Finding the key transition states and intermediates controlling net reaction rates and selectivity

In this paper Campbell's degree of rate control is extended to introduce the concepts of degree of kinetic rate control, degree of kinetic selectivity control, degree of thermodynamic rate control and degree of thermodynamic selectivity control. It is demonstrated by applying hypothetical but realistic kinetic models of varying complexity that the new methods offers a rigorous framework to analyze the importance of kinetic and thermodynamic parameters i.e. establishing the critical parameters of the kinetic model. The methods are general and can be applied to complex reaction networks with multiple overall reactions not only in heterogeneous catalysis but for all sorts of chemical kinetic models

ANALYSIS OF THE TAKE-OFF PHASE OF REVERSE DIVES PROM 3-M SPRINGBOARD: APPLICATION IN PRACTICAL TRAINING

NI

Hvem er hvem i Klagesangene?

In this article the different speaking voices and personae inLamentations are analysed with the intention of uncovering their dialogicalinteractions and the effect they have on communicating thethemes of the text. It is shown that there are four principal voices inLamentations: the lamenter, Zion, the Man and the community. An essentialelement in the polyphony in Lamentations is the personifi cationof the principal voices. Here it is the persona of Zion who particularlyasserts herself in her role as personifi ed city. She confronts God, whoremains silent in the discourse. The absence of God which is one of themain themes in Lamentations, becomes more obvious in the dynamicinteraction between the lamenter and Zion. The dialogical discoursein Lamentations communicates a many-faceted portrait of God whichresults in a corresponding many-sided theology

Requirements Study for System Implementation of an Atmospheric Laser Propagation Experiment Program, Volume II

Program planning, ground support and airborne equipment for laser space communication syste

STAT1 activation in association with JAK2 exon 12 mutations

La inclusión de la perspectiva de género en la actividad jurisdiccional es una demanda sostenida de los colectivos feministas y de mujeres, dado que las sentencias tienen un poder performativo y envían un mensaje a la sociedad: “[…] tienen un poder individual y colectivo que impactan en la vida de las personas y conforman la identidad del poder judicial como un actor imprescindible en la construcción de un Estado democrático de derecho” (Suprema Corte de Justicia de la Nación, 2013:7). La incorporación de la perspectiva de género viene a garantizar la igualdad de posiciones (Kessler, 2014) entre mujeres y varones como una meta, trascendiendo la mera igualdad de oportunidades que hasta el presente se ha demostrado insuficiente para que las mujeres consigamos una ciudadanía plena. Al momento de incorporar la perspectiva de género en las sentencias, quienes juzgan deben tener presente en primer lugar, el impacto diferenciado de las normas en base al sexo de las personas. En segundo lugar, la interpretación y aplicación de las leyes en relación con (y en base a) estereotipos de género. Si, por ejemplo, quienes imparten justicia no tienen presentes los estereotipos de género vigentes detrás de las violaciones a los derechos humanos de las mujeres, si no los detectan ni cuestionan, entonces los reproducen. Tal como sostiene Scott (1996) el género es una categoría imprescindible para el análisis social. En tercer lugar, al momento del juzgamiento, se deben tener en cuenta las exclusiones legitimadas por la ley por pensar el mundo en términos binarios y androcéntricos; en cuarto lugar, la distribución no equitativa de recursos y poder que opera entre varones y mujeres en el marco de una organización social patriarcal, y, por último, el trato diferenciado por género legitimado por las propias leyes.Eje 3: Tramas violentas y espacios de exclusión.Instituto de Cultura Jurídic

Impact of co-adsorbed oxygen on crotonaldehyde adsorption over gold nanoclusters : a computational study

Crotonaldehyde (2-butenal) adsorption over gold sub-nanometer particles, and the influence of co-adsorbed oxygen, has been systematically investigated by computational methods. Using density functional theory, the adsorption energetics of crotonaldehyde on bare and oxidised gold clusters (Au13, d = 0.8 nm) were determined as a function of oxygen coverage and coordination geometry. At low oxygen coverage, sites are available for which crotonaldehyde adsorption is enhanced relative to bare Au clusters by 10 kJ mol−1. At higher oxygen coverage, crotonaldehyde is forced to adsorb in close proximity to oxygen weakening adsorption by up to 60 kJ mol−1 relative to bare Au. Bonding geometries, density of states plots and Bader analysis, are used to elucidate crotonaldehyde bonding to gold nanoparticles in terms of partial electron transfer from Au to crotonaldehyde, and note that donation to gold from crotonaldehyde also becomes significant following metal oxidation. At high oxygen coverage we find that all molecular adsorption sites have a neighbouring, destabilising, oxygen adatom so that despite enhanced donation, crotonaldehyde adsorption is always weakened by steric interactions. For a larger cluster (Au38, d = 1.1 nm) crotonaldehyde adsorption is destabilized in this way even at a low oxygen coverage. These findings provide a quantitative framework to underpin the experimentally observed influence of oxygen on the selective oxidation of crotyl alcohol to crotonaldehyde over gold and gold–palladium alloys

Impact of co-adsorbed oxygen on crotonaldehyde adsorption over gold nanoclusters : a computational study

Crotonaldehyde (2-butenal) adsorption over gold sub-nanometer particles, and the influence of co-adsorbed oxygen, has been systematically investigated by computational methods. Using density functional theory, the adsorption energetics of crotonaldehyde on bare and oxidised gold clusters (Au13, d = 0.8 nm) were determined as a function of oxygen coverage and coordination geometry. At low oxygen coverage, sites are available for which crotonaldehyde adsorption is enhanced relative to bare Au clusters by 10 kJ mol−1. At higher oxygen coverage, crotonaldehyde is forced to adsorb in close proximity to oxygen weakening adsorption by up to 60 kJ mol−1 relative to bare Au. Bonding geometries, density of states plots and Bader analysis, are used to elucidate crotonaldehyde bonding to gold nanoparticles in terms of partial electron transfer from Au to crotonaldehyde, and note that donation to gold from crotonaldehyde also becomes significant following metal oxidation. At high oxygen coverage we find that all molecular adsorption sites have a neighbouring, destabilising, oxygen adatom so that despite enhanced donation, crotonaldehyde adsorption is always weakened by steric interactions. For a larger cluster (Au38, d = 1.1 nm) crotonaldehyde adsorption is destabilized in this way even at a low oxygen coverage. These findings provide a quantitative framework to underpin the experimentally observed influence of oxygen on the selective oxidation of crotyl alcohol to crotonaldehyde over gold and gold–palladium alloys

Genetic variation at MECOM, TERT, JAK2 and HBS1L-MYB predisposes to myeloproliferative neoplasms

Clonal proliferation in myeloproliferative neoplasms (MPN) is driven by somatic mutations in JAK2, CALR or MPL, but the contribution of inherited factors is poorly characterized. Using a three-stage genome-wide association study of 3,437 MPN cases and 10,083 controls, we identify two SNPs with genome-wide significance in JAK2V617F-negative MPN: rs12339666 (JAK2; meta-analysis P=1.27 × 10−10) and rs2201862 (MECOM; meta-analysis P=1.96 × 10−9). Two additional SNPs, rs2736100 (TERT) and rs9376092 (HBS1L/MYB), achieve genome-wide significance when including JAK2V617F-positive cases. rs9376092 has a stronger effect in JAK2V617F-negative cases with CALR and/or MPL mutations (Breslow–Day P=4.5 × 10−7), whereas in JAK2V617F-positive cases rs9376092 associates with essential thrombocythemia (ET) rather than polycythemia vera (allelic χ2 P=7.3 × 10−7). Reduced MYB expression, previously linked to development of an ET-like disease in model systems, associates with rs9376092 in normal myeloid cells. These findings demonstrate that multiple germline variants predispose to MPN and link constitutional differences in MYB expression to disease phenotype

Does the Constitution Provide More Ballot Access Protection for Presidential Elections Than for U.S. House Elections?

Both the U.S. Constitution and The Federalist Papers suggest that voters ought to have more freedom to vote for the candidate of their choice for the U.S. House of Representatives than they do for the President or the U.S. Senate. Yet, strangely, for the last thirty-three years, the U.S. Supreme Court and lower courts have ruled that the Constitution gives voters more freedom to vote for the candidate of their choice in presidential elections than in congressional elections. Also, state legislatures, which have been writing ballot access laws since 1888, have passed laws that make it easier for minor-party and independent candidates to get on the ballot for President than for the U.S. House. As a result, voters in virtually every state invariably have far more choices on their general election ballots for the President than they do for the House. This Article argues that the right of a voter to vote for someone other than a Democrat or a Republican for the House is just as important as a voter’s right to do so for President, and that courts should grant more ballot access protection to minor-party and independent candidates for the House

Balance between model detail and experimental information in steam methane reforming over a Ni/MgO-SiO2 catalyst

The optimization and full understanding of chemical reactions is aided by the construction of an adequate kinetic model. The development of such a kinetic model remains a challenging task. To tackle this challenge in the most efficient way, an iterative, systematic methodology, originally demonstrated for n-hexane hydroisomerization, is now extended aiming at finding the balance between the envisaged model detail and available information, often originating from time-consuming and expensive experiments. Steam methane reforming on the Ni/MgO-SiO2 case study is used for this purpose, that is, the construction of a kinetic model that embeds a maximum amount of information contained in the dataset. The kinetic model is expanded stepwise from a power law model over a model with reactant adsorption toward a Langmuir-Hinshelwood-Hougen-Watson model. The performance of the initially underparameterized model improved significantly by adding reactant adsorption, yet including product adsorption led to overparameterization rather than enhanced model performance