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  • Wiley-Blackwell  (955)
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  • 1
    Publication Date: 2014-01-31
    Description: [1]  The nitrogen and oxygen isotopic composition of nitrate in ice cores offers unique potential for examining reactive nitrogen oxide (NO x ) budgets and oxidation chemistry of past atmospheres. A low-latitude record is of particular interest given that the dominant natural sources of NO x and production of hydroxyl radical are most prevalent in the Tropics. Any interpretation of nitrate in ice cores, however, must first consider that nitrate in snow is vulnerable to post-depositional loss and isotopic alteration. We report and assess the integrity of nitrate–δ 15 N, –δ 18 O and –Δ 17 O in a 30 m ice core from a high-elevation site in the central Andes. Clear seasonality in δ 15 N, δ 18 O and nitrate concentration exists throughout most of the record and cannot be explained by photolysis or evaporation based on our current understanding of these processes. In contrast, nitrate in the upper ~12 m of the core and in a snowpit shows very different behavior. This may reflect alteration facilitated by recent melting at the surface. The relationships between δ 15 N, δ 18 O, Δ 17 O and concentration in the unaltered sections can be interpreted in terms of mixing of nitrate from discrete sources. Transport effects and an englacial contribution from nitrification cannot be ruled out at this time, but the observed isotopic compositions are consistent with expected signatures of known NO x sources and atmospheric oxidation pathways. Specifically, nitrate deposited during the wet season reflects biogenic soil emissions and hydroxyl/peroxy radical chemistry in the Amazon while dry season deposition reflects a lightning source and ozone chemistry at higher levels in the Troposphere.
    Print ISSN: 0148-0227
    Topics: Geosciences , Physics
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  • 2
    Publication Date: 2017-09-19
    Description: Data collected between 1974 and 2016 from snow pits and core samples from two Peruvian ice fields demonstrate the effect of the recent warming over the tropical Andes, augmented by El Niño, on the preservation of the climate record. As the 0 o C isotherm is approaching the summit of the Quelccaya ice cap in the Andes of southern Peru (5670 masl), the distinctive seasonal δ 18 O oscillations in the fresh snow deposited within each thermal year are attenuated at depth due to melting and percolation through the firn. This has become increasingly pronounced over 43 years. In the Andes of northern Peru, the ice field on the col of Nevado Huascarán (6050 masl) has retained its seasonal δ 18 O variations at depth due to its higher elevation. During the 2015/16 El Niño, snow on Quelccaya and Huascarán was isotopically (δ 18 O) enriched and the net sum of accumulation over the previous year (NSA) was below the mean for non-El Niño years, particularly on Quelccaya (up to 64% below the mean) which was more pronounced than the NSA decrease during the comparable 1982/83 El Niño. Interannual large-scale oceanic and middle to upper level atmospheric temperatures influence δ 18 O in precipitation on both ice fields, although the influences are variably affected by strong El Niño-Southern Oscillation events, especially on Quelccaya. The rate of ice wastage along Quelccaya's margin was dramatically higher during 2015/16 compared with that of the previous 15 years, suggesting that warming from future El Niños may accelerate mass loss on Peruvian glaciers.
    Print ISSN: 0148-0227
    Topics: Geosciences , Physics
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  • 3
    Publication Date: 2013-08-13
    Description: Current interferon-based therapy for hepatitis C virus (HCV) infection is inadequate, prompting a shift towards combinations of direct-acting antivirals (DAA) with the first protease-targeted drugs licensed in 2012. Many compounds are in the pipeline yet primarily target only three viral proteins, namely NS3/4A protease, NS5B polymerase and NS5A. With concerns growing over resistance, broadening the repertoire for DAA targets is a major priority. Here we describe the complete structure of the HCV p7 protein as a monomeric hairpin, solved using a novel combination of chemical shift and NOE based methods. This represents atomic resolution information for a full-length virus-coded ion channel, or “viroporin”, whose essential functions represent a clinically proven class of antiviral target exploited previously for influenza A virus therapy. Specific drug-protein interactions validate an allosteric site on the channel periphery and its relevance is demonstrated by the selection of novel, structurally diverse inhibitory small molecules with nanomolar potency in culture. Hit compounds represent a 10,000-fold improvement over prototypes, suppress rimantadine resistance polymorphisms at sub-micromolar concentrations and show activity against other HCV genotypes. Conclusions : This proof-of-principle that structure-guided design can lead to drug-like molecules affirms p7 as a much needed new target in the burgeoning era of HCV DAA. (H epatology 2013;)
    Print ISSN: 0270-9139
    Electronic ISSN: 1527-3350
    Topics: Medicine
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 9 (1963), S. 116-120 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Enthalpies of components in ideal gas mixtures can be computed from existing data. However the isothermal effects of pressure and composition on partial enthalpies of mixture components have not been completely characterized. An investigation of the application of the Redlich-Kwong equation of state to the calculation of partial enthalpies is reported here. Methods are developed for convenient hand calculations and for computations on the IBM-650.Calculated partial enthalpies are compared with values derived from experimental P-V-T-C data for binary hydrocarbon mixtures. The calculated values agree fairly well with the derived data for pressures up to 2,500 lb./sq. in. abs. Best agreement is generally obtained when the mixture is well above the critical temperature of the more abundant component. No consistent bias was indicated however.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 12 (1966), S. 117-124 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The horizontal rotating cylinder blood oxygenator has been developed to minimize shear, eliminate bubbles, reduce holdup, and provide for rapid change of the controlled temperature of the blood.To aid in the development of this apparatus a detailed mathematical model was formulated. A simplified model was also developed which yielded an analytical expression relating the amount of material transferred between the gas and liquid in the apparatus to operating variables. In developing these models an attempt was made to include a realistic mechanism for oxygen absorption in blood.Preliminary experiments were carried out by absorbing carbon dioxide into distilled water in the horizontal rotating cylinder. These preliminary results were found to be in good agreement with previous theoretical predictions and calculations that indicated that the equipment should be adequate to act as a lung substitute for a dog. When it was employed in this manner during open-heart surgery, insufficient oxygen was transferred to support the dog.It is concluded that the most probable reason for failure of the horizontal cylinder to act satisfactorily as a blood oxygenator is poor mixing in the blood pool.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 30 (1984), S. 496-500 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 31 (1985), S. 1275-1287 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model of the hydrodynamic processes occurring in a periodic cycled plate column is developed and experimentally confirmed. The model is applied to the prediction of the holdup distribution and the investigation of hydrodynamic problems. An effective manifold arrangement is proposed to minimize the uneven liquid draining encountered in previous experimental studies.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 34 (1988), S. 223-228 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The dispersion of emissions from a plume in a cross stream was studied using both experimental and theoretical techniques. Wind tunnel experiments were done for three jet to cross stream velocity ratios: R = 0.5, 1, and 2. The concentration in the plane perpendicular to the cross stream was measured using light scattering and photographic image analysis. The analysis of the negatives revealed the presence of two counterrotating vortices that greatly affected dispersion of smoke in the plume.Convection and random turbulent dispersion were modeled with a statistical convection simulator on a CYBER 205 computer. The input velocities to the convection model were obtained using experimental measurements. The model revealed the effects of the vortices on dispersion, and the concentration distributions across the plume were determined once the vortices had dissipated. The existence of the counterrotating vortices and their effects upon plume dispersion showed that the Gaussian plume model, which is widely used for modeling pollutant dispersion, is inapplicable in the near range of the model stack.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 35 (1989), S. 109-119 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Bimetallic Mo-Fe and Mo-Co sulfide clusters were anchored on Al2O3 and used for CO hydrogenation. In addition to methane, significant amounts of dimethyl ether were produced. The reaction orders obtained from power rate laws for methanation indicated that the surfaces of the catalytic ensembles were not completely saturated by CO, in contrast to the observations for most conventional CO hydrogenation catalysts. A kinetic analysis and parameter estimation was performed to identify the rate-determining step for methanation. A catalytic cycle was postulated that could account not only for the formation of methane and higher hydrocarbons, but also for dimethyl ether as a primary product.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1328-1340 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We present a method for synthesizing chemical process models that combines prior knowledge and artificial neural networks. The inclusion of prior knowledge is investigated as a means of improving the neural network predictions when trained on sparse and noisy process data. Prior knowledge enters the hybrid model as a simple process model and first principle equations. The simple model controls the extrapolation of the hybrid in the regions of input space that lack training data. The first principle equations, such as mass and component balances, enforce equality constraints. The neural network compensates for inaccuracy in the prior model. In addition, inequality constraints are imposed during parameter estimation. For illustration, the approach is applied in predicting cell biomass and secondary metabolite in a fed-batch penicillin fermentation. Our results show that prior knowledge enhances the generalization capabilities of a pure neural network model. The approach is shown to require less data for parameter estimation, produce more accurate and consistent predictions, and provide more reliable extrapolation.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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