Mechanism of iridium(III) catalysis in the oxidation of diols by N-bromoacetamide

Summary The kinetics of iridium(III)-catalysed oxidation of 1,2-ethanediol and 1,4-butanediol by N-bromoacetamide (NBA) in HClO₄ in the presence of [Hg(OAc)₂] as a scavenger for Br^– have been investigated. The reactions are zero-order with respect to both diols, and first-order in NBA at low NBA concentrations, tending to zero order at high concentrations. The order in Ir^III decreases from unity to zero at high iridium(III) concentrations. A positive effect on the oxidation rate is observed for [H⁺] and [Hg^II] whereas a negative effect is observed for acetamide and [Cl^–]. Ionic strength does not influence the oxidation rate. (H₂OBr)⁺ is postulated as the oxidizing species. A mechanism consistent with the observed kinetic data is proposed.     

Radioactive tracer study of adsorption and exchange reaction of lead ion selective electrode membrane

Summary The amount of adsorption and exchange of lead on the electrode membrane as a function of time was correlated to the potential measurement stability. The adsorption and exchange of lead in various organic solvents tend to be increased relating to the increase in the dielectric constant of solvents. Removal of O₂ and CO₂ and addition of methanol and formaldehyde are very effective means to improve the potential stability. The behavior of lead ISE exposed to solutions containing lead and other interfering ions was also studied.

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Radiochemische Untersuchung der Adsorptions- und Austauschreaktionen bleiionenspezifischer Elektroden

Zusammenfassung Adsorption und Austausch von Blei an der Elektrodenmembran als Funktion der Zeit wurden zur Stabilität der Potentialmessung in Beziehung gesetzt. In verschiedenen organischen Lösungsmitteln steigen Adsorption und Austausch mit der Dielektrizitätskonstante an. Die Entfernung von O₂ und CO₂ sowie der Zusatz von Methanol und Formaldehyd verbessern die Stabilität des Potentials. Das Verhalten von bleiionenspezifischen Elektroden gegenüber Lösungen, die Blei und andere störende Ionen enthalten, wurde untersucht.

     

Siderophore production by a marine Pseudomonas aeruginosa and its antagonistic action against phytopathogenic fungi

A marine isolate of fluorescent Pseudomonas sp. having the ability to produce the pyoverdine type of siderophores under low iron stress (up to 10 μM iron in the succinate medium) was identified as Pseudomonas aeruginosa by using BIOLOG Breathprint and siderotyping. Pyoverdine production was optimum at 0.2% (w/v) succinate, pH 6.0, in an iron-deficient medium. Studies carried out in vitro revealed that purified siderophores and Pseudomonas culture have good antifungal activity against the plant deleterious fungi, namely, Aspergillus niger, Aspergillus flavus, Aspergillus oryzae, Fusarium oxysporum, and Sclerotium rolfsii. Siderophore-based maximum inhibition was observed against A. niger. These in vitro antagonistic actions of marine Pseudomonas against phytopathogens suggest the potential of the organism to serve as a biocontrol agent.     

A novel bioassay for screening and quantification of taxanes

We report a novel method for screening and quantifying tubulin-binding antimitotic agents that promote microtubule formation. The method is based on the shift in the peak of the fluorescence emission difference spectrum of tubulin complexed to metal free tetrakis(4-carboxyphenyl)porphyrin (TCPP) in the presence of antimitotic agents. Taxol (paclitaxel), an anti-tumor drug approved for the treatment of a variety of cancers, caused the appearance of a new fluorescence peak at 645 nm at concentrations as low as 125 nM, the intensity of which was a function of the paclitaxel concentration. Cephalomannine caused the induction of a new fluorescence peak at 651 nm only above 1 muM. Baccatin did not induce the appearance of any new peak within detectable operating measurement conditions. These observations are in accordance with the biological activities/cytotoxicities of these compounds. Accordingly, it is proposed that the new method can be used for high throughput screening of antimitotic compounds.     

Theoretical study of 3d‐metal mononitrides using DFT method

3d‐Metal mononitrides are studied using the density functional theory method. The lowest spin state for these dimers is obtained using the B3LYP hybrid functional with the 6‐311+G* basis set. The equilibrium geometries, vibrational frequencies, binding energies, Mulliken, and natural orbital population analysis charges, natural orbital electronic configuration, electron affinity, and ionization potential are obtained. Mulliken as well as natural orbital population analysis charges indicate that for all dimers, in cations most of the positive charge localized on the transition metal atom where in anions most of the negative charge localized on nitrogen atom. The binding energies for 3d‐metal mononitrides are higher than those for monocarbides and monoxides. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Syntheses and characterization of poly(benzimidazolyl) thiaxanthones

Novel polybenzimidazoles containing thiaxanthone heterocyclic units were synthesised from 2,7-thiaxanthonedicarboxylic acid-5,5′-dioxide and 2,8-thiaxanthonedicarboxylic acid-5,5′-dioxide and two aromatic tetramine hydrochlorides by PPA solution polycondensation in 60–70% yield. Two model compounds, 2,7-bis(2-benzimidazolyl)thiaxanthone-5,5′-dioxide and 2,8-bis(2-benzimidazolyl)thiaxanthone-5,5′-dioxide, were prepared and characterized by spectral methods. The polybenzimidazoles have inherent viscosities in the range 1.13–1.50 dL/g and decomposition temperatures of 495–560°C. The effect of thiaxanthone units on polymer properties are discussed.     

Cationic vesicles as chiral selector for enantioseparations of nonsteroidal antiinflammatory drugs by micellar electrokinetic chromatography

A vesicle-forming chiral cationic surfactant (1R,2S)-(-)-N-dodecyl-N-methyl-ephedrinium bromide was evaluated as a pseudo-stationary phase in micellar electrokinetic chromatography (MEKC) for enantioseparation of eight non-steroidal anti-inflammatory drugs e.g., carprofen, flurbiprofen, fenoprofen, ibuprofen, indoprofen, ketoprofen, naproxen and suprofen by capillary electrophoresis. The effects of varying experimental conditions such as pH and concentration of surfactant in the running buffer on the enantiomer separation of the drugs are reported. A mixture of five of the above drugs was separated and each enantiomeric pair was also separated simultaneously in a single run by use of the surfactant. The strong electrostatic interactions between the analytes and the vesicles seemed to have a major role in the enantiomeric separation of the profens.     

Enhancement of dielectric and electro-optical parameters of a newly prepared ferroelectric liquid crystal mixture by dispersing nano-sized copper oxide

ABSTRACT

Here, we present the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared ferroelectric liquid crystal (FLC) mixture, namely W302. The FLC mixture, comprising of pyrimidine compounds, was characterised through dielectric spectroscopy, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and other electro-optical methods. The material parameters such as spontaneous polarisation, rotational viscosity, response time and tilt angle of W302 were found to be 14 nC/cm², 240 mPa.s, 150 µs and 28^?, respectively. The phase transition temperatures of W302 were observed through DSC and further confirmed by the dependence of dielectric loss factor in homogeneously aligned FLC sample with temperature. We also demonstrate the observance of a low-frequency dielectric relaxation mode due to the unwinding of the helix, called as partially unwound helical mode (p-UHM) along with Goldstone mode. The behaviour of p-UHM has been systematically studied with temperature and applied bias field. Further, dispersion of nCuO into host W302 has shown a significant increase in dielectric permittivity. Also, the p-UHM relaxation peak in the dielectric regime has disappeared with the incorporation of nCuO. These studies would be useful to fabricate better electro-optical devices for display, switching and beam steering applications. The formulation and characterization of a ferroelectric liquid crystal (FLC) mixture W302 composed of pyrimidine compounds is presented. Then, we observed the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared and characterized FLC mixture.     

Development of a bionematicide with Paecilomyces lilacinus to control Meloidogyne incognita

Root-knot disease caused by Meloidogyne incognita is a matter of grave concern because it affects several economically important crop plants. The use of solid-state fermentation (SSF) may help to elaborate efficient formulations with fungi to be employed in the biologic control of nematodes. Attempts were made to select low-cost substrates for spore production of a strain of Paecilomyces lilacinus with known nematicide capacity. Coffee husks, cassava bagasse, and defatted soybean cake were utilized as substrates, and sugarcane bagasse was used as support. Fermentations were carried out in flasks covered with filter paper at 28°C for 10 d. The products obtained by SSF were evaluated for their nematicide activity in pot experiments containing one seedling of the plant Coleus inoculated with the nematode M. incognita. The plants were evaluated 2 mo after inoculation. Fermented products showed a reduction in the number of nematodes. The best results were obtained with defatted soybean cake, which showed almost 100% reduction in the number of nematodes; the reduction with coffee husk was 80% and with cassava bagasse was about 60%.     

Mechanistic study of osmium(VIII) promoted oxidation of crotonic acid by aqueous alkaline solution of potassium bromate

Kinetics and mechanism of the Os(VIII) catalysed oxidation of crotonic acid (CA) by KBrO₃ in alkaline medium have been investigated. Zero order dependence in [KBrO₃] was observed, while first order with respect to CA in its lower concentration range tends to zero order at its higher concentration range. The order in [Os(VIII)] was found to be unity and a positive effect of [OH⁻] was observed. Variation of the ionic strength (μ) and dielectric constant of the medium and addition of Hg(OAc)₂ (used as Br⁻ scavenger) had an insignificant effect on the rate of reaction. Thermodynamic parameters have also been calculated and reported. A suitable mechanism consistent with the observed kinetic results has been suggested and the related rate law deduced.