Crystallographic and NMR studies on sterols from green alga Chaetomorpha basiretorsa Setchell

Chemical investigation of the ethanol extract of the marine green alga Chaetomorpha basiretorsa Setchell led to the isolation of a new sterol stigmast-4,28-dien-3 alpha 6 beta-diol 1 in addition to the five known sterols of beta-lawsaritol 2, saringosterol 3, 24-hydroperoxy-24-vinyl - cholesterol 4, beta-stigmasterol 5, 29-hydroxystigmasta-5, 24(28) -dien-3 beta-ol 6. Compounds were isolated by normal phase silica gel and Sephadex LH - 20 gel colum chromatography, reverse phase HPLC and recrystalization. Their structures were elucidated by spectroscopic methods including MS, IR 1D/2D NMR and X-ray analysis. Cytotoxicity of compounds was screened by using the standard WIT method. All these compounds were isolated from the green alga Chaetomorpha basiretorsa Setchell for the first time and they were inactive (50% inhibitory concentration was greater than 10 mu g /cm(3)) against KB, Bel -7402, PC - 3M, Ketr 3 and MCF - 7 cell lines.

Steroids from green alga Chaetomorpha basiretorsa Setchell

Six steroids have been isolated from ethanolic extract of green alga Chaetomorpha basiretorsa Setchell by a combination of repeated normal phase silica gel and Sephadex LH-20 gel column chromatography as well as recrystallization. Using spectroscopic methods including MS and NMR, their structures were determined as beta-lawsaritol (1), saringosterol (2), 24-hydroperoxy-24-vinyl-cholesterol (3), beta-stigmasterol (4), stigmast-4-en-3 alpha, 6 beta-diol (5), 29-hydroxystigmasta-5, 24 (28)-dien-3 beta-ol (6). All these compounds were obtained from this genus for the first time and they were inactive (IC50 > 10 mu g /ml) against KB, Bel-7402, PC-3M, Ketr 3 and MCF-7 cell lines.

Biosorption of copper (II) and lead (II) from aqueous solutions by nonliving green algae Cladophora fascicularis: Equilibrium, kinetics and environmental effects

Biosorption of Cu2+ and Pb2+ by Cladophora fascicularis was investigated as a function of initial pH, initial heavy metal concentrations, temperature and other co-existing ions. Adsorption equilibriums were well described by Langmuir and Freundlich isotherm models. The maximum adsorption capacities were 1.61 mmol/ g for Cu2+ and 0.96 mmol/ g for Pb2+ at 298K and pH 5.0. The adsorption processes were endothermic and biosorption heats calculated by the Langmuir constant b were 39.0 and 29.6 kJ/ mol for Cu2+ and Pb2+, respectively. The biosorption kinetics followed the pseudo- second order model. No significant effect on the uptake of Cu2+ and Pb2+ by co-existing cations and anions was observed, except EDTA. Desorption experiments indicated that Na(2)EDTA was an efficient desorbent for the recovery of Cu2+ and Pb2+ from biomass. The results showed that Cladophora fascicularis was an effective and economical biosorbent material for the removal and recovery of heavy metal ions from wastewater.

1-(4-fluorophenyl)-2-{4-phenyl-5-[(1H-1,2,4-triazol-1-yl) methyl]-4H-1,2,4-triazol-3-ylsulfanyl}ethanone

The crystal structure of the title compound, C19H15FN6OS, is stabilized by a weak intermolecular C-(HN)-N-... hydrogen-bond interaction.

5-[(1H-1,2,4-yriazol-1-yl)methyl]-4-(4-fluorobenzylideneamino)-2H-1,2,4-triazole-3(4H)-thione

In the title compound, C12H10FN7S, the dihedral angles made by the plane of the thione-substituted triazole ring with the planes of the other triazole ring and the benzene ring are 71.94 (3) and 40.10 (2)degrees, respectively. Inter- and intramolecular hydrogen-bond and pi-pi stacking interactions stabilize the structure.

Crystal structure and DFT studies of a triazole derivative: 4-(2-hydrobenzylideneamino)-3-(1,2,4-triazol-4-yl-methyl) 1H-1,2,4-triazole-5 (4H)-thione

A novel triazole derivative 4-(2-hydrobenzylideneamino)-3-(1, 2, 4-triazol-4-ylmethyl)-1H-1, 2, 4-triazole-5 (4H)-thione(1) was synthesized and characterized using elemental analysis, MR, and H-1 NMR, and its crystal structure was determined via X-ray single crystal diffraction analysis. Crystal data: monoclinic, P2 (1)/c, a = 0.83335 (9) nm, b = 1. 49777 (16) run, c = 1. 14724 (12) nm, beta = 107. 990 (2)degrees, D = 1. 470 Mg/m(3), and Z = 4. The geometries and the vibrational frequencies were determined using the density functional theory(DFT) method at the B3LYP/6-31G* level. To demonstrate the accuracy of the reaction route of compound 1, one of the important intermediates was also tested using the same method. The structural parameters of the two compounds calculated using the DFT study are close to those of the crystals, and the harmonic vibrations of the two compounds computed via the DFT method are in good agreement with those in the observed IR spectral data. The thermodynamic properties of the title compound were calculated, and the compound shows a good structural stability at normal temperature. The test results of biological activities show that it has a certain bactericidal ability.

Analysis of carbohydrates in a tibetan medicine using new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone, by HPLC with DAD detection and ESI-MS identification

A new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP), coupling with liquid chromatography (LC) with electrospray ionization mass spectrometry (ESI-MS) for the detection of carbohydrates from a famous Tibetan medicine is reported. Carbohydrates were derivatized to their bis-NMP-labeled derivatives. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose, and fucose could be successfully detected by UV and ESI-MS. Derivatives showed intense protonated molecular ion at m/z [M+H]+ in positive ion mode. The mass to charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative identification of carbohydrates; this characteristic fragment ion was from the cleavage of C2-C3 bond in the carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose, and glyceraldehydes, and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids, such as galacturonic acid and glucuronic acid (m=n-2, n is carbon atom number of carbohydrate). Compared with the traditional 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent, currently synthesized NMP show the advantage of higher sensitivity to carbohydrate compounds with UV and ESI-MS detection.

Detection of carbohydrates using new labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone by capillary zone electrophoresis with absorbance (UV)

A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupled with capillary electrophoresis (CE) with DAD detection for the determination of carbohydrates has been developed. The chromophore in the 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent is replaced by naphthyl functional group, which results in a reagent with very high molar absorptivity (epsilon(251nm) = 5.58 x 10(4) L mol(-1) cm(-1)). This pen-nits NMP-labeled carbohydrates to be detected with UV absorbance in standard 50-mu m-i.d. fused silica capillaries by zone electrophoresis. in this mode, nanomolar concentrations of detection limits are obtained. The method for the derivatization. of carbohydrates with NMP is simplified. The derivatization reaction is rapid and mild in the presence of ammonia catalyst without further transfer steps. Nine monosaccharide derivatives such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected in CE mode. Good reproducibility can be obtained with relative standard deviation (R.S.D.) values of the migration times and peak area, respectively, from 0.44 to 0.48 and from 3.2 to 4.8. Furthermore, the developed method has been successfully applied to the analysis of carbohydrates in the hydrolyzed rape bee pollen samples. (C) 2008 Published by Elsevier B.V.

Comparative analysis of allantoin quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid in Nitraria tangutorum Bobr. Seed by HPLC-APCI-MS and CE

This paper describes the simultaneous determination of allantoin, quercetin, and 1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid (MTCCA) in Nitraria tangutorum Bobr seed by HPLC-APCI-MS and CE (capillary electrophoresis) methods. The final optimized chromatographic conditions were investigated in a reversed-phase Eclipse XDB-C8 column (150 x 4.6 mm, 5 mu m). A seventeen-minute gradient elution, (A: aqueous acetonitrile 20% (v/v); B: aqueous acetonitrile 60% (v/v); C: pure acetonitrile 100%) at a flow rate of 1.0 mL/min was selected for the separation of three natural products with diode array detection (DAD) at 220 nm. A CE experiment was carried out in a fused silica capillary with 32 mmol/L boric acid (pH 10), 32 mmol/L SDS and acetonitrile (10.0%, v/v). The applied potential and temperature was, respectively, set at 19 kV and 25 degrees C. After development, the validation was performed in parallel for HPLC and CE, with the same standards and sample to avoid differences due to the manipulation. The validation parameters of both techniques were adequate for the intended purpose.

A combined DFT and SCRF study of solvent effects on 4-methyl-3-penten-2-one

The IR spectrum of 4-methyl-3-penten-2-one is interpreted with the aid of normal coordinate calculations within the Onsager self-consistent reaction field (SCRF) model, using a density functional theory (DFT) method at the Becke3LYP/6-31G* level. The solvent effects on the geometry, energy, dipole moment, and vibrational frequencies of 4-methyl-3-penten-2-one in the solution and in the liquid phase are calculated using the Onsager SCRF model. The calculated vibrational frequencies in the liquid-phase are in good agreement with the experimental values. The solvent reaction field has generally weak influence. For the two main bands of C=C and C=O mixed vibrational modes, small frequency shifts (5-6 cm(-1)), but relatively large changes in IR intensities (up to 101 km mol(-1) in the liquid phase) are found. (C) 1999 Elsevier Science BV. All rights reserved.