Multiple heart-cutting two-dimensional liquid chromatography/charged aerosol detector assay of ginsenosides for quality evaluation of ginseng from diverse Chinese patent medicines.

For quality control of Chinese patent medicines (CPMs) containing the same herbal medicine or different herbal medicines that have similar chemical composition, current ″one standard for one species″ research mode leads to poor universality of the analytical approaches unfavorable to discriminate easily confused species. Herein, we were aimed to elaborate a multiple heart-cutting two-dimensional liquid chromatography/charged aerosol detector (MHC-2DLC/CAD) approach to quantitatively assess ginseng from multiple CPMs. Targeting baseline resolution of 16 ginsenosides (noto-R1/Rg1/Re/Rf/Ra2/Rb1/Rc/Ro/Rb2/Rb3/Rd/Rh1/Rg2/Rg3/Rg3(R)/24(R)-p-F11), experiments were conducted to optimize key parameters and validate its performance. A Poroshell 120 EC-C18 column and an XBridge Shield RP18 column were separately utilized in the first-dimensional (1D) and the second-dimensional (2D) chromatography. Eight consecutive cuttings could achieve good separation of 16 ginsenosides within 85 min. The developed MHC-2DLC/CAD method showed good linearity (R2 > 0.999), repeatability (RSD < 6.73%), stability (RSD < 5.63%), inter- and intra-day precision (RSD < 5.57%), recovery (93.76-111.14%), and the limit of detection (LOD) and limit of quantification (LOQ) varied between 0.45-2.37 ng and 0.96-4.71 ng, respectively. We applied it to the content determination of 16 ginsenosides simultaneously from 28 different ginseng-containing CPMs, which unveiled the ginsenoside content difference among the tested CPMs, and gave useful information to discriminate ginseng in the preparation samples, as well. The MHC-2DLC/CAD approach exhibited advantages of high specificity, good separation ability, and relative high analysis efficiency, which also justified the feasibility of our proposed ″Monomethod Characterization of Structure Analogs″ strategy in quality evaluation of diverse CPMs that contained different ginseng.

Multi-level fingerprinting and cardiomyocyte protection evaluation for comparing polysaccharides from six Panax herbal medicines.

The role of polysaccharides in quality control of ginseng is underestimated. Large-scale comparison on the polysaccharides of Panax ginseng (PG), P. quinquefolius (PQ), P. notoginseng (PN), Red ginseng (RG), P. japonicus (ZJS), and P. japonicus var. major (ZZS), was performed by both chemical and biological approaches. Holistic fingerprinting at polysaccharide and the hydrolyzed oligosaccharide and monosaccharide levels utilized various chromatography methods, while OGD and OGD/R models on H9c2 cells were introduced to evaluate the protective effects on cell viability and mitochondrial function. Polysaccharides from six ginseng species exhibited remarkable content difference (RG > PG/ZZS/ZJS/PQ > PN), but weak differentiations in molecular weight distribution and oligosaccharide profiles, while Glc and GalA were richer for monosaccharide compositions of PG and RG polysaccharides, respectively. RG polysaccharides (25/50/100 µg/mL) showed significant cardiomyocyte protection by regulating mitochondrial functions. These new evidences may provide support for the supplementary role of polysaccharides in quality control of ginseng.

Advances in the Study of the Potential Hepatotoxic Components and Mechanism of Polygonum multiflorum.

The roots of Polygonum multiflorum (PM) (He Shou Wu in Chinese) are one of the most commonly used tonic traditional Chinese medicines (TCMs) in China. PM is traditionally valued for its antiaging, liver- and kidney-tonifying, and hair-blackening effects. However, an increasing number of hepatotoxicity cases induced by PM attract the attention of scholars worldwide. Thus far, the potential liver injury compounds and the mechanism are still uncertain. The aim of this review is to provide comprehensive information on the potential hepatotoxic components and mechanism of PM based on the scientific literature. Moreover, perspectives for future investigations of hepatotoxic components are discussed. This study will build a new foundation for further study on the hepatotoxic components and mechanism of PM.

New anthraquinone and eurotinone analogue from the seeds of Senna obtusifolia and their inhibitory effects on human organic anion transporters 1 and 3.

A continuous phytochemical study on the seeds of Senna obtusifolia (Syn.: Cassia obtusifolia) led to the isolation of a new anthraquinone analogue, obtusifolin-2-O-ß-D-(6'-O-α,ß-unsaturated butyryl)-glucopyranoside (1) and a new eurotinone analogue, epi-9-dehydroxyeurotinone-ß-D-glucopyranoside (2). Their structures were established mainly by NMR and MS experiments as well as the necessary chemical evidences. Their inhibitory effects on two organic anion transporters (OAT1 and OAT3) were investigated and the results showed that 1 exhibited a strongly specific inhibitory effect on OAT1 at 100 µM.

Two new naphthalene glycosides from the seeds of Cassia obtusifolia.

A phytochemical study on the seeds of Cassia obtusifolia was carried out, which finally led to obtain two naphthalenes (1 and 2), two naphthopyrans (3 and 4) and twelve anthraquinones (5-16). The structures of all compounds were established mainly by NMR and MS experiments as well as the necessary chemical evidence. Among them, 1 and 2 (obtusinaphthalensides A and B) were identified to be new naphthalene glycosides.

C21 steroid derivatives from the Dai herbal medicine Dai-Bai-Jie, the dried roots of Marsdenia tenacissima, and their screening for anti-HIV activity.

Twenty-three new C21 steroidal glycosides, marstenacissides C1-C10 (1-10), D1-D7 (11-17) and E1-E6 (18-23), and four new C21 steroids, 11α,12ß-O-ditigloyl-tenacigenin C (24), 11α-O-benzoyl-12ß-O-tigloyl-tenacigenin C (25), 11α-O-tigloyl-12ß-O-benzoyl-tenacigenin C (26) and 11α-O-tigloyl-12ß-O-benzoyl-marsdenin (27), were isolated from the Dai herbal medicine Dai-Bai-Jie, derived from the roots of Marsdenia tenacissima. The chemical structures of all compounds were established by spectroscopic techniques, including high-resolution mass spectrometry and NMR spectroscopy, as well as by comparison with reported spectral data. The anti-HIV activities of these compounds were screened, and the compounds obtained displayed inhibitory effects against HIV-1 with inhibition rates of 36.4-81.3% at 30 µM.

Combination of flavonoids from Oroxylum indicum seed extracts and acarbose improves the inhibition of postprandial blood glucose: In vivo and in vitro study.

The combined effect of Oroxylum indicum seed extracts (OISE) or major flavonoids from OISE and acarbose on reducing postprandial blood glucose (PBG) levels was investigated in vitro and in vivo. In vitro, the IC50 values of OISE and baicalein against α-glucosidase were 43.4±0.731µgmL-1 and 25.9±0.412µgmL-1 respectively. A combination of acarbose with OISE or baicalein synergistically inhibited rat intestinal α-glucosidase. The combination index (CI) values for acarbose with OISE ranged from 0.33 to 0.75, suggesting a synergistic but not additive effect. OISE was determined to be a non-competitive inhibitor of maltose-hydrolyzing activity. In vivo, OISE were administered to normoglycemic and diabetic mice, either alone or in combination with acarbose. At doses between 50 and 200mgkg-1, OISE enhanced the efficacy of acarbose by up to 5-fold. These results demonstrated that OISE enhances the efficacy of acarbose in vivo, and that the combination of OISE and acarbose displayed a synergistic effect in vitro. Therefore, OISE can be used to design dietary supplements to treat diabetes.

The Pharmacological Effects of Lutein and Zeaxanthin on Visual Disorders and Cognition Diseases.

Lutein (L) and zeaxanthin (Z) are dietary carotenoids derived from dark green leafy vegetables, orange and yellow fruits that form the macular pigment of the human eyes. It was hypothesized that they protect against visual disorders and cognition diseases, such as age-related macular degeneration (AMD), age-related cataract (ARC), cognition diseases, ischemic/hypoxia induced retinopathy, light damage of the retina, retinitis pigmentosa, retinal detachment, uveitis and diabetic retinopathy. The mechanism by which they are involved in the prevention of eye diseases may be due their physical blue light filtration properties and local antioxidant activity. In addition to their protective roles against light-induced oxidative damage, there are increasing evidences that L and Z may also improve normal ocular function by enhancing contrast sensitivity and by reducing glare disability. Surveys about L and Z supplementation have indicated that moderate intakes of L and Z are associated with decreased AMD risk and less visual impairment. Furthermore, this review discusses the appropriate consumption quantities, the consumption safety of L, side effects and future research directions.

Polyoxypregnane Glycosides from the Roots of Marsdenia tenacissima and Their Anti-HIV Activities.

A continuous phytochemical study on the roots of Marsdenia tenacissima led to the isolation and identification of 13 new polyoxypregnane glycosides named marstenacissides B10-B17 (1, 2, 4, 7, 8, 11, 12, and 14) and marstenacissides A8-A12 (3, 9, 10, 13, and 15) in addition to two known polyoxypregnane glycosides marsdenosides M and L (5 and 6). Their structures were established by spectroscopic techniques and by comparison with the reported data in the literature. Moreover, the anti-HIV activities of these isolates and the previous isolated marstenacissides A1-A7 and B1-B9 were assessed, some of which exhibited slight or negligible effects against HIV-1.

Steroidal Saponins from the Rhizomes of Aspidistra typica.

Eleven new furostanol saponins, typaspidosides B-L (1-11), one new spirostanol saponin, typaspidoside M (12), and five known spirostanol saponins, 25S-atropuroside (13), neoaspidistrin (14), (25S)-pratioside D1 (15), 25S-aspidistrin (16) and 25S-neosibiricoside (17) were isolated from the rhizomes of Aspidistra typica Baill. The structures of the new compounds were established using 1D and 2D NMR (1H-1H COSY, HMQC, HMBC and ROESY) spectroscopy, high resolution mass spectrometry, and chemical methods. The aglycones of 1-3 (unusual furostanol saponins with opened E ring type), 9 and 10 (the methoxyl substituent at C-23 position) were found, identified from natural products for the first time. Moreover, the anti-HIV activities of the isolated steroidal glycosides were assessed, and compounds 13, 14, 16 and 17 exhibited high active against HIV-1.

[Research on optimal modeling strategy for licorice extraction process based on near-infrared spectroscopy technology].

The manufacture of traditional Chinese medicine (TCM) products is always accompanied by processing complex raw materials and real-time monitoring of the manufacturing process. In this study, we investigated different modeling strategies for the extraction process of licorice. Near-infrared spectra associate with the extraction time was used to detemine the states of the extraction processes. Three modeling approaches, i.e., principal component analysis (PCA), partial least squares regression (PLSR) and parallel factor analysis-PLSR (PARAFAC-PLSR), were adopted for the prediction of the real-time status of the process. The overall results indicated that PCA, PLSR and PARAFAC-PLSR can effectively detect the errors in the extraction procedure and predict the process trajectories, which has important significance for the monitoring and controlling of the extraction processes.

Analysis of the Constituents in "Zhu She Yong Xue Shuan Tong" by Ultra High Performance Liquid Chromatography with Quadrupole Time-of-Flight Mass Spectrometry Combined with Preparative High Performance Liquid Chromatography.

"Zhu She Yong Xue Shuan Tong" lyophilized powder (ZSYXST), consists of a series of saponins extracted from Panax notoginseng, which has been widely used in China for the treatment of strokes. In this study, an ultra-high performance liquid chromatography with quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF/MS) combined with preparative high performance liquid chromatography (PHPLC) method was developed to rapidly identify both major and minor saponins in ZSYXST. Some high content components were removed through PHPLC in order to increase the sensitivity of the trace saponins. Then, specific characteristic fragment ions in both positive and negative mode were utilized to determine the types of aglycone, saccharide, as well as the saccharide chain linkages. As a result, 94 saponins, including 20 pairs of isomers and ten new compounds, which could represent higher than 98% components in ZSYXST, were identified or tentatively identified in commercial ZSYXST samples.

[Comparative Analysis of Content of Four Alkaloids in Fritillaria hupehensis and Fritillaria ebeiensis var. purpurea].

OBJECTIVE: To establish an assay method for simultaneous determination of peimine, peiminine, peimissine and hupehenine and to make a comparative analysis of the content of four alkaloids in Fritillaria hupehensis and Fritillaria ebeiensis var. purpurea for the first time. METHODS: A Unitary C18 column(250 mm x 4.6 mm, 5 µm) was chosen with acetonitrile-water (containing 0.05% diethylamine) as mobile phase in a gradient program. The column temperature was 35 degrees C and the flow-rate was 1.0 mL/min. RESULTS: There was high content of peiminine and the content of peimissine was inferior to peiminine in Fritillaria hupehensis. Relatively speaking, peimine and hupehenine were much lower than the other two ingredients. Fritillaria ebeiensis var. purpurea also contained high levels of peiminine, the minimum content of peimine and equivalent content of peimissine comparing with Fritillaria hupehensis. In addition, it didn't contain hupehenine in Fritillaria ebeiensis var. purpurea. CONCLUSION: This method is simple and fast, and it has good separation, reproducibility and reliable results. Also, it can be used as basis for the quality evaluation of Fritillaria hupehensis and Fritillaria ebeiensis var. purpurea.

New polyoxypregnane glycosides from the roots of Marsdenia tenacissima.

For the first time, a systematic phytochemical study was performed on the roots of Marsdenia tenacissima. Finally, sixteen new polyoxypregnane glycosides, marstenacissides A1-A7 (1-7) and marstenacissides B1-B9 (8-16), were isolated from M. tenacissima roots. The structures of these new compounds were established by various spectroscopic techniques, including 1D and 2D NMR spectroscopy and mass spectrometry.

Steroidal saponins from Tribulus terrestris.

Sixteen steroidal saponins, including seven previously unreported compounds, were isolated from Tribulus terrestris. The structures of the saponins were established using 1D and 2D NMR spectroscopy, mass spectrometry, and chemical methods. They were identified as: 26-O-ß-d-glucopyranosyl-(25R)-furost-4-en-2α,3ß,22α,26-tetrol-12-one (terrestrinin C), 26-O-ß-d-glucopyranosyl-(25R)-furost-4-en-22α,26-diol-3,12-dione (terrestrinin D), 26-O-ß-d-glucopyranosyl-(25S)-furost-4-en-22α,26-diol-3,6,12-trione (terrestrinin E), 26-O-ß-d-glucopyranosyl-(25R)-5α-furostan-3ß,22α,26-triol-12-one (terrestrinin F), 26-O-ß-d-glucopyranosyl-(25R)-furost-4-en-12ß,22α,26-triol-3-one (terrestrinin G), 26-O-ß-d-glucopyranosyl-(1→6)-ß-d-glucopyranosyl-(25R)-furost-4-en-22α,26-diol-3,12-dione (terrestrinin H), and 24-O-ß-d-glucopyranosyl-(25S)-5α-spirostan-3ß,24ß-diol-12-one-3-O-ß-d-glucopyranosyl-(1→4)-ß-d-galactopyranoside (terrestrinin I). The isolated compounds were evaluated for their platelet aggregation activities. Three of the known saponins exhibited strong effects on the induction of platelet aggregation.

[Study on steroidal saponins from Dioscorea zingiberensis and their platelet aggregation activities].

Using the absorbent resin, silica gel and ODS column chromatography as well as semi-preparative HPLC, ten compounds were isolated from 70% ethanol extract of tubers of Dioscorea zingiberensis C. H. Wright, and their structures were elucidated as trigoneoside XIIIa (1), parvifloside (2), trigoneoside IVa (3), deltoside (4), protobioside (5), lilioglycoside k (6), zingiberensis newsaponin I (7), deltonin (8), prosapogenin A of dioscin (9), and trillin (10) on the basis of NMR and MS spectral data analysis. Among these compounds, 1, 3, 5 and 6 were isolated from this plant for the first time. In the screening test on platelet aggregation, compounds 7 and 8 exhibited induction effect on platelet aggregation, while compound 9 exhibited significant inhibitory effect on platelet aggregation in vitro.

Selective hydrolysis of flavonoid glycosides by Curvularia lunata.

Twelve flavonoid glycosides were involved in the biotransformation of the glycosyl moieties by Curvularia lunata 3.4381, and the products were analyzed by UPLC/PDA-Q-TOF-MS(E). Curvularia lunata displayed hydrolyzing activities on the terminal Rha or Glc units of some flavonoid glycosides. Terminal Rha with a 1 → 2 linkage of isorhamnetin-3-O-neohesperidoside and typhaneoside could be hydrolyzed by Curvularia lunata, but terminal Rha with a 1 → 6 linkage of rutin, typhaneoside, and quercetin-3-O-apiosyl-(1 → 2)-[rhamnosyl-(1 → 6)]-glucoside could not be hydrolyzed. Curvularia lunata could also hydrolyze the Glc of icariin, floramanoside B, and naringin. This is the first report of the hydrolysis of glycosyl units of flavonoid glycosides by Curvularia lunata. A new way to convert naringin to naringenin was found in this research.

Two new furostanol saponins from Aspidistra typica.

Two new furostanol saponins (1 and 2), along with one known saponin (3), were obtained from the rhizomes of Aspidistra typica Baill. Their structures were elucidated as (25R)-26-O-ß-d-glucopyranosyl-furost-5-ene-12-one-3ß,22α,26-triol-3-O-ß-d-glucopyranosyl-(1 â†’ 2)-[ß-d-xylopyranosyl-(1 â†’ 3)]-ß-d-glucopyranosyl-(1 â†’ 4)-ß-d-galactopyranoside (1, typaspidoside A), (25S)-26-O-ß-d-glucopyranosyl-furost-5-ene-12-one-3ß,22α,26-triol-3-O-ß-d-glucopyranosyl-(1 â†’ 2)-[ß-d-xylopyranosyl-(1 â†’ 3)]-ß-d-glucopyranosyl-(1 â†’ 4)-ß-d-galactopyranoside (2, 25S-typaspidoside A), and timosaponin H1 (3), based on the integrative spectroscopic analysis of 1D- and 2D-NMR experiments, ESI-MS data and chemical evidence. The investigation on the chemical components of this plant is reported for the first time.

Two novel furostanol saponins from the tubers of Ophiopogon japonicus.

Phytochemical investigation of the fresh tubers of Ophiopogon japonicus led to the isolation of two new furostanol saponins (1 and 2) together with two known steroidal saponins (3 and 4). Comprehensive spectroscopic analysis allowed the chemical structures of two new compounds to be elucidated as (25R)-26-O-[ß-d-glucopyranosyl-(1 â†’ 2)-ß-d-glucopyranosyl]-5-ene-furost-1ß,3ß,22α,26-tetraol-3-O-α-l-rhamnopyranosyl-(1 â†’ 2)-[ß-d-xylopyranosyl-(1 â†’ 4)]-ß-d-glucopyranoside (1, ophiopogonin P) and (25R)-26-O-[ß-d-glucopyranosyl-(1 â†’ 6)-ß-d-glucopyranosyl]-5-ene-furost-1ß,3ß,22α,26-tetraol-3-O-α-l-rhamnopyranosyl-(1 â†’ 2)-[ß-d-xylopyranosyl-(1 â†’ 4)]-ß-d-glucopyranoside (2, ophiopogonin Q). Furostanol saponins with the disaccharide chain linked at C-26 hydroxy group of the aglycone have been rarely reported from natural sources.

New kaurene diterpenoid glycosides from fenugreek seeds.

Two new kaurene diterpenoid glycosides, named Graecumoside A (1) and B (2), were isolated from fenugreek seeds, along with three known flavonoid-C-glycosides, isoorientin (3), isovitexin (4) and vitexin (5). By combined analyses of 1D- and 2D-NMR, and MS spectroscopy, the structures of two new compounds were elucidated as 3-O-ß- D-glucopyranosyl kaur-5, 16-dien-3ß, 6, 13ß-trihydroxy-7-oxo-18-oic acid methyl ester and 3-O-ß-neohesperidosyl kaur-5, 16-dien-3ß, 6, 13ß-trihydroxy-7-oxo-18-oic acid methyl ester, respectively. The kaurene diterpenoid glycosides were first isolated and identified from fenugreek seeds.