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.

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.

Nonneutral network and the role of bargaining power in side payments

Representatives of several Internet access providers have expressed their wish to see a substantial change in the pricing policies of the Internet. In particular, they would like to see content providers pay for use of the network, given the large amount of resources they use. This would be in clear violation of the �network neutrality� principle that had characterized the development of the wireline Internet. Our first goal in this paper is to propose and study possible ways of implementing such payments and of regulating their amount. We introduce a model that includes the internaut�s behavior, the utilities of the ISP and of the content providers, and the monetary flow that involves the internauts, the ISP and content provider, and in particular, the content provider�s revenues from advertisements. We consider various game models and study the resulting equilibrium; they are all combinations of a noncooperative game (in which the service and content providers determine how much they will charge the internauts) with a cooperative one - the content provider and the service provider bargain with each other over payments to one another. We include in our model a possible asymmetric bargaining power which is represented by a parameter (that varies between zero to one). We then extend our model to study the case of several content providers. We also provide a very brief study of the equilibria that arise when one of the content providers enters into an exclusive contract with the ISP.

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.

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.

La idea de “Nación” en el lenguaje político hispanoamericano, 1808-1814 : los límites monárquicos de la imaginación liberal

Resumen: Este trabajo aborda el concepto de Nación y otros relacionados con la noción de soberanía en el lenguaje político hispanoamericano para el período 1808-1814. Se analizan algunos trabajos que dan cuenta de los diversos significados asociados a este concepto en los procesos revolucionarios americano y español. Las distintas concepciones sostenidas por los actores sociales del período señalado se vinculan luego en perspectiva con su posible derivación como proyección de la Nación en la cultura constituyente de Cádiz.

Management of northern fur seals on the Pribilof Islands, Alaska, 1786-1981

This paper includes information about the Pribilof Islands since their discovery by Russia in 1786 and the population of northern fur seals, Cailorhinus ursinus, that return there each summer to bear young and to breed. Russia exterminated the native population of sea Oilers, Enhydra lulris, here and nearly subjected the northern fur seal to the same fate before providing proper protection. The northern fur seal was twice more exposed to extinction following the purchase of Alaska and the Pribilof Islands by the United States in 1867. Excessive harvesting was stopped as a result of strict management by the United States of the animals while on land and a treaty between Japan, Russia, Great Britain (for Canada), and the United States that provided needed protection at sea. In 1941, Japan abrogated this treaty which was replaced by a provisional agreement between Canada and the United States that protected the fur seals in the eastern North Pacific Ocean. Japan, the U.S.S.R., Canada, and the United States again insured the survival of these animals with ratification in 1957 of the "Interim Convention on the Conservation of North Pacific Fur Seals," which is still in force. Under the auspices of this Convention, the United States launched an unprecedented manipulation of the resource through controlled removal during 1956-68 of over 300,000 females considered surplus. The biological rationale for the reduction was that production of fewer pups would result in a higher pregnancy rate and increased survival, which would, in turn, produce a sustained annual harvest of 55,000-60,000 males and 10,000-30,000 females. Predicted results did not occur. The herd reduction program instead coincided with the beginning of a decline in the number of males available for harvest. Suspected but unproven causes were changes in the toll normally accounted for by predation, disease, adverse weather, and hookworms. Depletion of the animals' food supply by foreign fishing Heets and the entanglement of fur seals in trawl webbing and other debris discarded at sea became a prime suspect in altering the average annual harvest of males on the Pribilof Islands from 71,500 (1940-56) to 40,000 (1957-59) to 36,000 (1960) to 82,000 (1961) and to 27,347 (1972-81). Thus was born the concept of a research control area for fur seals, which was agreed upon by members of the Convention in 1973 and instituted by the United States on St. George Island beginning in 1974. All commercial harvesting of fur seals was stopped on St. George Island and intensive behavioral studies were begun on the now unharvested population as it responds to the moratorium and attempts to reach its natural ceiling. The results of these and other studies here and on St. Paul Island are expected to eventually permit a comparison between the dynamics of unharvested and harvested populations, which should in turn permit more precise management of fur seals as nations continue to exploit the marine resources of the North Pacific Ocean and Bering Sea. (PDF file contains 32 pages.)

The long road of climate negotiations: From Kyoto to Paris stopping over in Doha

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Passive Q-switched mode locking of double-clading Yb : fiber laser with ion-implanted GaAs

We report the technique of the ion-implanted semi-insulating GaAs wafer used for passive Q-switched mode locking in double-cladding Yb:fiber laser. The wafer was implanted with 400-keV energy, 10(16)/cm(2) dose As+ ions, and was annealed at 600degreesC for 20 min. At the pump power of 5W, we achieved output power of 200mW. The repetition rate of envelope of Q-switched mode locking is 50-kHz with a FWHM envelope of 4mus. The repetition rate of mode locked pulse train was found to be 15-MHz. This is the first report of such a kind of laser to the best of our knowledge.