Kinetics of ceric ion oxidation of naphthalene and its derivatives. Formation of the radical cation intermediate in the rate limiting step

Ceric ammonium sulfate, CAS, oxidizes naphthalene to 1,4-naphthoquinone in essentially quantitative yield in CH3CN-dil. H2SO4. Stoichiometric studies indicate that 6 mol of CAS are required for the oxidation of 1 mol of naphthalene to 1,4-naphthoquinone. Kinetic investigations reveal that the reaction takes place through initial formation of a 1:1 complex of naphthalene and cerium(IV) in an equilibrium step followed by slow decomposition of the complex to naphthalene radical cation. Kinetic results on the effects of acid strength, polarity of the medium, temperature and substituents are in accordance with this mechanism. Further conversion of the radical cation into 1,4-naphthoquinone takes place in fast steps involving a further 5 mol of cerium(IV) and 2 mol of H2O.

Thiol-ene Clickable Hyperscaffolds Bearing Peripheral Allyl Groups

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type click reaction as it helps to expand the variability in reaction conditions as well as the range of clickable entities. Thus, direct generation of hyper-branched polymers bearing peripheral allyl groups that could be clicked using a variety of functional thiols would be of immense value. A specifically designed AB(2) type monomer, that carries two allyl benzyl ethers groups and one alcohol functionality, was shown to undergo self-condensation under acid-catalyzed melt-transetherification to yield a hyperbranched polyether that carries numerous allyl end-groups. Importantly, it was shown that the kinetics of polymerization is not dramatically affected by the change of the ether unit from previously studied methyl benzyl ether to an allyl benzyl ether. The peripheral allyl groups were readily clicked quantitatively, using a variety of thiols, to generate an hydrocarbon-soluble octadecyl-derivative, amphiphilic systems using 2-mercaptoethanol and chiral amino acid (N-benzoyl cystine) derivatized hyperbranched structures; thus demonstrating the versatility of this novel class of clickable hyperscaffolds. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49:1735-1744, 2011

Solution structure of BTK-2, a novel hK(v)1.1 inhibiting scorpion toxin, from the eastern Indian scorpion Mesobuthus tamulus

The three dimensional structure of a 32 residue three disulfide scorpion toxin, BTK-2, from the Indian red scorpion Mesobuthus tamulus has been determined using isotope edited solution NMR methods. Samples for structural and electrophysiological studies were prepared using recombinant DNA methods. Electrophysiological studies show that the peptide is active against hK(v)1.1 channels. The structure of BTK-2 was determined using 373 distance restraints from NOE data, 66 dihedral angle restraints from NOE, chemical shift and scalar coupling data, 6 constraints based on disulfide linkages and 8 constraints based on hydrogen bonds. The root mean square deviation (r.m.s.d) about the averaged co-ordinates of the backbone (N, C-alpha, C') and all heavy atoms are 0.81 +/- 0.23 angstrom and 1.51 +/- 0.29 angstrom respectively. The backbone dihedral angles (phi and psi) for all residues occupy the favorable and allowed regions of the Ramachandran map. The three dimensional structure of BTK-2 is composed of three well defined secondary structural regions that constitute the alpha-beta-beta, structural motif. Comparisons between the structure of BTK-2 and other closely related scorpion toxins pointed towards distinct differences in surface properties that provide insights into the structure-function relationships among this important class of voltage-gated potassium channel inhibiting peptides. (C) 2011 Elsevier B.V. All rights reserved.

Weak molecular complexes as studied by NMR spectroscopy of oriented molecules

Weak molecular interactions such as those in pyridine-iodine, benzene-iodine and benzene-chloroform systems oriented in thermotropic liquid crystals have been studied from the changes of the order parameters as a result of complex formation. The results indicate the formation of at least two types of charge transfer complexes in pyridine-iodine solutions. The pi-complexes in benzene-chloroform and benzene-iodine mixtures have also been detected. No detectable changes in the inter-proton distances in these systems were observed.

Dielectric Relaxation in CaO-Bi2O3-B2O3 Glasses

Glasses in the system CaO-Bi2O3-B2O3 (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond-West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent beta (0.5-0.6) is invariant with temperature for the present glasses.

Conformational basis for substrate recognition and regulation of catalytic activity in Staphylococcus aureus nucleoside di-phosphate kinase

Nucleoside diphosphate kinases (NDK) are characterized by high catalytic turnover rates and diverse substrate specificity. These features make this enzyme an effective activator of a pro-drug an application that has been actively pursued for a variety of therapeutic strategies. The catalytic mechanism of this enzyme is governed by a conserved histidine that coordinates a magnesium ion at the active site. Despite substantial structural and biochemical information on NDK, the mechanistic feature of the phospho-transfer that leads to auto-phosphorylation remains unclear. While the role of the histidine residue is well documented, the other active site residues, in particular the conserved serine remains poorly characterized. Studies on some homologues suggest no role for the serine residue at the active site, while others suggest a crucial role for this serine in the regulation and quaternary association of this enzyme in some species. Here we report the biochemical features of the Staphylococcus aureus NDK and the mutant enzymes. We also describe the crystal structures of the apo-NDK, as a transition state mimic with vanadate and in complex with different nucleotide substrates. These structures formed the basis for molecular dynamics simulations to understand the broad substrate specificity of this enzyme and the role of active site residues in the phospho-transfer mechanism and oligomerization. Put together, these data suggest that concerted changes in the conformation of specific residues facilitate the stabilization of nucleotide complexes thereby enabling the steps involved in the ping-pong reaction mechanism without large changes to the overall structure of this enzyme. (C) 2011 Elsevier B.V. All rights reserved.

Internal displacement reactions in multicomponent oxides: Part I. Line compounds with narrow homogeneity range

Structure and phase transition of LaO1−xF1+2x, prepared by solid-state reaction of La2O3 and LaF3, was investigated by X-ray powder diffraction and differential scanning calorimetry for both positive and negative values of the nonstoichiometric parameter x. The electrical conductivity was investigated as a function of temperature and oxygen partial pressure using AC impedance spectroscopy. Fluoride ion was identified as the migrating species in LaOF by coulometric titration and transport number determined by Tubandt technique and EMF measurements. Activation energy for conduction in LaOF was 58.5 (±0.8) kJ/mol. Conductivity increased with increasing fluorine concentration in the oxyfluoride phase, suggesting that interstitial fluoride ions are more mobile than vacancies. Although the values of ionic conductivity of cubic LaOF are lower, the oxygen partial pressure range for predominantly ionic conduction is larger than that for the commonly used stabilized-zirconia electrolytes. Thermodynamic analysis shows that the oxyfluoride is stable in atmospheres containing diatomic oxygen. However, the oxyfluoride phase can degrade with time at high temperatures in atmospheres containing water vapor, because of the higher stability of HF compared with H2O.

Mycobacterium leprae RecA is structurally analogous but functionally distinct from Mycobacterium tuberculosis RecA protein

Mycobacterium leprae is closely related to Mycobacterium tuberculosis, yet causes a very different illness. Detailed genomic comparison between these two species of mycobacteria reveals that the decaying M. leprae genome contains less than half of the M. tuberculosis functional genes. The reduction of genome size and accumulation of pseudogenes in the M. leprae genome is thought to result from multiple recombination events between related repetitive sequences, which provided the impetus to investigate the recombination-like activities of RecA protein. In this study, we have cloned, over-expressed and purified M. leprae RecA and compared its activities with that of M. tuberculosis RecA. Both proteins, despite being 91% identical at the amino acid level, exhibit strikingly different binding profiles for single-stranded DNA with varying GC contents, in the ability to catalyze the formation of D-loops and to promote DNA strand exchange. The kinetics and the extent of single-stranded DNA-dependent ATPase and coprotease activities were nearly equivalent between these two recombinases. However, the degree of inhibition exerted by a range of ATP:ADP ratios was greater on strand exchange promoted by M. leprae RecA compared to its M. tuberculosis counterpart. Taken together, our results provide insights into the mechanistic aspects of homologous recombination and coprotease activity promoted by M. lepare RecA, and further suggests that it differs from the M. tuberculosis counterpart. These results are consistent with an emerging concept of DNA-sequence influenced structural differences in RecA nucleoprotein filaments and how these differences reflect on the multiple activities associated with RecA protein. (C) 2011 Elsevier B.V. All rights reserved.

Fish distribution dynamics in the Aghanashini estuary of Uttara Kannada, west coast of India

Fish diversity (77 species) in the Aghanashini River estuary of the Indian west coast is linked to variable salinity conditions and zones I, II and III for high, medium and low salinity respectively. Zone I, the junction between Arabian Sea and the estuary, had all species in yearly succession due to freshwater conditions in monsoon to high salinity in pre-monsoon. The medium (zone II) and low (zone III) salinity mid and upstream portions had maximum of 67 and 39 fish species respectively. Maintenance of natural salinity regimes in estuary, among other ecological factors, is critical for its fish diversity.

Behaviour of Gaseous Chlorine and Alkali Metals During Biomass Thermal Utilisation

The behaviour of gaseous chlorine and alkali metals of three sorts of biomass (Danish straw, Swedish wood, and sewage sludge) in combustion or gasification is investigated by the chemical equilibrium calculating tool. The ranges of temperature, air-to-fuel ratio, and pressure are varied widely in the calculations (T=400-1800 K, gimel=0-1.8, and P=0.1-2.0 MPa). Results show that the air excess coefficient only has less significant influence on the release of gaseous chlorine and potassium or sodium during combustion. However, in biomass gasification, the influence of the air excess coefficient is very significant. Increasing air excess coefficient enhances the release of HCl(g), KOH(g), or NaOH(g) as well as it reduces the formation of KCl(g), NaCl(g), K(g), or Na(g). In biomass combustion or straw and sludge gasification, increasing pressure enhances the release of HCl(g) and reduces the amount of KCI(g), NaCl(g), KCI(g), or NaOH(g) at high temperatures. However, during wood gasification, the pressure enhances the formation of KOH(g) and KCI(g) and reduces the release of K(g) and HCl(g) at high temperatures. During wood and sewage sludge pyrolysis, nitrogen addition enhances the formation of KCN(g) and NaCN(g) and reduces the release of K(g) and Na(g). Kaolin addition in straw combustion may enhance the formation of potassium aluminosilicate in ash and significantly reduces the release of KCl(g) and KOH(g) and increases the formation of HCl(g).

Investigation of Laminar Plasma Remelting/Cladding Processing

Investigation of remelting and cladding processing with laminar plasma jets on several metals has been conducted looking for possible development of a new surface modification technique. The remelting tests illustrated that the new method could evidently improve the material microstructure and properties of cast iron. The cladding was done with Al2O3 ceramic powder on stainless steel. The energy dispersive spectra (EDS) analysis was used to determine the distribution of the major cladding element in the plasma-processed layers, for which the microstructure observations and hardness measurements were also performed.

Cría y liberación del parasitoide Diadegma insulare (Cresson) de la palomilla del repollo (Plutella xylostella L.) dentro de un contexto de MIP

Uno de los principales problemas del cultivo de repollo es Plutella xylostella que se ha convertido en una verdadera amenaza debido a su capacidad de reproducción y desarrollo de resistencia a los insecticidas usados contra ella. En Nicaragua se ha demostrado que los insecticidas comúnmente usados contra P. xylostella ya no son efectivos para su control. La práctica del control biológico de los insectos nocivos consiste en el uso de enemigos naturales, para reducir las poblaciones de las plagas, dichos enemigos naturales, o agentes de control biológico, incluyen patógenos, depredadores y parasitoides. Uno de los principales enemigos naturales de P. xylostella es el parasitoide D. insulare, en este ensayo se estableció una cría de este parasitoide para ser utilizado en liberaciones inoculativa en el cultivo de repollo, los insectos en estado de larvas y pupas fueron colectados en el campo y se trasladaron al laboratorio de cría de la Universidad Nacional Agraria de la Escuela de Sanidad Vegetal. Los adultos de D. insulare se colocaron en una jaula de cedazo, se les colocó plantas inoculadas con larvas de P. xylostella donde la hembra de D. insulare deposita un huevo por larva, estas lardas fueron expuestas por dos días, para seguir alimentándolas hasta alcanzar el estado de pupa, a continuación estas pupas se colocaron en vasos tapados para su constante observación y contabilización. Los parasitoides obtenidos de la cría en el laboratorio se liberaron en el campo, obteniendo que la mayor incidencia de P. xylostella se encontró en el tratamiento de químico (Thiocyclam) y menores en los tratamientos NIM y NIM + Liberaciones. Los porcentajes de parasitismo de D. insulare alcanzaron hasta 76% en el tratamiento nim+liberaciones superando la parcela tratada con producto químico, esto afirma que dicho producto tiene un efecto negativo en sus poblaciones y se encontró que el tratamiento nim+líberaciones fue económicamente rentable y compatible con prácticas tradicionales del productor Es necesario buscar prácticas que aumenten el parasitismo natural.

Evaluación del efecto de fertilización de diferentes niveles de fósforo y la extracción de macro y micronutrientes en tres variedades de frijol común (Phaseolus vulgaris L.)

El presente trabajo fue realizado en la estación Experimental la Compañía, Carazo, en época de postrera 1996, en suelos jóvenes de origen volcánico. El suelo es franco - limoso con altos contenidos de potasio y deficiente en fósforo. De acuerdo a sus propiedades, este suelo puede ser considerado como adecuado para la mayoría de los cultivos. El propósito del experimento fue determinar el efecto de tres niveles de superfosfato triple en tres variedades de frijol común (Phaseolus vulgaris L.) en cuanto a la acumulación de materia seca y rendimiento, así como la extracción de macro y micronutrientes. Las variedades evaluadas fueron: Dor-364, H-46 y Revolución 79, los niveles que se utilizaron O kg/ha, 45 kg/ha y 90 kg/ha. El diseño utilizado fue un bloque completamente al azar (B.C.A), con nueve tratamientos y cuatro repeticiones. Las variables evaluadas fueron: altura de planta, numero de Planta por hectárea, número de vaina por planta, granos por vaina, porcentaje de grano bueno y malo, peso de 100 granos, rendimiento, extracción de macro y micro elementos, número de nódulos, peso de nódulos, peso de cada nódulo. Los datos se procesaron usando análisis de varianza (ANDEVA), y se utilizó la prueba de rangos múltiples de DUNCAN (P< 0.05) los resultados obtenidos se pueden sintetizar de la siguiente forma: la variedad Dor-364 presento un mejor comportamiento en cuanto a la altura, granos por vaina, porcentaje de grano bueno, rendimiento, nódulos efectivos, extracción de nitrógeno, potasio, calcio, y magnesio por parte del grano. la variedad H-46 su mejor comportamiento fue en vaina por planta, densidad poblacional, mustia hilachosa, extracción de nitrógeno, fósforo, potasio, calcio, magnesio, boro, hierro, cobre, manganeso y zinc por parte del follaje y fósforo, azufre, boro, hierro, cobre, manganeso, y zinc por parte del grano y la variedad Rev-79 presento el mejor comportamiento en peso de 100 granos, número de nódulo por planta, peso de cada nódulo. En cuanto a los niveles el mejor comportamiento se obtuvo en el nivel 90 kg/ha con mayor densidad poblacional, granos por vaina, porcentaje de grano bueno, rendimiento, extracción de nitrógeno, fósforo, potasio, calcio manganeso y azufre por el follaje y potasio por el grano. Seguido del nivel 45 kg/ha con el peso de 100 grano, número de nódulos por planta, peso de nódulos por planta, mustia hilachosa, calcio, magnesio y azufre por parte del grano y por último el testigo O kg/ha en cuanto a la altura, numero de vaina por planta, nitrógeno y fósforo por parte del grano. En lo que se refiere a los micro elementos presentaron un comportamiento similar tanto en el follaje como en el grano.