphenol (6) exhibited moderate activity. Part of this report was presented at the 57th and 58th Annual Meetings of the Japan Wood Research Society, Hiroshima and Tsukuba, August 2007 and March 2008, respectively     

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).     

neo-Clerodane diterpenes from Ajuga ciliata Bunge and their neuroprotective activities

Three new (1–3) and three known (4–6) neo-clerodane diterpenes have been isolated from the whole plants of Ajuga ciliata Bunge. The structures of the new compounds were elucidated as (12S)-1β,6α,19-triacetoxy-18-chloro-4α,12-dihydroxy-neo-clerod-13-en-15,16-olide (1), (12S,2′S)-12,19-diacetoxy-18-chloro-4α,6α-dihydroxy-1β-(2-methylbutanoyloxy)-neo-clerod-13-en-15,16-olide (2), and (12S)-6α,18,19-triacetoxy-4α,12-dihydroxy-1β-tigloyloxy-neo-clerod-13-en-15,16-olide (3), on the basis of spectroscopic data analysis. All the diterpenes were evaluated for the neuroprotective effects against MPP⁺-induced neuronal cell death in dopaminergic neuroblastoma SH-SY5Y cells and compounds 2–5 exhibited moderate neuroprotective effects.     

Revisiting the mechanism of <Emphasis Type="Italic">β-O</Emphasis>-4 bond cleavage during acidolysis of lignin IV: dependence of acidolysis reaction on the type of acid

The dependence of the acidolysis reaction of a C₆-C₃ dimeric nonphenolic β-O-4 type lignin model compound, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl) propane-1,3-diol (veratrylglycerol-β-guaiacyl ether, VG), on the type of acid applied was examined using three different acids [0.2 mol/l HCl, 0.2 mol/l HBr, and 0.1 mol/l (0.2 N) H₂SO₄ in 82% aqueous 1,4-dioxane at 85°C]. In the HCl system, the major reaction modes of the corresponding benzyl cation-type intermediate (BC), which is produced by protonation of the α-hydroxyl group of VG and successive release of the water molecule, are the abstraction of the β-proton and hydride transfer from the β-to the α-position. The liberation of formaldehyde from the γ-hydroxymethyl group of BC is the predominant reaction mode in the H₂SO₄ system. Apparently, an unknown reaction mode or modes is operative in the early stage of the HBr system that causes rapid disappearance of VG accompanied by the quantitative formation of 2-methoxyphenol without affording the common counterpart of a Hibbert’s ketone, 1-hydroxy-3-(3,4-dimethoxyphenyl) propan-2-one. The reaction mode in the HBr system changes with the progress of the reaction and is the same as that in the HCl system after the early stage.     

New lignan, isoactifolin, fromChamaecyparis obtusa cv. Breviramea

A new lignan isoactifolin was isolated from young shoots (with leaves) ofChamaecyparis obtusa cv. Breviramea. The structure of the compound was determined based on spectroscopic evidence.Parts of this report were presented at the 44th lignin symposium, Gifu, October 1999     

An anti-inflammatory and immunomodulatory polysaccharide from Orbignya phalerata

A polysaccharide, a glucan with mean M_r of 1.0×10⁶ (MP1), was isolated from the mesocarp of fruits of Orbignya phalerata. Chemical and spectroscopic studies indicated that MP1 has a highly branched glucan type structure composed of α-(1→4) linked -glucopyranose residues with (3→4), (4→6), and with (3→6) branching points. MP1 enhanced phagocytosis in vivo and exhibited anti-inflammatory activity.     

Stereochemistry and biosynthesis of (+)-lyoniresinol, a syringyl tetrahydronaphthalene lignan in Lyonia ovalifolia var. elliptica I: isolation and stereochemistry of syringyl lignans and predicted precursors to (+)-lyoniresinol from wood

Steps leading to the biosynthesis of syringyl lignans and tetrahydronaphthalene and naphthalene lignans, especially the formation of the C2–C7′ linkage, have not been elucidated. Lyoniresinol is a typical syringyl lignan, as well as a tetrahydronaphthalene lignan found in Lyonia ovalifolia var. elliptica. To demonstrate the biosynthetic pathway for (+)-lyoniresinol, three putative biosynthetic intermediates of lyoniresinol, syringaresinol, 5,5′-dimethoxylariciresinol, and 5,5′-dimethoxysecoisolariciresinol, were isolated from wood. The identity of the putative intermediates was confirmed by spectroscopic analyses, as well as by comparison of spectral and chromatographic data with those of authentic samples previously synthesized. The stereochemistry (enantiomeric composition and absolute configuration) of the isolated lignans were determined as (±)-syringaresinol, (8S,8′S)-(−)-5,5′-dimethoxylariciresinol [46% enantiomeric excess (e.e.)], (8S,8′S)-(+)-5,5′-dimethoxysecoisolariciresinol (91% e.e.), and (8R,8′R)-(+)-lyoniresinol (42% e.e.). The absolute configurations of (+)-and (-)-5,5′-dimethoxylariciresinols, and (+)-and (-)-5,5′-dimethoxysecoisolariciresinols were determined by their synthesis (catalytic reduction) from (8R,8′R)-(+)-and (8S,8′S)-(-)-syringaresinols and by subsequent chiral high-performance liquid chromatography analysis. This report was presented at the 55th Annual Meeting of the Japan Wood Research Society, Kyoto, March 2005     

3, 4-seco-Labdane diterpenoids from the leaves of Callicarpa nudiflora and their inhibitory effects on nitric oxide production

As a part of our ongoing search for bioactive compounds from the leaves of Callicarpa nudiflora that inhibit nitric oxide (NO) production, the 90% EtOH fraction eluted by macroporous resin adsorption was found to show significant inhibitory activity against the production of NO in RAW 264.7 stimulated by lipopolysaccharide (LPS). Bioactivity-guided isolation of the fraction yielded three new bioactive diterpenoids, named ent-3, 4-seco-14-carbonyl-15, 16-epoxy-4(18), 8(17), 13(14)-labdatrien-3-oic acid (1), syn-3, 4-seco-12R-hydroxy-15, 16-epoxy-4(18), 8(17), 13(16), 14(15)-labdatetraen-3-oic acid (2) and syn-3, 4-seco-12S-hydroxy-15, 16-epoxy-4(18), 8(17), 13(16), 14(15)-labdatetraen-3-oic acid (3). Their structures and configurations were elucidated by comprehensive spectroscopic analysis. All the three compounds exhibited potent inhibitory activity on NO production in LPS-activated RAW 264.7 macrophage cells.     

云南甜龙竹和黄竹种子灭菌条件和萌发特性初步研究

目的]筛选云南甜龙竹和黄竹种子最佳表面灭菌条件,研究其萌发特性。[方法]筛选NaClO(2%、3%、4%)与HgCl_2(0.01%、0.1%)最佳消毒浓度组合;采用流水冲洗时间(6、12、18 h)、2%NaClO浸泡时间(5、10、15 min)和0.1%Hg Cl_2浸泡时间(5、10、15 min),设计正交试验实验,探讨2种竹种最佳表面灭菌处理的时间组合,并对竹种分别在滤纸、MS培养基以及经3 mg·L~(-1)GA_3浸泡后在MS培养基上的发芽率进行了探讨。[结果]NaClO、Hg Cl_2最佳消毒浓度组合为2%NaClO+0.1%HgCl_2;2种竹种最佳表面灭菌时间组合均为:流水冲洗6 h、2%Na Cl O浸泡10min、0.1%HgCl_2浸泡15 min,经此处理后云南甜龙竹和黄竹的发芽率分别为84.4%、72.2%,污染率分别为18.7%、29.6%。不同处理种子萌发率差异t检验结果显示:2种竹子种子是否经过3 mg·L~(-1)GA_3浸泡,对其在MS培养基上的发芽率无显著影响,但种子在MS培养基上的发芽率显著高于滤纸上的发芽率。经相同处理黄竹的发芽率均低于云南甜龙竹。[结论]云南甜龙竹、黄竹最佳表面灭菌组合均为:流水冲洗6 h、2%NaClO浸泡10 min、0.1%HgCl_2浸泡15 min;3 mg·L~(-1)GA_3浸泡处理对云南甜龙竹和黄竹种子在MS培养基上的发芽率无显著影响,但MS培养基上种子的发芽率显著高于其在滤纸上的发芽率。