Two new norneolignans from Callicarpa kwangtungensis.

Two new norneolignans, (7S,8R)-3-methoxy-3',4,9-trihydroxy-4',7-epoxy-8,3'-neolignane-1'-carboxylic acid (1) and (7R,8R)-3-methoxyl-4,9-dihydroxy-3':7,4':8-diepoxyneolignan-1'-carboxylic acid methyl ester (2) were isolated from Callicarpa kwangtungensis, together with ten known compounds, genistin (3), daidzin (4), silybin A (5), isosilybin A (6), isosilybin B (7), p-hydroxybenzaldehyde (8), syringic acid (9), lanceolatin A (10), icariside C5 (11), and (3S,6E,10R)-10-ß-D-glucopyranosyloxy-3,11-dihydroxy-3,7,11-trimethyldodeca-1,6-diene (12). Compounds 1 and 2 were evaluated for their effects on the inhibition of nitric oxide (NO) production in lipopolysaccharide induced RAW264.7 cells. Compounds 1 and 2 exhibited inhibitory activity with IC50 values of 31.45 ± 0.38 and 40.72 ± 0.54 µM, respectively.

Validated UHPLC-MS/MS method for simultaneous determination of four triterpene saponins from Akebia trifoliata extract in rat plasma and its application to a pharmacokinetic study.

Saponin PH, akemisaponins E, saponin PJ1 and scheffoleoside A, the main bioactive triterpene saponins of Chinese traditional medicine Akebia trifoliata, contribute to its diuretic pharmacological activity. Because of interactions of the multiple ingredients in vivo, pharmacokinetic studies of multiple triterpenes after administration of A. trifoliata extract are essential to clarify their pharmacological effects. The purpose of this study was to develop an efficient and sensitive UHPLC-MS/MS method for simultaneous determination of these four triterpene saponins in rat plasma. The biosamples were prepared by liquid-liquid extraction with n-butanol. The chromatographic separation was performed on a Phenomenex Luna® C18 (150 × 2 mm, 3 µm) with a mobile phase consisting of acetonitrile and water at a flow rate of 0.5 mL/min. The MS/MS system was operated in a negative multiple reaction monitoring mode, and the precursor-product ion transitions were optimized as m/z 941.6 → 471.1 for saponin PH, 941.7 → 471.2 for akemisaponins E, 1089.7 → 601.1 for saponin PJ1 , 957.6 → 487.4 for scheffoleoside A and 799.5 → 637.3 for ginsenoside Rg1 (Rg1 , internal standard). Method validation parameters (calibration curve linearity, lower limit of detection, recovery, matrix effect, intra- and inter-day precision) were within the acceptable ranges. This is the first reported on the UHPLC-MS/MS detection of saponin PH, akemisaponins E, saponin PJ1 and scheffoleoside A, and applied to a preclinical pharmacokinetic study after oral administration of A. trifoliata extract in rats. This study provides a basis for clinical application and further development of A. trifoliata extract.

Cytotoxic triterpenoid saponins from the defatted seeds of Camellia oleifera Abel.

Five new oleanane-type triterpenoid saponins, oleiferasaponins D1-D5 (1-5), were isolated from the defatted seeds of Camellia oleifera Abel. Their structures were elucidated by spectroscopic and chemical methods. The cytotoxic activities of compounds 1-5 were evaluated against five human tumor cell lines (HCT-116, HepG2, BGC-823, NCI-H1650, and A2780). Compounds 1-2 exhibited cytotoxic activity against five human cancer cell lines, with IC50 values ranging from 3.31 to 10.23 µM. Compounds 3-5 showed moderate cytotoxic activities toward the tested cell lines.

A simple and selective UHPLC-MS/MS method for quantification of plantagoguanidinic acid in rat plasma and its application to a pharmacokinetic study.

A simple, sensitive and specific UHPLC-MS/MS method for quantification of plantagoguanidinic acid (PGA) in rat plasma was applied to investigate the pharmacokinetic behavior in vivo, using protopine as internal standard. The chromatography was separated on a Phenomenex® Luna-C18 column (2.1 × 150 mm, 3.0 µm) within 7.0 min using a mobile phase consisting of acetonitrile-0.1% formic acid solution under gradient elution at a flow rate of 0.4 mL/min. Prepared samples were monitored by multiple reaction monitoring mode, with the target fragmentions m/z 226.2 → 84.2 for PGA and m/z 354.2 → 188.9 for IS in positive electrospray ionization. The calibration curve of PGA was linear throughout the range 1-1000 ng/mL (r = 0.9962). The lower limit of quantitation in plasma for PGA was 0.1 ng/mL, and the recovery was >88.6%. Intra- and interday accuracy ranged from -8.6 to 4.9%. Furthermore, this validated method was successfully used for a pre-clinical pharmacokinetic study of PGA at a single dose of 20 and 5 mg/kg in rats via oral and intravenous administration. The study showed that PGA was absorpted rapidly and eliminated gradually with a greater absolute oral bioavailability of 70.1% in rats.

Two new triterpenoid glycosides from the stems of Camellia oleifera Abel.

Two new oleanane-type triterpenoid glycosides, 3-O-ß-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl-(1→3)-[ß-D-glucuronopyranosyl-(1→2)]-ß-D-glucuronopyranosyl-22α-angeloyloxyolean-12-ene-15α,16α,28-triol(1) and 3-O-ß-D-xylopyranosyl-(1→2)-α-L-arabinopyranosyl-(1→3)-[ß-D-glucuronopyranosyl-(1→2)]-ß-D-glucuronopyranosyl-21ß-acetyl-22α-angeloyloxyolean-12-ene-16α,28-diol (2) were isolated from the stems of Camellia oleifera Abel. Their structures were elucidated by means of spectroscopic methods and chemical evidence. The cytotoxic activities of compounds 1-2 were evaluated against five human tumour cell lines (HCT-8, BGC-823, A5049, and A2780). Compounds 1-2 showed cytotoxic activity against five human cancer cell lines, with IC50 values ranging from 3.15 to 7.32 µM.

Four New Triterpenoids from Callicarpa kwangtungensis.

Four new triterpenoids which were identifed as 2α,3ß,6ß,19α-tetrahydroxy- oleanolic acid 28-O-ß-D-glucopyranoside (1), 2-O-ß-D-glucopyranosyloxy-3α,19α-di-hydroxyoleanolic acid (2), 2-O-ß-D-glucopyranosyloxy-3α,19α-dihydroxyursolic acid (3), 2α,3α,6ß,19α-tetrahydroxyursolic acid 28-O-ß-D-glucopyranoside (4), were isolated from the aerial parts of Callicarpa kwangtungensis together with three known triterpenoids identified as 2α,3ß,21ß-trihydroxyursolic acid 28-O-ß-D-glucopyranoside (5), 2α,3α,19α,23-tetrahydroxyoleanolic acid 28-O-ß-D-glucopyranoside (6), 2α,3α,19α,23-tetrahydroxyursolic acid 28-O-ß-D-glucopyranoside (7). Their structures were elucidated by the combination of mass spectrometry (MS), one and two-dimensional NMR experiments.

Three new labdane-type diterpene glycosides from fruits of Rubus chingii and their cytotoxic activities against five humor cell lines.

Three new labdane-type diterpene glycosides, 15,18-di-O-ß-d-glucopyranosyl-13(E)-ent-labda-7(8),13(14)-diene-3ß,15,18-triol (1), 15,18-di-O-ß-d-glucopyranosyl-13(E)-ent-labda-8(9),13(14)-diene-3ß,15,18-triol (2), and 15-O-ß-d-apiofuranosyl-(1→2)-ß-d-glucopyranosyl-18-O-ß-d-glucopyranosyl-13(E)-ent-labda-8(9),13(14)-diene-3ß,15,18-triol (3), were isolated from the fruits of Rubus chingii. Their structures were elucidated on the basis of spectroscopic data and chemical methods. The cytotoxic activities of compounds 1-3 were evaluated against five human tumor cell lines (HCT-8, BGC-823, A549, and A2780). Compounds 3 showed cytotoxic activity against A549 with an IC50 value of 2.32µM.

[Chemical Constituents from Camellia oleifera Stem].

OBJECTIVE: To study the chemical constituents of stem of Camellia oleifera. METHODS: The chemical constituents were isolated and purified by column chromatography on silica gel, ODS, Sephadex LH-20 and MPLC. Their structures were elucidated on the basis of physicochemical properties and special analysis. RESULTS: Seven compounds were isolated from the stem of Camellia oleifera, whose structures were elucidated as (-) -pinoresinol (1), (-) -medioresinol (2), skullcapflavone II (3), betulinic acid (4), ursolic acid (5), 3-O-ß-D-glucopyranosyl- (1 --> 2) -ß-D-xylopyransoyl-(1 --> 3) -[ß-D-glucopyranosyl- (1 --> 2)] -ß-D-glucuronopyranosyl-22α-angeloyloxyolean-12-ene-15α,16α,28-triol (6) and oleanolic acid (7). CONCLUSION: Compounds 1 - 6 are isolated from this plant for the first time, and compounds 1 - 3 are isolated from this genus for the first time.

Two new triterpenoids from Callicarpa kwangtungensis.

Two new triterpenoids, 2α,3ß,16α,19α,23-pentahydroxyolean-12-en-28-oic acid (1) and 2α,3α,11α,21α,23-pentahydroxyurs-12-en-28-oic acid (2), were isolated from the aerial parts of Callicarpa kwangtungensis. Their structures were elucidated by 1D and 2D analyses, as well as MS and IR spectra.

[Ethyl acetate-soluble chemical constituents from Callicarpa kwangtungensis].

OBJECTIVE: To study the ethyl acetate-soluble chemical constituents of Callicarpa kwangtungensis. METHODS: The chemical constituents were isolated by column chromatography on silica gel, Sephadex LH-20 and MPLC. Their chemical structures were elucidated on the basis of special analysis. RESULTS: Seven compounds were isolated from ethyl acetate part, whose structures were elucidated as caffeic acid(1),2α,3α, 19α-trihyhydroxy-urs-12-en-28-O-ß-D-glucopyranoside (2),2α,3, 19α-trihyhydroxy-olean-12-en-28-O-ß-D-glucopyranoside (3), 2α, 3α, 19α-trihyhydroxy-olean-12-en-28-O-ß-D-glucopyranoside (4), ferulic acid (5), 2α, 3ß, 19α-trihyhydroxy-urs-12-en-28-O-ß-D-glucopyranoside(6), and ( + )-isolariciresinol-9-O-ß-D-glucopyranoside(7). CONCLUSION: All these compounds are isolated from this plant for the first time.

[Chemical Constituents from Leaves of Liquidambar formosana].

OBJECTIVE: To study the chemical constituents of the leaves of Liquidambarformosana. METHODS: The chemical constituents were isolated and purified by column chromatography on silicagel, Sephadex LH-20 and MPLC. Their structures were elucidated on the basis of physicochemical properties and special analysis. RESULTS: Eight compounds were isolated from the leaves of Liquidambar formosana, whose structures were elucidated as gallic acid (1), p-hydroxy-benzoic acid (2), 3-methoxy-4-hydroxy-benzoic acid (3), 3,5-dihydroxy-4-methoxy-benzoic acid (4) kaempferol (5), 3,4-dihydroxy-benzoic acid (6), 3,4-dihydroxy-5-methoxy-benzoic acid (7) and 3ß,23,29-trihydroxy-olean-12-en-28-oic acid-ß-D-glucopyranosyl ester (8). CONCLUSION: Compounds 1-8 are isolated from the leaves of Liquidambar formosana for the first time.

Three new compounds from the leaves of Liquidambar formosana.

Two new flavan glycosides, (2S)-5,7,4'-trihydroxyflavan-7-O-ß-D-glucopyranoside and (2S)-5,7,4'-trihydroxyflavan-5-O-ß-D-glucopyranoside, and a new neolignan, (7S,8S)-3-methoxyl-3'-O-ß-D-glucopyrannosyl-4':8,5':7-diepoxyneolignan-4,9'-diol, were isolated from the leaves of Liquidambar formosana Hance. Their structures were elucidated on the basis of spectroscopic data and chemical evidence.

A new protopanaxadiol-type ginsenoside from the roots of Panax notoginseng.

A new protopanaxadiol-type ginsenoside, 6-O-ß-d-glucopyranosyl-20-O-ß-d-glucopyranosyl-20(S)-protopanaxadiol-3-one (1), along with three known compounds, was isolated from the roots of Panax notoginseng. Their structures were determined based on some pieces of spectroscopic and chemical evidence. Compound 1 exhibited cytotoxic activity against five human cancer cell lines, with IC50 values ranging from 5.4 to 8.6 µg/ml.