Kinetics and electrochemical studies on superoxide

Rate constants for the reaction of superoxide O^- ₂ with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O^- ₂ + AH^{- k2}Product, are, AH = isopropanol (k₂ < 0.01 M^-1 s^-1); ethanol (k₂ = 1.42 × 10² M^-1 s^-1); methanol (k₂ = 1.1 × 10⁷ M^-1 s^-1), H₂O (k₂ = 1.0 × 10⁵ M^-1 s^-1). In MeCN, O^-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O^- ₂reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O^- ₂ with the substrates (AH) is proposed as O^- ₃ + AH k₂O, AH^k2 _k-1 k [O₂H + AH]^-, _k-2O₂H + A^- with k₁ = 10⁹ M^-1 s^-1 and k^-1 = 10⁸ -10⁹ s^-1. With these values of k_-1 and k₁, k k₂(obs). The reversible E_1/2 for O₂ + e O^- ₂ in various solvents: MeCN, acetone, isopropanol, methanol, H₂O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E_1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE.     

Optimization of the extraction of paclitaxel from Taxus baccata L. by the use of microwave energy

A simple and rapid microwave-assisted extraction (MAE) procedure was developed and optimized for the extraction of paclitaxel (Taxol) from the needles of yew trees Taxus baccata L. grown in Iranian habitats. The samples, immersed in a methanol-water mixture, were irradiated with microwaves in a closed-vessel system. The method was evaluated using a factorial design approach based on parameters such as extraction time, temperature, methanol concentration in water (v/v), and the ratio of grams of sample to 10 mL of solvent. Statistical treatment of the results revealed that the selected parameters were all significant except the extraction time. Optimum conditions would be 1.5 g samples in 10 mL solvent (90% methanol), an extraction temperature of 95 degrees C, and an extraction time of 7 min. The extracts has been analyzed by reverse-phase high-performance liquid chromatography with UV detection (LC/UV) at 227 nm for quantification. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for confirmation. The main advantage of the proposed MAE method versus conventional solvent extraction (CSE) are the considerable reductions in time (7 min versus 16 h) and in solvent consumption (20 mL versus 150 mL). The MAE procedure yielded extracts that could be analyzed directly without any preliminary clean-up or solvent exchange steps. Both extraction methods show RSDs lower than 10% and lead to comparable recoveries of paclitaxel (87-92%).     

One-pot Three-component Condensation Reactions in Water. An Efficient and Improved Procedure for the Synthesis of Furan Annulated Heterocycles

Summary. The environment-friendly one-pot three-component condensation reactions of 4-hydroxycoumarin or 4-hydroxy-6-methylpyrone, p-substituted benzaldehyde, and alkyl or aryl isocyanides to afford furocoumarines or furopyranones in water in good yields after about one hour at 75°C are reported.     

New computer program to calculate the symmetry of molecules

In this paper we, present some MATLAB and GAP programs and use them to find the automorphism group of the Euclidean graph of the C₈₀ fullerence with connectivity and geometry of I _h symmetry point group. It is proved that this group has order 120 and is isomorphic to I _h ≊Z₂×A₅, where Z₂ is, a cyclic group of order 2 and A₅ is the alternating group on five symbols.     

The preparation and characterization of mono- and bis-chelated cadmium(II) complexes of the di-2-pyridylketone Schiff base of S-methyldithiocarbazate (Hdpksme) and the X-ray crystal structure of the [Cd(dpksme)2] · 0.5 MeOH complex

New cadmium(II) complexes of empirical formulae, [Cd(dpksme)X] (dpksme = anionic form of the Schiff base; X = NCS^–, Cl^–, I^–) and [Cd(dpksme)₂] · 0.5MeOH, respectively have been prepared and characterized. The mono-ligated cadmium(II) complexes, [Cd(dpksme)X] are four-coordinate and tetrahedral but the bis-ligand complex, [Cd(dpksme)₂] · 0.5MeOH is six-coordinate and octahedral. The crystal and molecular structure of [Cd(dpksme)₂] · 0.5MeOH has been determined by X-ray diffraction. The complex has a distorted mer-octahedral structure in which the ligands are coordinated as uninegatively charged tridentate chelating agents via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. The distortion from regular octahedral geometry is ascribed to the restricted bite angles of the ligands. The Schiff base and its cadmium(II) complexes exhibit mild antibacterial activities against Shigella dysenteriae, Bacillus cereus, Staphylococcus aureus and Escherichia coli. They are also mildly fungitoxic against the phytopathogenic fungi, Alternaria alternata and Macrophomina phaseolina.     

Preconcentration and Determination of Chromium Species Using Octadecyl Silica Membrane Disks and Flame Atomic Absorption Spectrometry

A novel and selective method for the fast determination of trace amounts of chromium species in water samples has been developed. The procedure is based on the selective formation of chromium diethyldithiocarbamate complexes at different pH in the presence of Mn(II) as an enhancement agent of chromium signals followed by elution with organic eluents and determination by atomic flame absorption spectrometry. The maximum capacity of the employed disks was found to be (396±3) µg and (376±2) µg for Cr(III) and Cr(VI), respectively. The detection limit of the proposed method is 49 and 43 ng·L^?1 for Cr(III) and Cr(VI), respectively. The proposed method was successfully applied for determination of chromium species Cr(III) and Cr(VI) in different water samples.     

Determination of trace amounts of cadmium and copper by atomic absorption spectrometry after simultaneous extraction and preconcentration using a new water-soluble polyacrylic acid/alumina sorbent

An analytical method using alumina modified with water-soluble polyacrylic acid polymer for the simultaneous separation and preconcentration of trace Cu and Cd in a column system, and their determination by flame atomic absorption spectrometry was developed. The conditions for coating Al₂O₃ with polyacrylic acid were optimized, then the column was packed with 50 mg of this sorbent. Cd and Cu solution was passed through a glass column at pH 4.5, and elution was carried out with 5 mL of 0.05 M HCl at a flow rate of 1 mL min⁻¹. A sorption capacity of 10 mg Cu and 12 mg Cd was obtained for 1 g sorbent. The detection limit was calculated as 4.5 μg L⁻¹ for Cu and 1.54 μg L⁻¹ for Cd in the final solution. Enrichment factors of 300 for Cd and 400 for Cu were obtained.     

Highly oxygenated triterpenes from the roots of Atropa acuminata

Two new oleanane triterpenes; 2alpha,3alpha,24-trihydroxyolean-12-ene-28,30-dioic acid ([structure: see text]) and 2alpha,3alpha,24,28-tetrahydroxyolean-12-ene ([structure: see text]) have been isolated from the roots of Atropa acuminata. Anti-oxidant p-hydroxyphenethyl trans-ferulate ([structure: see text]), beta-sitosterol-3-O-beta-D-glucopyranoside ([structure: see text]) and oleanolic acid ([structure: see text]) have also been reported for the first time from this species. The structures were determined by spectroscopic studies including 2D-NMR.     

Aristoserratin,ein neues Indolalkaloid aus Aristotelia serrata W.R.B. OLIVER und A. peduncularis (LABILL.) HOOK. F. 178. Mitteilung über organische Naturstoffe

Aristoserratine, a New Indole Alkaloid from Aristotelia serrata W.R.B. OLIVER and from A. peduncularis (LABILL .) HOOK . F. The new indole alkaloid aristoserratine (2) has been isolated from Aristotelia. Its structure and absolute configuration were elucidated on the basis of spectroscopic data.     

Energetic and topological analyses of the oxidation reaction between Mo(n) (n = 1, 2) and N2O

The interaction between molybdenum, atom, and dimer, with nitrous oxide has been investigated using density functional theory. The analysis of the potential energy surfaces for both reactions has revealed that a single molybdenum atom can activate the N--O bond of N2O requiring a small activation energy. However, the presence of several intersystem crossings between three different spin states, namely, septet, quintet and triplet states, seems to be the major constraint to the Mo + N2O reaction. Contrarily, the low-lying excited states (triplet and quintet) do not participate in the reaction between the molybdenum dimer and N2O. The latter reaction fully evolves on the singlet spin surface. Three different regions have been distinguished along the pathway: formation of an adduct complex, formation of an inserted compound, and the N2 detachment. The connection between the two first regions has been characterized by the formation of a special complex in which the N--O bond is so weakened that it could be considered as a first step in the insertion process. It has been shown that the topological changes along the pathways provide a clear explanation for the geometrical changes that occur along the reaction pathway. In summary, the detachment of the N2 molecule is found to be kinetically an effective process for both reactions, owing to the high exothermicity and consequently to the high internal energy of the insertion intermediates. However, in the case of Mo atom, the reaction should be a slow process due to the presence of spin-forbidden transitions. These results fully agree with previous experimental works.