Lignan Glucosides Research Articles

A new lignan glycoside and phenolics from the branch wood of Pinus banksiana Lambert

Abstract Phytochemical investigation of branch wood of Pinus banksiana Lambert resulted in the isolation of a new lignan glycoside, which was named phillyrin-6″-α-rhamnoside. The structure of the new compound was mainly elucidated by chemical and spectral evidence including 2D nuclear magnetic resonance studies. In addition, four known phenolics, including a phenylpropanoid glucoside (trans-isoconiferin), a phenolic acid (caffeic acid), a neolignan (cedrusin), and a lignan glucoside (phillyrin), were reported for the first time to be present in P. banksiana.

New lignan glucosides with tyrosinase inhibitory activities from exocarp of Castanea henryi

Three novel lignan glycosides, 1-[4-(β-glucopyranosyl (1→2)-[β-glucopyranosyl (1→6)]-β-glucopyranosyloxy)-3-methoxyphenyl]-2-[4-(3-hydroxypropyl)-2-methoxyphenoxy]-1,3-propanediol (1), 2,3-dihydro-2-[4-(β-glucopyranosyl (1→2)-[β-glucopyranosyl (1→6)]-β-glucopyranosyloxy)-3-methoxyphenyl]-3-(hydroxymethyl)-7-methoxy-5-benzofuranpropanol (2), 7-hydroxy-9′-β-glucopyranosyloxyl secoisolariciresinol (3) and two known lignans were isolated from exocarp of Castanea henryi. Their structures were established by spectroscopic means, and their tyrosinase inhibitory potentials were evaluated in vitro using mushroom tyrosinase.

Chemical constituents from the fruits of Gardenia jasminoides Ellis

A new lignan glucoside, (+)-(7S,8R,8′R)-lyoniresinol 9-O-β-D-(6″-O-trans-sinapoyl)glucopyranoside (1), and a new iridoid glucoside, 10-O-trans-sinapoylgeniposide (2), together with eight known compounds, were isolated from the fruits of Gardenia jasminoides Ellis. The structures of the isolates were elucidated by extensive spectroscopic studies, including UV, IR, 1D and 2D NMR, ESI-MS, HR-ESI-MS, and CD experiments. The short-term-memory-enhancement activities of some compounds were evaluated on an Aβ transgenic drosophila model.

Constituents of Dalbergia sissoo Roxb. leaves with osteogenic activity

One new isoflavone glucoside, caviunin 7-O-[β-d-apiofuranosyl-(1→6)-β-d-glucopyranoside] (10) and a new itaconic derivative, (E)-4-methoxy-2-(3,4-dihydroxybenzylidene)-4-oxobutanoic acid (15) along with series of isoflavones and flavonols with their glucosides (1-9 and 11-14) and a lignan glucoside (16) were isolated from the ethanolic extract of Dalbergia sissoo leaves. The structures of these compounds were established on the basis of IR, UV, (1)H and (13)C NMR, DEPT, COSY, HSQC, HMBC and MS data. All compounds (1-16) were assessed for osteogenic activity in primary calvarial osteoblast cultures. Compounds 1-4 and 10 increased alkaline phosphatase activity and mineralization thus resulting in significant osteogenic activity.

A new iridoid glycoside and NO production inhibitory activity of compounds isolated from Russelia equisetiformis

From the 1-BuOH-soluble fraction of a MeOH extract of the leaves of Russelia equisetiformis, one new iridoid glucoside was isolated along with 24 known compounds, comprising iridoids and iridoid glucosides, phenyl propane glucosides, phenyl ethanoids, lignan glucosides, and flavonoid glucosides. The structure of the new compound was elucidated to be 10-O-cinnamoyl sinuatol. Of the 25 compounds isolated, rehmaglutin B exhibited moderate inhibitory activity toward NO production, which was not associated with cytotoxicity.

Antinociceptive, Free Radical–Scavenging, and Cytotoxic Activities of Acanthus hirsutus Boiss

In vivo antinociceptive and in vitro radical scavenging and cytotoxic activities of Acanthus hirsutus Boiss. aqueous extract were investigated to give a new insight into plant usage in traditional medicine. The extract showed significant antinociceptive activity in acetic acid-induced writhing test in mice after oral application and did not change the hind-leg retraction period in the hot-plate test for any dose applied. In addition, the extract showed radical-scavenging activity against 2,2-diphenyl-1-picryl-hydrazyl, nitric oxide, and superoxide radicals similar to those of standard compounds 3-t-butyl-4-hydroxyanisole, ascorbic acid (vitamin C), and quercetin. The gallic acid equivalent total phenolic content of the plant was found to be 65.4 mg/g dry extract. Cytotoxic activity of the aqueous extract was tested against 3 different cancer cell lines-Hep-2 (human larynx epidermoid carcinoma), RD (human rhabdomyosarcoma), and L20B (transgenic murine L cells)-and 1 noncancerous cell line (VERO) using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide method. Through the phytochemical studies, the following compounds were isolated: 3 lignan glucosides [(-)-syringaresinol-di-O-β-glucopyranoside, (-)-medioresinol-di-O-β-D-glucopyranoside, (-)-pinoresinol-4'-O-β-glucopyranoside], 2 benzoxazinoids [2-hydroxy-1,4-benzoxazin-3(4H)-one, (2R)-2-O-β-glucopyranosyl-1,4-benzoxazin-3(4H)-one], 4 phenylethanoid glycosides (acteoside, leucosceptoside A, martynoside, hattushoside), and 2 phenylpropanoid glucosides (sinapyl aldehyde-4-O-β-glucopyranoside, sinapyl alcohol-4-O-β-glucopyranoside). Cytotoxic and radical-scavenging activities of the isolated compounds were also determined. 2-hydroxy-1,4-benzoxazin-3(4H)-one and acteoside were the most active compounds in both experiments.

Potent anti-platelet constituents from Centaurea iberica.

New naturally occurring nitrogenous compounds 1 and 2, along with a new dimeric lignan glucoside 3, have been isolated from the ethyl acetate soluble fraction of Centaurea iberica. Their structures have been elucidated through spectroscopic techniques. All the isolated compounds showed significant platelet aggregation inhibition.

Lignan glucoside from Sinopodophyllum emodi and its cytotoxic activity

Abstract A new lignan glycoside was isolated from the n -butanol extract of the roots and rhizomes of Sinopodophyllum emodi . On the basis of spectral evidences, its structure was established and named as 4,5-didemethylpodophyllotoxin 7′- O - β - d -glucopyranoside. This compound showed cytotoxicity against four human cancer cell lines (Hela, K562, SH-SY5Y and CNE) in vitro .

Antioxidant, antibacterial and antigiardial activities of Walsura robusta Roxb.

Walsura robusta Roxb. (Family: Meliaceae) is a well-known multi-purpose medicinal plant, and has been employed for a wide range of disease conditions without documented scientific data. In the current study, four pure isolated compounds, 3,4,5-trimethoxyphenyl β-D-glucopyranoside (1), turpinionoside A (2), (+)-lyoniresinol 3α-O-β-D-glucopyranoside (3) and (−)-lyoniresinol 3α-O-β-D-glucopyranoside (4), were isolated from the leaves and twigs of W. robusta. Biological evaluation for free radical scavenging, antibacterial and antigiardial activities was performed. We investigated antioxidant effects of the crude extracts as well as the isolated compounds using 1,1-diphenyl-2-picrylhydrazyl radical (DPPH), hydroxyl radical (OH), and superoxide anion (O2) scavenging assays. Three phenolic glucosides (1, 3 and 4) were found to possess strong antioxidant activity. They scavenged DPPH• with IC50 values in the range of 51.5–86.6 µM. We also detected the superoxide dismutase-like activities in compounds 3 and 4 which are lignan glucosides, demonstrating potent superoxide scavenging activity with IC50 values in the range of 0.8 and 0.7 µM, respectively. Other biological activities including antibacterial and antigiardial assays were carried out. Preliminary results demonstrated that most extracts, except the diethyl ether extract, exhibited inhibition zones against all Gram-positive bacteria including Bacillus cereus, Staphylococcus aureus, Streptococcus mutans, and S. pyogenes. Aqueous extracts of this plant species could inhibit Gram-positive and some Gram-negative bacteria such as Escherichia coli, Salmonella typhi and Shigella sonnei. However, the determination of minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) of W. robusta on all tested bacterial strains showed only weak activity, and their MBCs were greater than 25 mg mL−1. For antigiardial activity, incubation with 2 × 105 trophozoites mL−1 of the culture medium with the crude extracts at concentration ranged from 31.25 to 1000 µg mL−1 demonstrated no activity (MIC > 1000 µg mL−1).

Antioxidant Components as Potential Neuroprotective Agents in Sesame (Sesamum indicum L.)

Sesame (Sesamum indicum L.) is one of the most important oilseed crops, having seeds and its edible oil that are highly valued as a traditional food. Many studies have examined the health value of sesame seeds and oil. Among the bioactive components in sesame seeds, lignans and tocopherols have been identified as the major antioxidants responsible for the resistant oxidative deterioration of sesame seeds and oil. These same antioxidants have been reported to have protective effects against human disease such as neurodegenerative disease. This review summarizes the chemical properties of lignans including lipid-soluble lignans, lignan glucosides and tocopherols, and their bioactivities such as antioxidativity and neuroprotection. We also review the biosynthesis of lignan in sesame seeds and transformation of lignans during food processing in sesame oil. Sesame seeds and its antioxidants may be a potent natural agent with both therapeutic applications and use in preventing human illness such as neurodegenerative disease.

Structural discrimination of isomeric tetrahydrofuran lignan glucosides by tandem mass spectrometry

Due to the possible role in human health, the number of analytical studies on lignans aimed at their quali- and quantitative analysis in plant extracts, biological fluids and foods is continuously increasing. However, helpful systematic mass spectrometric investigations on these compounds are few and rather limited to specific lignan sub-classes. To increase the comprehension of the previously outlined picture of the gas-phase properties of furofuran lignans, we extended the study to tetrahydrofuran lignans and here we reported the collision-activated dissociation (CAD) fragmentation patterns of the alkali metal cation adducts, [M+Alk](+), and [M-H](-) ions of three isomeric tetrahydrofuran lignans, (+)-8'-hydroxylariciresinol 4'-O-beta-D-glucopyranoside (1), (+)-7'-hydroxylariciresinol 7'-O-beta-D-glucopyranoside (2) and 4-O-beta-D-glucopyranosyloxy-3,3'-dimethoxy-7,9'-epoxylignan-5',8',9-triol (3) investigated by electrospray ionization triple quadrupole mass spectrometry (ESI-TQMS). Hydrogen/deuterium (H/D) solution exchange experiments, allowing the selective H/D exchange of all the acidic hydrogen atoms, proved to be a very effective tool to obtain information on the nature of fragments generated during TQ/CAD processes. The [M+Na](+) CAD mass spectra of the three isomeric tetrahydrofurans revealed four different pathways involving the loss of the glucose moiety, which allowed the assignment of the glycosylation site. In the negative ion mode, the main fragmentation channel of the [M-H](-) ions of O-glucosylated lignans at the phenolic oxygen atoms is represented by the loss of 162 Da. When the sugar is bound to a benzylic OH group the loss of the sugar as a 180 Da unit occurs eventually following the loss of a water molecule involving both the C(9)H(2)OH chain and the sugar.

Absolute configuration of (+)-pinoresinol 4- O-[6″- O-galloyl]- β- d-glucopyranoside, macarangiosides E, and F isolated from the leaves of Macarangatanarius

A lignan glucoside, (+)-pinoresinol 4- O-[6″- O-galloyl]- β- d-glucopyranoside ( 1), and two megastigmane glucosides, named macarangiosides E and F ( 2, 3), together with 15 known compounds ( 4– 18) were isolated from leaves of Macaranga tanarius (L.) Müll.-Arg. (Euphorbiaceae). Their structures were elucidated by spectroscopic and chemical analyses. In addition, the absolute stereochemistry of macarangiosides B and C isolated previously from the same plant was also determined for the first time. Compounds 1 and 2 were galloylated on glucose and possessed potent DPPH radical-scavenging activity.

Tarennanosides A–H, Eight New Lignan Glucosides from Tarenna attenuata and Their Protective Effect on H2O2‐Induced Impairment in PC12 Cells

Eight new lignan glucosides, tarennanosides A-H (1-8, resp.), were isolated from the whole plant of Tarenna attenuata, together with three known compounds, fernandoside, (-)-lyoniresinol, and (-)-isolariciresinol. The planar structures of new compounds were elucidated mainly by analysis of physical and spectroscopic data, and the absolute configurations were determined by acid hydrolysis as well as CD spectroscopy. Compounds 1 and 2 exhibited potent antioxidant activities against H2O2-induced impairment in PC12 cells. Preliminary mechanism study by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method showed that these two compounds could act as radical scavengers.

A new flavonol galloylrhamnoside and a new lignan glucoside from the leaves of Koelreuteria henryi Dummer

A new flavonol galloylrhamnoside, kaempferol 3-O-(2'',3''-di-O-galloyl)-alpha-L: -rhamnopyranoside, and a new lignan glycoside, hinokinin 7-O-beta-D: -glucopyranoside were isolated from the leaves of Koelreuteria henryi, along with 18 known compounds, including six flavonol glycosides (3-8), three lignans (9-11), four chlorophyll derivatives (12-15), two steroids (16, 17), and three aromatic compounds (18-20). The structures were determined on the basis of spectral analysis and chemical evidence. The scavenging effect of 1-8 and 20 on the stable free radical 1,1-diphenyl-2-picrylhydrazyl was examined. Compounds 1, 5, 6, and 20 showed more potent activity than that of trolox.

A new lignan glucoside from the stems of Callicarpa japonica Thunb. var. luxurians Rehd.

A new lignan glucoside (1) was isolated from the stems of Callicarpa japonica Thunb. var. luxurians Rehd. (Verbenaceae), along with six known lignan glucosides and three known triterpenoids. The chemical structure of 1 was characterized as (+)-lyoniresinol 3 alpha-O-(6''-3,5-dimethoxy-4-hydroxybenzoyl)-beta-D-glucopyranoside on the basis of spectroscopic data. In addition, the radical-scavenging effect of four lignans on the stable free radical 1,1-diphenyl-2-picrylhydrazyl was examined. Among the tested compounds, three compounds, including 1, showed almost the same scavenging activity as that of alpha-tocopherol.

Phytochemical and biological studies on Acanthus hirsutus Boiss

Acanthus L. is a genus of 30 species of flowering plants in the family Acanthaceae and represented by five species in Turkish flora [1]. Some of the Acanthus species are used as a herbal remedy for various ailments such as cough, chest pain, snake bite, paralysis, asthma, stomach upset, urinary disorders and rheumatic pains in different countries [2, 3]. The titled plant, Acanthus hirsutus Boiss. is endemic for Turkey and used as expectorant, for wound healing and against constipation in Anatolia [4]. There is no phytochemical or biological record in the literature for this species up to now. After serial chromatographies of the methanol extract of the plant, three lignan glucosides (-)-syringaresinol-di-O-β-D-glucopyranoside, (-)-medioresinol-di-O- β -D-glucopyranoside, (-)-pinoresinol-4'-O- β -D-glucopyranoside), two benzoxazinoids (4-hydroxy-2H-1,4-benzoxazin-3(4H)-one, (2R)-2-O- β -D-glucopyranosyl-4-hydroxy-2H-1,4-benzoxazin-3(4H)-one), four phenylethanoid glycosides (acteoside, martynoside, leucosceptoside A, hattushoside) and two phenylpropanoid glucosides (sinapyl aldehyde-4-O- β -D-glucopyranoside, sinapyl alcohol-4-O- β -D-glucopyranoside) were isolated. Aqueous A. hirsutus extract (IC50=201–700µg/ml) and its isolated compounds (IC50=11.17–262.42µg/ml) showed significant cytotoxic activity in vitro against Hep-2, RD and L20B cell lines in MTT assay. Their radical scavenging activities were also found against 2,2-diphenyl-1-picryl-hydrazyl (DPPH) radical (IC50=86.30µg/ml for the extract, IC50=10–200µg/ml for the compouds.

Glucosides from the Roots of Capparis tenera

Two new lignan glucosides, compounds 2 and 3, two new 1H-indole-alkaloid glucosides, 5 and 6, as well as two new phenolic glucosides, 7 and 10, were isolated from the roots of Capparis tenera, together with five known compounds. Their structures were characterized by chemical and spectroscopic methods. Most of these isolates were obtained for the first time from Capparidaceae. The antioxidant and anti-inflammatory activities of the new compounds were investigated.

UDP-glucose:(6-methoxy)podophyllotoxin 7- O-glucosyltransferase from suspension cultures of Linum nodiflorum

Cell cultures of Linum species store 6-methoxypodophyllotoxin (MPTOX), podophyllotoxin (PTOX) and related lignans as O-glucosides. UDP-glucose:(M)PTOX 7- O-glucosyltransferase has been detected and characterised in protein preparations of suspension-cultured cells of Linum nodiflorum L. (Linaceae). The maximal lignan glucoside contents in the cells are preceded by a rapid increase of the specific glucosyltransferase activity on day six of the culture period. MPTOX glucoside is the major lignan with up to 1.18 mg g −1 of the cell dry wt which is more than 30-fold of the PTOX glucoside content. Of the three aryltetralin lignans tested as substrates, PTOX and MPTOX display comparable apparent K m values of 4.7 and 5.4 μM, respectively. 5′-Demethoxy-6-methoxypodophyllotoxin is converted with the highest velocity of 25.2 pkat mg −1 while also possessing a higher K m of 14.7 μM. Two-substrate test series indicate that all three compounds compete for the active site of a single protein. The structurally similar lignan β-peltatin acts as competitive inhibitor as well. However, the 6- O-glucosidation is most likely catalysed by a separate enzyme. The (M)PTOX 7- O-glucosyltransferase works best at a pH around 9 and a temperature around 35 °C. A 15–30% increase of the reaction rate is effected by the addition of 0.9 mM Mn 2+.

Two new lignan glucosides from the fruit of Vitex cannabifolia

Two new phenyldihydronaphthalene-type lignan glucosides, vitecannasides A (1) and B (2) were isolated from the fruit of Vitex cannabifolia Sieb. et. Zucc. (Verbenaceae) along with the six known lignan derivatives (3-8), four known iridoid glucosides (9-12), three known flavonoids (13-15), and one known phenylbutanone glucoside (16). Their chemical structures were determined on the basis of spectroscopic data as well as chemical evidence. The scavenging effect of 1, 2, and 11-16 on the stable free radical 1,1-diphenyl-2-picrylhydrazyl was examined. Compounds 1, 2, 14, and 15 exhibited stronger activity than that of L: -cysteine. Especially, 14 and 15 showed more potent activity than that of alpha-tocopherol.

Lignan Glucosides and Serotonin Phenylpropanoids from the Seeds of Leuzea carthamoides

Two lignan glucosides, the known tracheloside and the new carthamoside, together with their two known aglycones, trachelogenin and (7E,8'S)-7,8-didehydroarctigenin (cf. cartha- mogenin), were isolated from the seeds of Leuzea carthamoides. Additional four phenylpropanoid derivatives of tryptamine, the E and Z isomers of N-feruloylserotonin and N-isoferuloylserotonin, were also isolated and identified. Their structure determination and identification were performed by spectroscopic, mainly NMR analysis.