935 resultados para kinetic resolution of activated cyclopropanes


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In the first part of the study, an RF coupled, atmospheric pressure, laminar plasma jet of argon was investigated for thermodynamic equilibrium and some rate processes.

Improved values of transition probabilities for 17 lines of argon I were developed from known values for 7 lines. The effect of inhomogeneity of the source was pointed out.

The temperatures, T, and the electron densities, ne , were determined spectroscopically from the population densities of the higher excited states assuming the Saha-Boltzmann relationship to be valid for these states. The axial velocities, vz, were measured by tracing the paths of particles of boron nitride using a three-dimentional mapping technique. The above quantities varied in the following ranges: 1012 ˂ ne ˂ 1015 particles/cm3, 3500 ˂ T ˂ 11000 °K, and 200 ˂ vz ˂ 1200 cm/sec.

The absence of excitation equilibrium for the lower excitation population including the ground state under certain conditions of T and ne was established and the departure from equilibrium was examined quantitatively. The ground state was shown to be highly underpopulated for the decaying plasma.

Rates of recombination between electrons and ions were obtained by solving the steady-state equation of continuity for electrons. The observed rates were consistent with a dissociative-molecular ion mechanism with a steady-state assumption for the molecular ions.

In the second part of the study, decomposition of NO was studied in the plasma at lower temperatures. The mole fractions of NO denoted by xNO were determined gas-chromatographically and varied between 0.0012 ˂ xNO ˂ 0.0055. The temperatures were measured pyrometrically and varied between 1300 ˂ T ˂ 1750°K. The observed rates of decomposition were orders of magnitude greater than those obtained by the previous workers under purely thermal reaction conditions. The overall activation energy was about 9 kcal/g mol which was considerably lower than the value under thermal conditions. The effect of excess nitrogen was to reduce the rate of decomposition of NO and to increase the order of the reaction with respect to NO from 1.33 to 1.85. The observed rates were consistent with a chain mechanism in which atomic nitrogen and oxygen act as chain carriers. The increased rates of decomposition and the reduced activation energy in the presence of the plasma could be explained on the basis of the observed large amount of atomic nitrogen which was probably formed as the result of reactions between excited atoms and ions of argon and the molecular nitrogen.

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Sediments in Santa Barbara Basin contain microfossil and sedimentological information that allows reconstruction of major features of the California Current such as water temperature, strength of upwelling, and productivity. ... Until now, investigations of Santa Barbara Basin sediments have utilized analytical techniques that could not resolve seasonal laminae, permitting annual resolution of variations in sediment composition and structure only. ... Based on a successful technique for preparation of epoxy-embedded and highly polished thin-sections that permit economical optical and electron microscope evaluation of laminated sequences, it is our long-term goal to reconstruct, with unprecedented detail, the history of sedimentation processes in the Santa Barbara Basin by developing ultra-high-resolution time series of biotic and detrital proxies.

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A hemorrhagic proteinase, jerdohagin, was purified from Trimeresurus jerdonii venom by gel filtration and ion-exchange chromatographies. It was a single chain polypeptide with an apparent molecular weight of 96 kDa as estimated by SDS-PAGE under the non-reducing and reducing conditions. Internal peptide sequencing indicated that it consisted of metalloproteinase, disintegrin-like and cysteine-rich domains and belonged to the class III snake venom metalloproteinases (class P-III SVMPs). Like other typical metalloproteinases, hemorrhagic activities of jerdohagin were completely inhibited by EDTA, but not by PMSF. Jerdohagin preferentially degraded a-chain of human fibrinogen. Interestingly, jerdohagin did not activate human prothrombin, whereas it cleaved human prothrombin and fragment F1 of activated human prothrombin. (C) 2004 Elsevier Ltd. All rights reserved.

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Background: Despite the small number of ursid species, bear phylogeny has long been a focus of study due to their conservation value, as all bear genera have been classified as endangered at either the species or subspecies level. The Ursidae family repre

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Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.

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Microcystins (MCs) are a family of related cyclic hepatotoxic heptapeptides, of which more than 70 types have been identified. The chemically unique nature of the C20 beta-amino acid, (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca4,6-dienoic acid (Adda), portion of the MCs has been exploited to develop a strategy to analyze the entirety. Oxidation of MCs causes the cleavage of MC Adda to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB). In the present study, we investigated the kinetics of MMPB produced by oxidation of the most-often-studied MC variant, MC-LR (L = leucine, R = arginine), with permanganate-periodate. This investigation allowed insight regarding the influence of the reaction conditions (concentration of the reactants, temperature, and pH) on the conversion rate. The results indicated that the reaction was second order overall and first order with respect to both permanganate and MC-LR. The second-order rate constant ranged from 0.66 to 1.35 M/s at temperatures from 10 to 30 degrees C, and the activation energy was 24.44 kJ/mol. The rates of MMPB production can be accelerated through increasing reaction temperature and oxidant concentration, and sufficient periodate is necessary for the formation of MMPB. The initial reaction rate under alkaline and neutral conditions is higher than that under acidic conditions, but the former decreases faster than the latter except under weakly acidic conditions. These results provided new insight concerning selection of the permanganate-periodate concentration, pH, and temperature needed for the oxidation of MCs with a high and stable yield of MMPB.

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In order to improve algal biofuel production on a commercial-scale, an understanding of algal growth and fuel molecule accumulation is essential. A mathematical model is presented that describes biomass growth and storage molecule (TAG lipid and starch) accumulation in the freshwater microalga Chlorella vulgaris, under mixotrophic and autotrophic conditions. Biomass growth was formulated based on the Droop model, while the storage molecule production was calculated based on the carbon balance within the algal cells incorporating carbon fixation via photosynthesis, organic carbon uptake and functional biomass growth. The model was validated with experimental growth data of C. vulgaris and was found to fit the data well. Sensitivity analysis showed that the model performance was highly sensitive to variations in parameters associated with nutrient factors, photosynthesis and light intensity. The maximum productivity and biomass concentration were achieved under mixotrophic nitrogen sufficient conditions, while the maximum storage content was obtained under mixotrophic nitrogen deficient conditions.

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In order to improve algal biofuel production on a commercial-scale, an understanding of algal growth and fuel molecule accumulation is essential. A mathematical model is presented that describes biomass growth and storage molecule (TAG lipid and starch) accumulation in the freshwater microalga Chlorella vulgaris, under mixotrophic and autotrophic conditions. Biomass growth was formulated based on the Droop model, while the storage molecule production was calculated based on the carbon balance within the algal cells incorporating carbon fixation via photosynthesis, organic carbon uptake and functional biomass growth. The model was validated with experimental growth data of C. vulgaris and was found to fit the data well. Sensitivity analysis showed that the model performance was highly sensitive to variations in parameters associated with nutrient factors, photosynthesis and light intensity. The maximum productivity and biomass concentration were achieved under mixotrophic nitrogen sufficient conditions, while the maximum storage content was obtained under mixotrophic nitrogen deficient conditions. © 2014 Elsevier Ltd.

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Seasonal variation of the kinetic parameters of total alkaline phosphatase activity (APA) was studied in a shallow Chinese freshwater lake (Donghu Lake). At the three experimental stations the values of V-max of APA were higher and the negative correlation between orthophosphate and the total APA specific activity (V-max/Chl.) was stronger during summer (from June to September) P depletion. At the same time, the values of Michaelis constant (K-m) of APA at the three stations decreased. Phytoplankton seem to compensate for their phosphorus deficiency not only by an increase in enzyme production but also by an improved ability to use low substrate concentrations. (C) 1997 Elsevier Science Ltd.

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The kinetics of MOCVD GaInAsSb and AlGaAsSb was studied by the growth rate as a function of growth temperature and partial pressure of III and V MO species. The diffusion theory was used to explain the mass transport processes in MOCVD III-V quaternary antimonides. On the basis of the discussion about their growth kinetics and epilayer properties, the good quality multi-epilayers of these two quaternary antimonides and their photodetectors and arrays with wavelength of 1.8 similar to 2.3 mu m and detectivities of D* > 10(9) cm Hz(1/2) W-1 were obtained.