New lignan glycosides with potent antiinflammatory effect, isolated from Justicia ciliata

Two new lignan glycosides, 4-O-[alpha-L-arabinopyranosyl-(1' "-->2' ')-beta-D-xylopyranosyl-(1' " '-->5' ')-beta-D-apiofuranosyl]diphyllin (1), named ciliatoside A (1), and 4-O-?[beta-D-apiofuranosyl-(1' " "-->3' ")-alpha-L-arabinopyranosyl-(1' "-->2' ')][beta-D-xylopyranosyl-(1' " '-->5' ')]-beta-D-apiofuranosyl?diphyllin (2), named ciliatoside B (2), were isolated from the whole plant of Justicia ciliata. The structures of 1 and 2 were determined by spectral and chemical methods. Compounds 1 and 2 strongly inhibited the accumulation of NO(2)(-) in lipopolysaccharide-stimulated RAW 264.7 cells in a concentration-dependent manner with IC(50) values of 27.1 +/- 1.6 and 29.4 +/- 1.4 microM, respectively.     

Oleanane saponins in "kancolla", a sweet variety of Chenopodium quinoa

Seven triterpenoid saponins were isolated from the seeds of "kancolla", a sweet variety of Chenopodium quinoa. Their structures were phytolaccagenic acid 3-O-[alpha-L-arabinopyranosyl-(1' '-->3')-beta-D-glucuronopyranosyl]-28-O-beta-D-glucopyranoside, oleanolic acid 3-O-[beta-D-glucopyranosyl-(1'-->3')-alpha-L-arabinopyranosyl]-28-O-beta-D-glucopyranoside, hederagenin 3-O-[beta-D-glucopyranosyl-(1'-->3')-alpha-L-arabinopyranosyl]-28-O-beta-D-glucopyranoside, phytolaccagenic acid 3-O-[beta-D-glucopyranosyl-(1'-->3')-alpha-L-arabinopyranosyl]-28-O-beta-D-glucopyranoside, oleanolic acid 3-O-[beta-D-glucuronopyranosyl]-28-O-beta-D-glucopyranoside, oleanolic acid 3-O-[alpha-L-arabinopyranosyl-(1'-->3')-beta-D-glucuronopyranosyl]-28-O-beta-D-glucopyranoside, and the new compound serjanic acid 3-O-[beta-D-glucopyranosyl-(1'-->3')-alpha-L-arabinopyranosyl]-28-O-beta-D-glucopyranoside (1). The structure of 1 was characterized on the basis of spectroscopic and chemical evidence.     

乌桕叶化学成分研究

通过利用正相硅胶色谱、大孔吸附树脂柱色谱、葡聚糖凝胶LH-20色谱、制备薄层色谱和半制备HPLC等多种分离方法,运用现代波谱技术对所分离的化合物进行结构鉴定,从乌桕Sapium sebiferum叶中分离得到15个化合物,分别鉴定为(+)-(7R,7′R,7"S,7(')S,8S,8′S,8"S,8(')S)-4",4(')-dihydroxy-3,3′,3",3('),5,5′-hexamethoxy-7,9';7',9-diepoxy-4,8";4′,8(')-bisoxy-8,8′-dineo-lignan-7",7('),9",9(')-tetraol(1),1-(4′-hydroxy-3'-methoxyphenyl)-2-[4"-(3-hydroxy propyl)-2",6"-dimethoxyphenoxy]propane-1,3-dio1(2),苏式-2,3-二-(4-羟基-3-甲氧基苯)-3-甲氧基丙醇(3),threo-5-hydroxy-3,7-dimethoxyphenylpropane-8,9-diol(4),boropinol B(5),threo-8S-7-methoxysyringylglycerol(6),5-羟甲基糠醛(7),5-甲氧甲基-1H-吡咯-2-甲醛(8),槲皮素(9),山柰酚(10),没食子酸乙酯(11),松柏醛(12),香草醛(13),7-羟基-6-甲氧基香豆素(14),正二十七烷醇(15),除化合物9～ 11,14外,以上化合物均为首次从乌桕中分离得到.     

Megastigmane glycosides and an acylated triterpenoid from Eriobotrya japonica.

Two new megastigmane glycosides, eriojaposides A (1) and B (2), and a new acylated triterpenoid (3) were isolated along with nine known compounds from a leaf extract of Eriobotrya japonica. The structures of 1--3 were characterized as (6R,9R)-3-oxo-alpha-ionyl-9-O-beta-xylopyranosyl-(1' '-->6')-beta-glucopyranoside, (6R,9R)-3-oxo-alpha-ionyl-9-O-alpha-rhamnopyranosyl-(1' '-->6')-beta-glucopyranoside, and 3 alpha-trans-feruloyloxy-2 alpha-hydroxyurs-12-en-28-oic acid, respectively, on the basis of spectral and chemical evidence.     

HPLC同时测定火麻仁中α-亚麻酸、亚油酸和油酸含量

目的:建立同时测定火麻仁中的α-亚麻酸、亚油酸和油酸含量的HPLC方法.方法:色谱柱为Kromasil 100-5 C18(4.6 mm×250 mm,5 μm),以乙腈-o.1％磷酸(80∶20)为流动相,流速1 mL? min-1,柱温30℃,检测波长203 nm.结果:α-亚麻酸在34.625～554 mg? L-1(r=0.999 9),亚油酸在56.375～902 mg?L -1(r=1),油酸在17.125 ～ 274 mg? L-1(r =0.999 9)呈良好的线性关系;平均回收率α-亚麻酸为96.38％,RSD0.93％(n=6);亚油酸为97.79％,RSD 0.92％(n=6);油酸为97.06％,RSD 1.51％ (n =6).结论:本法简便准确,专属性强,重复性好,可作为火麻仁的质量控制的参考.     

Bromophenols from the red alga Rhodomela confervoides

Six new bromophenols, 3-bromo-4,5-bis(2,3-dibromo-4,5-dihydroxybenzyl)pyrocatechol (1), 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-hydroxymethyldiphenylmethane (2), 2,2',3-tribromo-3',4,4',5-tetrahydroxy-6'-ethyloxymethyldiphenylmethane (3), (+/-)-2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde (4), (+/-)-2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde dimethyl acetal (5), and 3-bromo-4,5-dihydroxybenzoic acid methyl ester (6), together with eight known bromophenols, 3-bromo-4,5-dihydroxybenzaldehyde (7), 2,3-dibromo-4,5-dihydroxybenzyl alcohol (lanosol, 8), 2,3-dibromo-4,5-dihydroxybenzyl methyl ether (9), 2,3-dibromo-4,5-dihydroxybenzyl ethyl ether (10), 2,3-dibromo-4,5-dihydroxybenzylaldehyde (11), bis(2,3-dibromo-4,5-dihydroxybenzyl) ether (12), 3-bromo-4-(2,3-dibromo-4,5-dihydroxybenzyl)-5-methoxymethylpyrocatechol (13), and 2,2',3,3'-tetrabromo-4,4',5,5'-tetrahydroxydiphenyl methane (14), were isolated from the red alga Rhodomela confervoides. Their structures were elucidated by chemical and spectroscopic methods including IR, HRFABMS, and 1D and 2D NMR techniques.     

The absolute configuration of 1-(3',4'-dihydroxycinnamoyl)cyclopentane-2,3-diol from the amazonian tree Chimarrhis turbinata

An antioxidant, 1-(3',4'-dihydroxycinnamoyl)cyclopentane-2,3-diol [or (E)-2,3-dihydroxycyclopentyl-3-(3',4'-dihydroxyphenyl)acrylate (1)], and two known trans- and cis-chlorogenic acid methyl esters were isolated from the ethanolic extract of the leaves of Chimarrhis turbinata. The relative configuration of 1 was determined by NMR and by comparison of the circular dichroic spectrum (CD) with those of the enantiomers of synthetic 3',4'-dimethoxycinnamoyl analogues. The absolute configuration of one of the synthetic enantiomers was determined using the CD exciton chirality method. This established the structure of naturally occurring 1 as (E)-2,3-dihydroxycyclopentyl-3-(3',4'-dihydroxyphenyl)acrylate.     

Coumarins from the fruits of Seseli devenyense

Eight new coumarins were isolated from the fruits of Seseli devenyense Simonkai. Their structures were established from NMR and mass data and their absolute configurations from chemical degradation correlation reactions. The new structures are the decanoic and dodecanoic esters of (+)-lomatin (3, 4), the decanoates of (+)-cis-khellactone at positions 4' (5) and 3' (6) as well as the 2'S epimer of 8-(2,3-dihydroxy-3-methylbutyl)-7-hydroxychromen-2-one (7) named devenyol, its two O-monoglucosides at positions 3' and 7 named devenyosides A (8) and B (9), and the corresponding 3'- and 7-O-diglucoside named devenyoside C (10). This plant is an interesting example of stereochemical diversity based on biodiversity given that other members of the Apiaceae family produce exclusively the 2'R epimers of compounds 7-9.     

Bromophenol derivatives from the red alga Rhodomela confervoides

Eight new bromophenol derivatives, 2,3-dibromo-4,5-dihydroxybenzyl methyl sulfoxide (1), 4-(2,3-dibromo-4,5-dihydroxyphenyl)-3-butene-2-one (2), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (3), 2-(3-bromo-5-hydroxy-4-methoxyphenyl)-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid methyl ester (4), 2-phenyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propionic acid (5), 4'-methoxy-2',3',3'-tribromo-4',5',5'-trihydroxydiphenylacetic acid (6), and 3-bromo-5-hydroxy-4-methoxyphenylacetic acid (7) and its methyl ester (8), together with a known bromophenol, 3-bromo-5-hydroxy-4-methoxybenzoic acid (9), were isolated from the red alga Rhodomela confervoides. Their structures were elucidated by spectroscopic methods including IR, EIMS, FABMS, ESIMS, HRFABMS, HRESIMS, 1D and 2D NMR, and single-crystal X-ray structure analysis. Compounds 1-4, 8, and 9 were found inactive against several human cancer cell lines and microorganisms.     

Isoflavone diglycosides from Glycosmis pentaphylla

Six new apiosyl-(1-->6)-glucosyl isoflavones (1-6) and four known ones were isolated from the stems of Glycosmis pentaphylla. The structures of the new glycosides are 3',7-dihydroxy-4',5,6-trimethoxyisoflavone 7-O-(5-O-trans-p-coumaroyl)-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (1), 2',7-dihydroxy-4',5',5,6-tetramethoxyisoflavone 7-O-(5-O-trans-p-coumaroyl)-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (2), 2',7-dihydroxy-4',5',5,6-tetramethoxyisoflavone 7-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (3), 7-hydroxy-4',8-dimethoxyisoflavone 7-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (4), 7-hydroxy-4',6-dimethoxyisoflavone 7-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (5), and 4',5-dihydroxy-3',7-dimethoxyisoflavone 4'-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside (6). Their structures were established primarily by NMR experiments and chemical methods.     

Novel oligorhamnosides from the stem bark of Cleistopholis glauca

A reinvestigation of the stem bark of Cleistopholis glauca yielded 14 compounds, of which seven were either novel or had not been previously reported from this species. These were identified as the farnesane sesquiterpene methyl-(2E,6E)-10-oxo-3,7, 11-trimethyl-dodeca-2,6-dienoate (1); the azaanthracene alkaloid cleistopholine (4); two partially acetylated oligorhamnoside derivatives, 1-O-dodecanyl-2,3, 4-tri-O-acetyl-alpha-rhamnopyranosyl-(1-->3)-2, 4-di-O-acetyl-alpha-rhamnopyranosyl-(1-->3)-4-O-acetyl-alpha-rhamnopy ranosyl-(1-->4)-alpha-rhamnopyranoside (6) and 1-O-dodecanyl-2, 4-di-O-acetyl-alpha-rhamnopyranosyl-(1-->3)-2, 4-di-O-acetyl-alpha-rhamnopyranosyl-(1-->3)-4-O-acetyl-alpha-rhamnopy ranosyl-(1-->4)-alpha-rhamnopyranoside (8), for which the trivial names cleistetroside-7 and cleistetroside-6 were assigned, respectively; the dihydrobenzofuran neolignan rel-(2alpha, 3beta)-7-O-methylcedrusin (12); and the flavonoids dihydroquercetin (13) and quercetin (14). Structure assignments of all compounds were established by spectroscopic methods and comparison with published data. The chemosystematic significance of the occurrence of the isolated components is mentioned. Compounds 1, 6, and 8 are novel natural products.     

Sesquiterpenes and flavonol glycosides from Zingiber aromaticum and their CYP3A4 and CYP2D6 inhibitory activities

Three new sesquiterpenes, (2R,3S,5R)-2,3-epoxy-6,9-humuladien-5-ol-8-one (1), (2R,3R,5R)-2,3-epoxy-6,9-humuladien-5-ol-8-one (2), and (5R)-2,6,9-humulatrien-5-ol-8-one (3), and two new flavonol glycosides, kaempferol-3-O-(2,3-di-O-acetyl-alpha-l-rhamnopyranoside) (4) and kaempferol-3-O-(2,3,4-tri-O-acetyl-alpha-l-rhamnopyranoside) (5), were isolated from the EtOAc-soluble fraction of the water extract of Zingiber aromaticum, along with 13 known compounds (6-18). The structures of the isolated compounds were elucidated on the basis of spectroscopic and chemical analyses. The isolated compounds were tested for their inhibitory activity on the metabolism mediated by CYP3A4 or CYP2D6 using [N-methyl-(14)C]erythromycin or [O-methyl-(14)C]dextromethorphan as a substrate, respectively. Kaempferol-3-O-(2,3,4-tri-O-acetyl-alpha-l-rhamnopyranoside) (5) showed the most potent inhibitory activity (IC(50), 14.4 microM) on the metabolism mediated by CYP3A4, and kaempferol-3-O-methyl ether (14) inhibited CYP2D6 most potently (IC(50), 4.63 microM).     

Reinvestigation of structure of porritoxin,a phytotoxin of Alternaria porri

The structure of porritoxin, a phytotoxin of Alternaria porri, was reinvestigated by detailed 2D NMR analysis including (1)H-(13)C and (1)H-(15)N HMBC experiments. The structure of porritoxin was determined to be 2-(2'-hydroxyethyl)-4-methoxy-5-methyl-6-(3' '-methyl-2' '-butenyloxy)-2,3-dihydro-1H-isoindol-1-one (1). Thus our previous proposed structure, 8-(3',3'-dimethylallyloxy)-10-methoxy-9-methyl-1H-3,4-dihydro-2,5-benzoxazocin-6(5H)-one (2), is incorrect.     

血满草化学成分的研究

首次对采自峨眉山的接骨木属植物血满草进行了化学成分的研究,从氯仿部分及总浸膏的水悬浮液中分离得到5个化合物:分别是1-(3-羟基-4-甲氧基)乙烷-1′,2′-二醇(1-(3-hydroxy-4-methoxyphenyl)-1′,2′-ethane-diol,1),熊果酸(ursolic acid,2),1-(3,4,5-三甲氧基苯基)乙烷-1′,2′-二醇(1-(3,4,5-trimethoxyphenyl)-1′,2′-ethanediol,3),落叶松脂醇(lariciresinol,4),5,7,3′,4′-四羟基黄酮-3-O-吡喃鼠李糖(1→6)吡喃葡萄糖苷(5,7,3′,4′-tetramethoxyflavone-3-O-rhamnopyranosyl-(1→6)-glucopyranoside,5)。其中1、3、4、5为首次从该植物中分离得到。     

Inhibitors of osteoclast differentiation from Cephalotaxus koreana

Three new flavonoid glycosides ( 1- 3), 11-hydroxyhainanolidol ( 4), and a new dibenzylbutyrolactone lignan glycoside ( 5) were isolated from the aerial parts of Cephalotaxus koreana Nakai, along with 19 known flavonoids. The structures of the new compounds were elucidated using spectroscopic evidence, primarily NMR and MS. Twenty-four compounds were isolated, and among these isoscutellarein 5-O-beta-D-glucopyranoside ( 3), apigenin ( 6), kaempferol 3-O-alpha-L-rhamnopyranosyl(1'-->6')-beta-D-glucopyranoside ( 7), tamarixetin 3-O-alpha-L-rhamnopyranosyl(1'-->6')-beta-D-glucopyranoside ( 8), quercetin 3-O-[6'-O-acetyl]-beta-D-glucopyranoside ( 9), and quercetin 3-O-alpha-L-rhamnopyranoside ( 10) showed significant inhibitory activities against osteoclast differentiation at concentrations of 0.1 and 1.0 microg/mL.     

Biphenyl glycosides from the fruit of Pyracantha fortuneana

Five new biphenyl glycosides, fortuneanosides A (1), B (2), C (3), D (4), and E (5), were isolated from the fruit of Pyracantha fortuneana. Their structures were established as 3,3'-dihydroxy-5'-methoxy-(1,1'-biphenyl)-4-O-beta-d-glucoside, 4'-hydroxy-2,3',5'-trimethoxy-(1,1'-biphenyl)-2'-O-beta-d-glucoside, 4'-hydroxy-3',5'-dimethoxy-(1,1'-biphenyl)-2-O-beta-d-glucoside, 2,4'-dihydroxy-3',5'-dimethoxy-(1,1'-biphenyl)-3-O-beta-d-glucoside, and 3,4'-dihydroxy-3',5'-dimethoxy-(1,1'-biphenyl)-4-O-beta-d-glucoside by spectroscopic analysis. All compounds were evaluated for inhibitory activity against tyrosinase. Compared with arbutin (IC(50) = 0.23 mM), fortuneanoside D possessed more potency, with an IC(50) value of 0.07 mM.     

Bioactive constituents of the roots of Cynanchum atratum

A novel biphenylneolignan, 2,6,2',6'-tetramethoxy-4,4'-bis(2,3-epoxy-1-hydroxypropyl)biphenyl (1), and two new glycosides named atratoglaucosides A (2) and B (3), were isolated from the roots of Cynanchum atratum, and their structures were determined on the basis of chemical and spectroscopic evidence. The aglycons of 2 and 3 were identified as glaucogenin C and 7-desoxyneocynapanogenin A, a new disecopregnane. A known compound, glaucogenin C 3-O-beta-D-cymaropyranosyl-(1-->4)-alpha-L-diginopyranosyl-(1-->4)-beta-D-thevetopyranoside (4), isolated from the same source, showed a significant cytotoxic effect against 212 cells. This substance also gave a significant inhibitory effect on TNF-alpha (tumor necrosis factor-alpha) formation from the RAW 264.7 mouse macrophage-like cell line stimulated with LPS (lipopolysaccharide) and on the N9 microglial cell line stimulated with LPS/IFN-gamma (interferon-gamma).     

Phenolic glycosides from Viscum angulatum

Three new glycosides, pinocembrin 7-O-apiosyl(1-->5)apiosyl(1-->2)-beta-D-glucopyranoside (1), 2',3',4',3' '-tetramethoxy-1,3-diphenylpropane 5',4' '-di-O-beta-D-glucopyranoside (2), and rhamnocitrin 3-O-apiosyl(1-->5)apiosyl(1-->2)-[alpha-L-rhamnopyranosyl(1-->6)]-beta-D-glucopyranoside (3), were isolated from Viscum angulatumalong with viscumneoside V, naringenin, and homoeriodictyol. Their structures were established by spectral and chemical methods.     

Rat lens aldose reductase inhibitory constituents of Nelumbo nucifera stamens

Aldose reductase, the principal enzyme of the polyol pathway, has been shown to play an important role in the complications associated with diabetes. A methanol extract of the stamens of Nelumbo nucifera Gaertn. was shown to exert an inhibitory effect on rat lens aldose reductase (RLAR), and thus was fractionated using several organic solvents, including dichloromethane, ethyl acetate and n-butanol. The ethyl acetate-soluble fraction, which manifested potent RLAR-inhibitory properties, was then purified further via repeated measures of silica gel and Sephadex LH-20 column chromatography. Thirteen flavonoids: kaempferol (1) and seven of its glycosides (2-9), myricetin 3',5'-dimethylether 3-O-beta-d-glucopyranoside (10), quercetin 3-O-beta-d-glucopyranoside (11) and two isorhamnetin glycosides (12, 13) were isolated from N. nucifera, as well as four non-flavonoid compounds: adenine (14), myo-inositol (15), arbutin (16) and beta-sitosterol glucopyranoside (17). These compounds were all assessed with regard to their RLAR-inhibitory properties. Among the isolated flavonoids, those harboring 3-O-alpha-l-rhamnopyranosyl-(1-->6)-beta-d-glucopyranoside groups in their C rings, including kaempferol 3-O-alpha-l-rhamnopyranosyl-(1-->6)-beta-d-glucopyranoside (5) and isorhamnetin 3-O-alpha-l-rhamnopyranosyl-(1-->6)-beta-d-glucopyranoside (13), were determined to exhibit the highest degree of rat lens aldose reductase inhibitory activity in vitro, evidencing IC(50) values (concentration required for a 50% inhibition of enzyme activity) of 5.6 and 9.0 microm, respectively.     

Cytotoxic sesquiterpene lactones from Eupatorium lindleyanum

Ten new guaiane type sesquiterpene lactones, namely, eupalinilides A-J (1-10), as well as nine known compounds, eupachinilide C (11), eupachifolin D (12), eupachinilide E (13), 2alpha-hydroxyeupatolide (14), 3-deacetyleupalinin A (15), heliangine (16), 8beta-tigloyloxy-2,3-seco-6betaH,7alphaH-helianga-4Z,11(13)-diene-3,10beta;6, 12-diolid-2-oic acid (17), 8beta-(4'-hydroxytigloyloxy)-3beta,14-dihydroxy-6betaH,7alphaH-germacra-1(10)Z,4Z,11(13)-trien-6,12-olide (18), and 8beta-tigloyloxy-3beta,14-dihydroxy-6betaH,7alphaH-germacra-1(10)Z,4E,11(13)-trien-6,12-olide (19), were isolated from the whole plant of Eupatorium lindleyanum. Eupalinilides B (2), C (3), E (5), F (6), and I (9) have been tested for cytotoxicity against P-388 and A-549 tumor cell lines. The results showed that eupalinilides B (2) and E (5) demonstrated potent cytotoxicity. The structures of these compounds were determined by spectroscopic methods including 1D and 2D NMR spectra.