Structure characterization and immunomodulatory activity of a polysaccharide from Saposhnikoviae Radix.

A new polysaccharide, named SP800201 with Mw of 2.17 × 105 g/mol, was isolated from Saposhnikoviae Radix. The monosaccharide composition of SP800201 mainly contained Gal, GalA, Ara, and Rha. SP800201 has a core structure containing GalA as the backbone and side chains consisting of GalA, Gal, Ara and Rha. Cell and zebrafish experiments were used to explore the immunomodulatory activity of SP800201. Results of vitro RAW264.7 cell experiments showed that SP800201 could significantly improve the proliferation and phagocytosis of macrophages, and promote the release of NO, TNF-α, IL-1ß, and IL-6. Results of vivo experiments in immunocompromised zebrafish showed that SP800201 could also significantly increase the density of immune cells, the number of macrophages, and reduce NO, TNF-α, IL-1ß, and IL-6. The above results showed that the Saposhnikoviae Radix polysaccharide has certain immunomodulatory activity.

Synthesis and evaluation of panaxatriol derivatives as Na+, K+-ATPase inhibitors.

Panaxatriol, a triterpene bearing a steroid-like structure similar to cardiac glycosides, was presumed to share the same bioactivity with cardiac glycosides, and may be a potential Na+, K+-ATPase inhibitor. In this paper, a series of panaxatriol derivatives were synthesized and evaluated for Na+, K+-ATPase inhibitory activities. The results of biological tests showed that more than half of the synthesized derivatives presented increased inhibitory activities compared with panaxatriol. Of these compounds, 13a with a 3, 4-seco skeleton showed the most potent inhibitory activity, which was equal to that of the standard drug digoxin. To understand the binding mode of the most active compound, molecular docking study of 13a with Na+, K+-ATPase was conducted. Therefore, 13a may serve as a new lead compound for the development of novel Na+, K+-ATPase inhibitors.

Anti-inflammatory and antiproliferative prenylated chalcones from Hedysarum gmelinii.

Five new prenylated chalcones hedysarumines C-G (1-5), along with eight known chalcones (6-13) all of which were isolated from the genus Hedysarum for the first time, were isolated from the roots of Hedysarum gmelinii by chromatographic methods. Their structures were determined by extensive spectroscopic techniques. The isolated chalcones (2-13) and previously isolated prenylated chalcones (14-16) were evaluated for antiproliferative activity against five human cancer cell lines (HepG2, A549, Du145, BGC823, and HCT116) and in vitro anti-inflammatory activity. Compounds 5, 10, and 15 inhibited NO production induced by lipopolysaccharide in BV-2 cells, with IC50 values ranging from 3.25 to 8.48 µM. Compounds 4 and 11 showed moderate antiproliferative activity to selective human cancer cell lines, with the IC50 values of 4 and 11 against A549 cell line being 7.79 and 9.67 µM, respectively, and the IC50 value of 11 against HCT116 cell line being 8.85 µM.

Structurally Diverse Cytotoxic Dimeric Chalcones from Oxytropis chiliophylla.

Ten isomeric cyclobutane- and cyclohexene-containing chalcone dimers, oxyfadichalcones A-G, were isolated from the aerial parts of Oxytropis chiliophylla. These included six new compounds and three pairs of enantiomers that are being reported from natural sources for the first time. The relative configurations were elucidated by spectroscopic data analysis, while the absolute configurations were determined by comparing the experimental and calculated electronic circular dichroism spectra. Quantitative LC-MS analysis of the main dimers from different parts of the plant revealed their characteristic accumulation in the viscous secretion and provided supporting evidence for the hypothesized photochemical biosynthesis. In addition, the cytotoxic activities of all isolates against the PC-3 human prostate cancer cell line are reported.

New Lignans and Iridoid Glycosides from Dipsacus asper Wall.

Six new compounds, including four new lignans, dipsalignan A (1), B-D (3-5), and two new bis-iridoid glycoside dimmers, dipsanosides M (7) and N (8), together with two known compounds (2) and (6), have been isolated from the roots of Dipsacus asper Wall. Their structures were established on the basis of spectroscopic data (MS, 1D, 2D NMR, and CD) and chemical methods. All the isolated compounds were tested against human immunodeficiency virus-1 (HIV-1) integrase inhibition activities, and only compounds 1, 2, 7, and 8 displayed weak activities.

3-Hydroxy-3-methylglutaryl flavonol glycosides from Oxytropis falcata.

Five new 3-hydroxy-3-methylglutaryl (HMG) flavonol 3-O-glycosides, named oxytroflavosides A-E (1-5), and two new rhamnocitrin 3-O-glycosides, oxytroflavosides F and G (6 and 7) were isolated from the n-BuOH-soluble fraction of an EtOH extract of Oxytropis falcata together with seven known kaempferol glycosides (8-14), of which six were isolated from the genus Oxytropis for the first time. The structures of these compounds were elucidated by spectroscopic techniques and chemical methods. The absolute configuration of HMG in compounds 1-5 was determined to be S through spectroscopic analysis of the mevalonamide obtained by amidation and reduction of the HMG moiety. Compounds 1-10 were evaluated for anti-inflammatory activities using lipopolysaccharide-induced RAW 264.7 cells, but none of them showed inhibitory effects on NO production.

Triterpenoid saponins from Dipsacus asper and their activities in vitro.

Two new triterpenoid saponins 1 and 2, along with six known saponins 3-8, were isolated from the roots of Dipsacus asper. The structures of new compounds were established as 3-O-ß-d-glucopyranosyl-(1 â†’ 4)-[α-l-rhamnopyranosyl-(1 â†’ 3)]-ß-d-glucopyranosyl-(1 â†’ 3)-α-l-rhamnopyranosyl-(1 â†’ 2)-α-l-arabinopyranosyl-hederagenin-28-O-ß-d-glucopyranoside (dipsacus saponin J, 1) and 3-O-α-l-arabinopyranosyl-hederagenin-28-O-ß-d-glucopyranosyl-(1 â†’ 6)-ß-d-glucopyranosyl-(1 â†’ 6)-ß-d-glucopyranoside (dipsacus saponin K, 2). The structures were determined by extensive analysis of their spectroscopic data. Compounds 6 and 7 could significantly stimulate UMR106 cell proliferation and increase alkaline phosphatase activities in UMR106 cell at the concentration of 4 µM.

Structure elucidation of a sodium salified anthraquinone from the seeds of Cassia obtusifolia by NMR technique assisted with acid-alkali titration.

A new sodium salt of anthraquinone named sodium emodin-1-O-ß-gentiobioside, together with nine known compounds, viz. rubrofusarin-6-O-ß-D-gentiobioside, chrysophanol-1-O-ß-D-glucopyranosyl-(1-3)-ß-D-glucopyranosyl-(1-6)-ß-D-glucopyranoside, obtusifolin-2-O-ß-D-glucopyranoside, aurantio-obtusin-6-O-ß-D-glucopyranoside, physcion-8-O-ß-D-glucopyranoside, 1-hydroxyl-2-acetyl-3,8-dimethoxy-6-O-ß-D-apiofuranosyl-(1-2)-ß-D-glucosylnaphthalene, toralactone-9-O-ß-D-gentiobioside, aurantio-obtusin, rubrofusarin-6-O-ß-D-apiofuranosyl-(1-6)-O-ß-D-glucopyranoside, was isolated from the seeds of Cassia obtusifolia and its structure was elucidated by (1)H and (13)C NMR technique assisted with acid-alkali titration. The change of chemical shifts of sodium emodin-1-O-ß-gentiobioside before and after acid-alkali titration was also characterized.

A new natural azulene-type pigment from Oreocnide frutescens.

A new natural red-purple azulene-type pigment, 1,1,6-trimethylazuleno[1,8-cd]pyran-3(1H)-one, named oreolactone (1), together with nine known compounds, scopoletin (2), pomolic acid (3), friedelin (4), 3ß-friedelinol (5), 3α-friedelinol (6), stigmast-4-en-3-one (7), stigmast-4, 22-dien-3-one (8), ß-sitosterol (9), and daucosterol (10), was isolated from the rhizomes of Oreocnide frutescens. The structures were elucidated on the basis of spectroscopic analysis.

Phenylpropanoyl esters from Horseweed (Conyza canadensis) and their inhibitory effects on catecholamine secretion.

Three unique phenylpropanoyl 2,7-anhydro-3-deoxy-2-octulosonic acid derivatives were isolated from Conyza canadensis (horseweed). Their structures were defined as rel-(1S,2R,3R,5S,7R)-methyl 7-caffeoyloxymethyl-2-hydroxy-3-feruloyloxy-6,8-dioxabicyclo[3.2.1]octane-5-carboxylate (1), rel-(1S,2R,3R,5S,7R)-methyl 7-feruloyloxymethyl-2-hydroxy-3-feruloyloxy-6,8-dioxabicyclo[3.2.1]octane-5-carboxylate (2), and rel-(1R,2R,3R,5S,7R)-methyl 7-feruloyloxymethyl-2-feruloyloxy-3-hydroxy-6,8-dioxabicyclo[3.2.1]octane-5-carboxylate (3). Compound 1 and a 5:3 mixture of compounds 2 and 3 were demonstrated to inhibit the catecholamine secretion induced by acetylcholine with IC(50) values of 94.65 and 42.35 microM, respectively, and to inhibit the catecholamine secretion induced by veratridine and high [K(+)] at a dose of 100 microM in cultured bovine adrenal medullary cells.

[A study on the NMR spectrum of methyl-ofloxacin].

Ofloxacin ((+/-)-9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2, 3-dihydro-7H-pyrido[1,2,3-de]-1, 4-benzoxazine-6-carboxylic acid) is a totally synthetic fluoroquinolone antimicrobial agent with a broad spectrum of activity against Gram-positive and Gram-negative bacteria and atypical pathogens such as Mycoplasma, Chlamydia and Legionella. Even though it is widely used for the treatment of gastrointestinal, pulmonary, urinary, and other infections, the comprehensive mechanism of action at molecular level has not been known so far. It is very important to understand the structural characteristics of the drug and the effects that are caused by the environments. With the purpose of deeply investigating the structure of Ofloxacin, an analog of Ofloxacin, Methyl-Ofloxacin (Me-OFL), was synthesized by methylation of 4'N in piperazine ring from Ofloxacin with CH3I. Then appropriate Me-OFL was dissolved in DC1/D2O and NaOH/D2O to prepare corresponding acidic and alkaline solutions. Systematic NMR spectroscopic investigation on Me-OFL in both acidic and alkaline solution was conducted using quantitative 1H and 13C spectra, DEPT, HSQC together with HMBC techniques. The spectra were recorded with Bruker AM-300 spectrometer and DRX500 spectrometer. Chemical shifts have been given in values referred to dioxane (deltaJ = 3.7, deltac = 67.8). Complete assignments on 1H and 13C signals of Me-OFL were obtained in different pH environments where the coupling constant between 13 C and 19F was found to be very helpful for the assignment of aromatic 13C signals. A comprehensive comparison between the 1H, 13C chemical shifts, together with the structural transformation in acidic and alkaline solutions was made and discussed in details. Due to the formation of hydrogen bond between COOH and C==O, the COOH and aromatic ring are in the same plane. As a result, a weak O...H--C hydrogen bond forms between C==O from the carboxyl group and 5-H from aromatic ring. In alkaline solution, the deprivation of H+ from COOH destroys not only the hydrogen bond between COOH and carbonyl group but also the weak hydrogen between the C==O from COOH and 5H. As a result, the 5H exhibited remarkable shift toward high field (1.02). Meanwhile, the chemical shift of 6C, 13C, 7C, 15C also exhibited remarkable shift to low field at 12. 04, 7.46, 4.33, 2.88 respectively. Such variations were related to the changes of p electrons from carboxyl group caused by the transformation between the carboxyl group and the carboxylate group in different pH environments. Comparison of deltaH, deltac data between Me-OFL and OFL in acidic solution and OFL in alkaline was made. In Me-OFL acidic solution, the chemical shift of 3'C, 5'C, 7'C, 8'C also exhibited remarkable shift to low field at 6.66-7.32 respectively, the chemical shift of 2'C and 6'C also exhibited remarkable shift to high field 6.04. In OFL acidic solution, the chemical shift of 2'C, 3'C, 5'C, 6'C, 7'C, 8'C also exhibited remarkable shift to high field within 2.39, Comparison between the protonation and the methylation on the 4'N atom from the piperazine ring was also made. The distribution of positive charge also showed difference. When protonation occurred on the piperazine ring, the positive charge was on the proton connected with 4'N. However, if methylation occurred, the positive charge is on the 4'-N atom.

A new 5,11-epoxymegastigmane glucoside from Acanthus ilicifolius.

From a China mangrove plant Acanthus ilicifolius Linn., a new compound, 5,11-epoxymegastigmane glucoside (1) was isolated along with one known compound of megastigmane glucosides, (6S, 9S)-roseoside (2). The structure of compound 1 was determined on the basis of 1D- and 2D-NMR techniques (DEPT, COSY, HMBC, HMQC, NOESY) and HR-FABMS. The structure of 1 was established as (1S, 3S, 5R, 6R, 7E)-5,11-epoxy-3-hydroxymegastigman-7-en-9-one-3-O-beta-D-glucopyranoside.

[A novel triterpenoid saponin from Prunella vulgaris].

To study the constituents of the Prunella vulgaris L, the constituents were isolated by various column chromatography and the structures were identified on the basis of chemical and spectral analysis. One saponin compound (I) and one flavone glycoside compound (II) were obtained from Prunella vulgaris L. Their structures were elucidated as 16-oxo-17-demethyl-3beta,24-dihydroxylolean-12-en-3-O-beta-D-glucuronoside (I), and acacetin-7-O-beta-D-glucopyranoside (II). Compound I is a novel triterpenoid saponin and named as prunelloside A. Compound II was obtained for the first time from the Prunella genus.

[Chemical constituents from Spatholobus sinensis].

Spatholobus sinensis is a plant of the Spatholobus genus (Leguminosae family). Its caulis are used as "ji-xue-teng" regionally. However, to our knowledge, no phytochemical investigation on S. sinensis has been reported to date. In this study, eight compounds were isolated from the ethanol extract of the caulis of S. sinensis, by solvents extraction and column chromatography methods. By analysis of their physic-chemical constants and spectral data, the structures of 8 compounds were identified as spatholosineside A (1), 2',4',5,7-tetrahydroxyisoflavone (2), isoliquiritigenin (3), lupinalbin A (4), coumestrol (5), naringenin (6), protocatechuic acid (7), leonuriside A (8). Compound 1 is a new compound.

Three new phenolic glycosides from the caulis of Millettia speciosa.

Three new phenolic glycosides, millettiaspecosides A--C (1-3), were isolated from the caulis of Millettia speciosa along with three known phenolic glycosides, khaephuoside B (4), seguinoside K (5), albibrissinoside B (6). Their structures were established by spectroscopic methods. The spectral analysis permitted correct assignments for (1)H and (13)C NMR data of compounds 4 and 5.

[Isolation and structure identification of chemical constituents from Saposhnikovia divaricata (Turcz.) Schischk].

Fourteen compounds were isolated from the ethanol extraction of Saposhnikovia divaricata (Turcz.) Schischk using column chromatographic methods after enrichment by macroporous adsorptive resins. They were identified as fangfengalpyrimidine (1), clemiscosin A (2), 5-hydroxy-8-methoxypsoralen (3), sec-O-glucosylhamaudol (4), hamaudol (5), nodakenetin (6), prim-O-glucosylcimifugin (7), cimifugin (8), 4'-O-beta-D-glucosyl-5-O-methylvisamminol (9), 5-O-methylvisamminol (10), marmesin (11), adenosine (12), daucosterol (13) and beta-sitosterol (14) by physico-chemical properties and spectral data. Compound 1 is a new compound. Compounds 2 and 3 were isolated from umbelliferae plants and Saposhnikovia divaricata (Turcz.) Schischk for the first time respectively.

A pair of diastereoisomeric steroidal saponins from cytotoxic extracts of Tupistra chinensis rhizomes.

A pair of diastereoisomeric steroidal saponins were obtained from the saponin fraction (SF) of methanol extracts from Tupistra chinensis rhizomes, collected in Shennongjia Forest District, China. Based on the chemical and spectroscopic evidences, their structures were determined as shown in Fig. 1. The sample SF displayed marked inhibitory action in vitro towards HeLa and HL-60 cancer cell lines at 10 microg/ml by MTT method.

Cyclolanostane triterpene glycosides from Souliea vaginata.

Five new cyclolanostane triterpene glycosides, 12-deacetyloxy-15alpha-hydroxy-23-epi-26-deoxyactein, 12-deacetyloxy-23-epi-26-deoxyactein, 24-O-acetyldahurinol-3-O-beta-D-xylopyranoside, 12beta-hydroxycimigenol-3-O-beta-D-xylopyranosyl-(1-->3)-beta-D-xylopyranoside, 25-anhydrocimicigenol-3-O-beta-D-(2'-O-acetyl)xylopyranoside, were isolated from the rhizome of Souliea vaginata collected in China. Their structures were elucidated by spectroscopic techniques, including 2D NMR spectra, and in the case of 5, by chemical correlation.

[Studies on the chemical constituents in root of Gentiana macrophylla from Shaanxi].

OBJECTIVE: To in vestigate the constituents in root of Gentiana macrophylla. METHOD: Various column chromatographic techniques were used for isolation and purification of the principles. The structures were elucidated on the basis of spectral data (UV, IR, MS, 1H-, 13C-NMR etc.) and identified by comparing with standard substance. RESULT: Eight compounds were identified. Four compounds isolated from the chloroform fraction are: 5-carboxyl-3,4-dihydrogen-1H-2-benzopyran-1-one (1), erythrocentauric acid (2), roburic acid (3), oleanolic acid (4). Water fraction gave four known secoiridoid glucosides. They were: gentiopicroside (5), swertiamarine (6), sweroside (7), 6'-O-beta-D-glucosylgentiopicroside (8). CONCLUSION: 1 is a novel compound. It was named as erythrocentauric acid. 2 was isolated from genus Gentiana and 8 was isolated from G. macrophylla for the first time.