Analysis of Four Solvatomorphs of Betulin by TG-DTA-EI/PI-MS System Equipped with the Skimmer-Type Interface.

Betulin (BE) has exceedingly become a potential natural product, providing multiple pharmacological and biological activities, including anti-cancer, anti-viral, and anti-inflammatory benefits. Previous research indicated that the solvatomorphism of BE can easily occur through crystallization with different organic solvents. This property of BE can directly affect its extraction, isolation, and preparation process. In this study, a system of thermogravimetry (TG)-differential thermal analysis (DTA) coupled with mass spectrometry (MS) with electron ionization (EI) and photoionization (PI) capability, equipped with the skimmer-type interface (i.e., skimmer-type interfaced TG-DTA-EI/PI-MS system), as a real-time and onsite analysis technique, was employed. Then, four solvatomorphs of BE, namely, with pyridine and water (A), sec-butanol (B), n,n-dimethylformamide (DMF) (C), and isopropanol (V), were analyzed for the first time. Finally, five kinds of the main volatile gaseous species, including H2O, pyridine, sec-butanol, DMF, and isopropanol, were identified clearly. Furthermore, the multi-step desolvation processes of the four solvatomorphs of BE were revealed by this system for the first time. This system showed great potential for the rapid and accurate analysis of various solvatomorphs of natural products.

New crystal forms and amorphous phase of sophoricoside: X-ray structures and characterization.

Sophoricoside, which is an isoflavone glycoside found in many plant species, has recently attracted attention because of its anti-fertility activity. One solvent-free form, two solvatomorphs and an amorphous phase of sophoricoside are reported for the first time. X-ray diffractometry, differential scanning calorimetry, thermal gravimetric analysis and Fourier-transform infrared spectroscopy were used to characterize the different forms. The results show that factors such as crystal symmetry, intermolecular arrangement, conformational flexibility, hydrogen-bonding interactions and solvent incorporation lead to different solid-state forms. An investigation of the transformations of the four forms showed that they can interconvert with each other under certain conditions. Amorphous phase and solvatomorphism were unstable but can improve the solubility of sophoricoside in water.

New coumarins from the roots of Angelica dahurica var. formosana cv. Chuanbaizhi and their inhibition on NO production in LPS-activated RAW264.7 cells.

A new linear pyranocoumarin named (-)-hydroxydecursinol (1) and a new biscoumarin named (±)-dahuribiscoumarin (2), together with six known compounds isoimperatorin (3), imperatorin (4), phellopterin (5), isodemethylfuropinarine (6), demethylfuropinarine (7), and (+)-decursinol (8) were isolated from the 75% ethanolic extract of the roots of Angelica dahurica var. formosana cv. Chuanbaizhi. Their structures were elucidated by extensive spectroscopic techniques, including 2D NMR spectroscopy and mass spectrometry, and the structure of 2 was confirmed by single-crystal X-ray diffraction. All of the isolated compounds were evaluated for the inhibition against nitric oxide (NO) production in the lipopolysaccharide (LPS)-activated RAW264.7 macrophage cell line, and exhibited the inhibitory activity on NO production in a concentration-dependent manner. Furthermore, real-time PCR analysis revealed that compounds 2, 5-8 could significantly suppress the expression levels of inducible nitric oxide synthase mRNA in a concentration-dependent manner. And their primary structure-activity relationships of NO inhibitory effects were also briefly discussed. These compounds are potential candidates for further bioassay studies to determine their suitability as drug leads.

Antiviral spirooliganones A and B with unprecedented skeletons from the roots of Illicium oligandrum.

Two novel spirooliganones A (1) and (2), a pair of spiro carbon epimers, with a rare dioxaspiro skeleton were isolated from the roots of Illicium oligandrum. The structures were fully determined by spectroscopic analysis and chemical methods, especially modified Mosher's method, and X-ray diffraction analysis. Spirooliganone B was found to exhibit more potent activities against coxsackie virus B3 and influenza virus A (H3N2) (IC50 3.70-5.05 µM) than spirooliganone A. The biosynthetic pathway involving a hetero-Diels-Alder reaction of the epimers was proposed.

Scopariusic acid, a new meroditerpenoid with a unique cyclobutane ring isolated from Isodon scoparius.

Scopariusic acid (1), a new ent-clerodane-based meroditerpenoid with a unique cyclobutane ring and an unusual 1-octen-3-ol substituent, together with its biosynthetic related compound 2, were isolated from the aerial parts of Isodon scoparius. The structures of 1 and 2, including their absolute configurations, were determined by spectroscopic methods, single-crystal X-ray diffraction analysis, and chemical methods. Compound 1 showed weak cytotoxicity and moderate immunosuppressive activity.

New 23-spirocholestane derivatives from Ypsilandra thibetica.

Three new unusual 23-spirocholestane derivatives, ypsilanogenin (1), ypsilanogenin 3-O-ß-D-glucopyranoside (2), and 4'-acetylypsilanogenin 3-O-ß-D-glucopyranoside (3), were isolated from the whole plants of Ypsilandra thibetica. The structures of compounds 1-3 were deduced by spectroscopic and chemical methods, and the structure of 1 was further confirmed by a single-crystal diffraction analysis. All isolates were evaluated for their inhibitory activities against HIV-1.

Limonoid constituents of Euodia rutaecarpa var. bodinieri and their inhibition on NO production in lipopolysaccharide-activated RAW264.7 macrophages.

A new limonoid compound, named evorubodinin (1), was isolated from the dried and nearly ripe fruits of Euodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang (family Rutaceae), together with two known limonoid compounds, limonin (2) and evolimorutanin (3). The chemical structure of 1 was elucidated by spectroscopic method and single-crystal X-ray diffraction. The inhibitory effects of the isolated compounds 1-3 and the structurally related compounds evodol (4), shihulimonin A1 (5), evodirutaenin (6), 12α-hydroxyrutaevin (7), and rutaevin (8) on nitric oxide (NO) production in lipopolysaccharide-activated RAW264.7 macrophages were also assayed. All compounds 1-8 showed the inhibitory activity, in which both 7 and 8 with the uncommon 5ß-H configuration more efficiently inhibited NO production. The results provided valuable information for further investigation of compounds 1-8 as anti-inflammatory agents or lead compounds.

Antidepressant abietane diterpenoids from Chinese eaglewood.

Ten new abietane diterpenoids, aquilarabietic acids A-J (1-10), and a new podocarpane diterpenoid, aquilarabietic acid K (11), were isolated from the petroleum ether and ethanol extracts of Chinese eaglewood. Among them, 3, 9, and 10 are artifacts. Their structures were established on the basis of data from extensive spectroscopic and X-ray diffraction analyses. Bioassay results indicated that 1 at 10 µM demonstrated remarkable antidepressant activity in vitro by inhibiting norepinephrine reuptake in rat brain synaptosomes by 81.4% and with an IC(50) value of 9.1 × 10(-7) M.

Sesquiterpenoids from Chloranthus multistachys.

An 8,9-seco-lindenane disesquiterpenoid, chloramultiol G, four eudesmane sesquiterpenoids, ent-(3R)-3-hydroxyatractylenolide III and multistalactones A-C, and four guaiane sesquiterpenoids, (1R,4S,5R,8S,10S)-zedoalactone A and multistalactones D-F, along with 14 known compounds, were isolated from whole plant tissues of Chloranthus multistachys. Their structures were established by extensive NMR experiments in conjunction with mass spectrometry. Except for chloramultiol G, the absolute stereochemistries of the other eight were confirmed by single-crystal X-ray crystallography and CD spectra. Nine compounds were tested for cytotoxicity against five human tumor cell lines and for antifungal activity against four microorganisms in vitro, but all were inactive.

Lindenane disesquiterpenoids with anti-HIV-1 activity from Chloranthus japonicus.

Five new lindenane disesquiterpenoids, chlorajaponilides A-E (1-5), together with 11 known analogues were isolated from whole plants of Chloranthus japonicus. The structure and absolute configuration of 1 was confirmed by X-ray crystallography. Compounds 1 and 2 represent the first examples of lindenane disesquiterpenoids with a C-5 hydroxy group and a C-4-C-15 double bond. Compounds 8, 9, 11, and 12 showed anti-HIV-1 replication activities in both wild-type HIV-1 and two NNRTIs-resistant strains. Shizukaol B (8) exhibited the best activity against HIV(wt), HIV(RT-K103N), and HIV(RT-K103N) with EC50 values of 0.22, 0.47, and 0.50 µM, respectively. Compounds 8, 9, 11, and 12 had significant cytotoxicities against C8166 cells with CC50 values of 0.020, 0.089, 0.047, and 0.022, respectively, and exhibited inhibitory activities against HIV-1 with EC50 values of 0.0014, 0.016, 0.0043, and 0.0033 µM, respectively.

[A quantitation method for andrographolide and dehydroandrographolide by X-ray powder diffraction Fourier fingerprint pattern technique].

The powder X-ray diffraction Fourier fingerprint pattern technique was used to develop a new quantitation method for the analysis of andrographolide and dehydroandrographolide. And the high performance liquid chromatography method was used to evaluate the quantity of andrographolide and dehydroandrographolide. The relationship of diffraction peak intensity and content of andrographolide and dehydroandrographolide was investigated. The powder X-ray diffraction Fourier fingerprint pattern analysis technique can be used to evaluate the quantity of andrographolide and dehydroandrographolide in the herb simultaneously.

A new chiratane type triterpenoid from the rhizomes of Drynaria fortunei.

Chiratone (1), a rare new chiratane type triterpenoid, together with five known triterpenoids were isolated from the rhizomes of Drynaria fortunei (Kunze) J. Sm. The structure was characterized as 20ß-hydroxychiratan-22-one on the basis of extensive 1D and 2D NMR, and MS spectroscopic analyses, and was further confirmed by X-ray crystal diffraction. Primary bioassays showed that compound 1 had significant cytotoxic activity against Hela, PC3 and HepG2 cells, with IC(50) of 2.92 µM, 1.08 µM and 2.45 µM, respectively.

Camellisins A-C, three new triterpenoids from the roots of Camellia sinensis.

Eighteen compounds, including three new triterpenoids, camellisins A-C (1-3), were isolated from the roots of Camellia sinensis. Their structures were determined on the basis of detailed spectroscopic analysis.

11ß,17,21-Trihydr-oxy-6α-methyl-3,20-dioxopregna-1,4-dien-21-yl 3-carboxy-propionate.

The mol-ecule of the title compound, C(26)H(34)O(8), a prednisolone derivative, contains three six-membered rings (A, B and C) and one five-membered ring (D). Ring A is planar and rings B and C adopt chair conformations, while ring D adopts an envelope conformation with the C atom bonded to the methyl group at the flap. The crystal structure is stabilized by intermolecular O-H⋯O hydrogen bonds.

Daphnogirins A and B, two biflavones from Daphne giraldii.

Two new biflavonoids, daphnogirins A (1) and B (2), were obtained from the roots of Daphne giraldii. Their structures were established on the basis of the spectral data and X-ray diffraction data of the co-crystal of 1 and 2. Daphnogrins A and B have the same configuration at C-1 and opposite configurations at C-16 and C-17. Oxygen radical scavenging assay has indicated that they are of significant antioxidative activity.

Rubriflordilactones A and B, two novel bisnortriterpenoids from Schisandra rubriflora and their biological activities.

Rubriflordilactones A (1) and B (2), two novel highly unsaturated rearranged bisnortriterpenoids possessing a biosynthetically modified aromatic D-ring, were isolated from the leaves and stems of Schisandra rubriflora. Their structures were established on the basis of extensive spectroscopic methods, including two-dimensional NMR techniques, and confirmed by X-ray crystallographic analysis. Compound 1 showed weak anti-HIV-1 activity, and compound 2 exhibited an EC50 value of 9.75 microg/mL (SI=12.39) against HIV-1 replication with low cytotoxicity.

[Study on selective isolation of volatile oil in the seed of Fructus foeniculi].

OBJECTIVE: To study the selective isolation of a single chemical component from volatile oil of Fructus foeniculi by inclucion method. METHOD: The host molecule was selected and a single chemical component isolated from volatile oil by the host-guest recognition. RESULT: X-ray single crystal analysis showed that 1,1,6,6-tetraphenylhexa-2, 4-diyne-1, 6-diol could successfully include 4-[1-propenyl] benzaldehyde from volatile oil of Fructus foeniculi. CONCLUSION: The host-guest inclusion technology can be used to isolate a single component selectively from mixture.

Beesiosides G, H, and J-N, seven new cycloartane triterpene glycosides from Beesia calthifolia.

Seven new cycloartane glycosides (1-7), beesiosides G, H, and J-N, together with beesioside I (8) and beesioside A, were isolated from the rhizomes of Beesia calthifolia, and their structures were established by spectroscopic and chemical methods. Beesiosides G, H, and J-N were assigned as 20xi(1),24xi(2)-epoxy-9,19-cyclolanostane-3beta,16beta,18,25-tetraol-3-O-beta-D-glucopyranoside (1), 20xi(1),24xi(2)-epoxy-9,19-cyclolanostane-3beta,16beta,18,25-tetraol-3-O-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside (2), (20S,24R)-15alpha,16beta-diacetoxy-20,24-epoxy-9,19-cyclolanostane-3beta,18,25-triol-3-O-beta-D-xylopyranoside (3), (20S,24S)-16beta-acetoxy-18,24;20,24-diepoxy-9,19-cyclanostane-3beta,15beta,25-triol-3-O-beta-D-xylopyranoside (4), (20S,24S)-16beta-acetoxy-18,24;20,24-diepoxy-9,19-cyclanostane-3beta,25-diol-3-O-beta-D-xylopyranoside (5), 20xi(1),24xi(2)-epoxy-15alpha-acetoxy-9,19-cyclolanostane-3beta,16beta,25-triol-3-O-beta-D-xylopyranoside (6), and 20xi(1),24xi(2)-epoxy-9,19-cyclolanostane-3beta,12alpha,15alpha,16beta,25-pentaol-3-O-beta-D-xylopyranoside (7), respectively.