Search results for "physical chemistry"
showing 10 items of 1199 documents
QM/MM Determination of Kinetic Isotope Effects for COMT-Catalyzed Methyl Transfer Does Not Support Compression Hypothesis
2004
Secondary alpha-D3 kinetic isotope effects calculated by the hybrid AM1/TIP3P/CHARMM method for the reaction of S-adenosylmethionine with catecholate anion in aqueous solution and catalyzed by rat liver catechol O-methyltransferase at 298 K are 0.94 and 0.85, respectively, in good accord with experiment. The large inverse effect for the enzymatic reaction is not due to compression but arises from significant increases in the stretching and bending force constants involving the isotopically substituted atoms of the transferring methyl group as between the reactant complex and the transition structure, larger than for the reaction in water.
A kinetic study of the cracking, isomerization, and disproportionation of n-heptane on a chromium-exchanged Y zeolite
1982
The kinetic rate constants for the cracking, isomerization, and disproportionation of n-heptane over a CrHNaY (32% chromium exchanged) zeolite catalyst at 400, 450, and 470 °C have been calculated. The interaction of n-heptane with a model Lewis acid such as BF3 and progress along the reaction coordinate have been studied by means of molecular orbital calculations. From the kinetic results, i.e., activation energies and frequency factors, and the theoretical calculations, it can be concluded that the controlling step in these reactions is not the formation of the carbonium ion, but the subsequent transformation of this carbonium ion. In addition, the theoretical calculations show that the a…
Reversible switching of the electronic ground state in a pentacoordinated Cu(ii) complex.
2013
International audience; An easy reversible switching of the electronic ground state in a pentacoordinated copper(ii) complex is reported for the first time. The simple protonation of a carboxylic group in a Cu(ii) complex with a {dx(2)-y(2)}(1) electronic configuration leads to a flip of the ground electronic configuration from {dx(2)-y(2)}(1) to {dz(2)}(1) in the metal ion.
Porous thin films obtained by DLI-CVD as mu-PEMFC catalysts to replace platinum
2016
This work is focused on development of growth protocols by direct liquid injection chemical vapor deposition (DLI-CVD) of catalytic porous films which could be used in proton exchange membrane fuel cells (PEMFC). The aim of this work was to reduce or even proscribe platinum in catalysts having large specific surface area i.e. being very porous. Besides, the aim is also to use mainly low cost precursors.Cerium oxide, which is a material widely used as catalyst, has been chosen to partially substitute platinum. Porous CeO2 layers were obtained by the optimization of processing parameters such as deposition temperature or precursors flow rates. Controlled platinum doping of cerium oxide surfac…
Linking Electrostatic Effects and Protein Motions in Enzymatic Catalysis. A Theoretical Analysis of Catechol O-Methyltransferase
2014
The role of protein motions in enzymatic catalysis is the subject of a hot scientific debate. We here propose the use of an explicit solvent coordinate to analyze the impact of environmental motions during the reaction process. The example analyzed here is the reaction catalyzed by catechol O-methyltransferase, a methyl transfer reaction from S-adenosylmethionine (SAM) to the nucleophilic oxygen atom of catecholate. This reaction proceeds from a charged reactant to a neutral product, and then a large electrostatic coupling with the environment could be expected. By means of a two-dimensional free energy surface, we show that a large fraction of the environmental motions needed to attain the…
Re-investigation of the conformational interconversion of the 1,2,3,6,7,8-hexahydropyrene cation radical by EPR, ENDOR and TRIPLE spectroscopy
1985
The conformational interconversion of the 1,2,3,6,7,8-hexahydropyrene cation radical has been re-examined by EPR, ENDOR and TRIPLE spectroscopy, and the Arrhenius plot is presented for a wider temperature range than that used earlier. The EPR spectra were measured from 143 to 369 K and the ENDOR spectra from 143 to 263 K. The thermodynamic constants of the conformational interconversion of the cation radical were determined on the basis of the temperature-dependent spectra. The high-resolution spectra clearly show that there are two overlapping spectra at low temperature, and this is confirmed by simulation.
Nucleation and cavitation in parahydrogen
2012
We have used a density functional approach to investigate thermal homogeneous nucleation and cavitation in parahydrogen. The effect of electrons as seeds of heterogeneous cavitation in liquid parahydrogen is also discussed within the capillary model. (C) 2011 Elsevier B.V. All rights reserved.
Intrinsic Acidity of Surface Sites in Calcium Silicate Hydrates and Its Implication to Their Electrokinetic Properties
2014
Calcium Silicate Hydrates (C–S–H) are the major hydration products of portland cement paste. The accurate description of acid–base reactions at the surface of C–S–H particles is essential for both understanding the ion sorption equilibrium in cement and prediction of mechanical properties of the hardened cement paste. Ab initio molecular dynamics simulations at the density functional level of theory were applied to calculate intrinsic acidity constants (pKa’s) of the relevant ≡SiOH and ≡CaOH2 groups on the C–S–H surfaces using a thermodynamic integration technique. Ion sorption equilibrium in C–S–H was modeled applying ab initio calculated pKa’s in titrating Grand Canonical Monte Carlo simu…
Elaboration of metal / ceramic functionally graded materials by SPS for ballistic protection
2016
The objective is to improve ballistic performance of armors. A perfect armor combines ductility to resistto the impact and high hardness to stop projectile’s fragments. However, such an association of properties is inconsistent witha single material. The solution is to perform a functionally graded material (FGM) with a ductile metal at the back side of thesample and a hard ceramic on the top side. Non-conventional technologies like Spark Plasma Sintering allow joining orsintering all types of materials with different and additional properties. Furthermore, with this technique, high heating ratescan be achieved, limiting grain growth and resulting in a fine microstructure. The goal is to st…
Enhanced quantum sieving of hydrogen isotopes via molecular rearrangement of the adsorbed phase in chabazite
2020
Coadsorption experiments reveal an unexpected increase of the D2/H2 selectivity with loading in pure silica chabazite at 47 K. This effect is correlated with the appearance of a step in the adsorption isotherms of H2 and D2. Grand canonical Monte Carlo simulations show that this phenomenon is related to a molecular rearrangement of the adsorbed phase induced by its strong confinement. In the case of a H2 and D2 mixture, this rearrangement favors the adsorption of D2 having a smaller size due to quantum effects.