Search results for "Reaction step"
showing 10 items of 17 documents
Kinetic and Electrochemical Studies of the Oxidative Addition of Demanding Organic Halides to Pd(0): the Efficiency of Polyphosphane Ligands in Low P…
2013
International audience; Oxidative addition (OA) of organic halides to palladium(0) species is a fundamental reaction step which initiates the C–C bond formation catalytic processes typical of Pd(0)/Pd(II) chemistry. The use of structurally congested polyphosphane ligands in palladium-catalyzed C–C bond formation has generated very high turnover numbers (TONs) in topical reactions such as Heck, Suzuki, Sonogashira couplings, and direct sp2C–H functionalization. Herein, the OA of aryl bromides to Pd(0) complexes stabilized by ferrocenylpolyphosphane ligands L1 (tetraphosphane), L2 (triphosphane), and L3 (diphosphane) is considered. The investigation of kinetic constants for the addition of Ph…
In-line capillary electrophoretic evaluation of the enantioselective metabolism of verapamil by cytochrome P3A4
2013
Abstract In this paper a methodology for the in-line evaluation of enantioselective metabolism by capillary electrophoresis has been developed and applied to the study of verapamil metabolism by cytochrome P3A4. The developed methodology comprises an in-capillary reaction step carried out by electrophoretically mediated microanalysis and a separation step in which highly sulfated β-cyclodextrin with partial filling technique has been employed as chiral selector for verapamil and norverapamil enantiomers resolution, joining the advantages of both methodologies in a unique assay. Kinetic parameters of the enzymatic reaction (Km and Vmax) have been evaluated for both verapamil enantiomers by n…
Synthesis of Tripyreno[2,3,4-abc: 2,3,4-ghi: 2,3,4-mno][18]annulenes
2000
The title compounds were prepared in a multi-step synthesis in which primarily the pyrene building blocks were formed (1,2 11a,b). The final reaction step 11a,b 12a,b consisted of a threefold trans selective cyclocondensation process that generated the central 18-membered ring. Hexyloxy or dodecyloxy sidechains attached on the periphery led to the formation of liquid crystalline phases.
Multiple catenanes based on tetraloop derivatives of calix[4]arenes
2009
Abstract Four novel tetraarylurea calix[4]arenes ( 4a – d ) have been synthesized, substituted by ω-alkenyloxy residues in 3,5-positions of the arylurea residues. The eight alkenyl groups were pairwise connected by olefin metathesis and subsequent hydrogenation. The ring-closure reaction was carried out with heterodimers exclusively formed by 4 with a tetratosylurea calix[4]arene 1 , which serves as a template in this reaction step. The potential trans-cavity bridging is entirely suppressed in this way. Bis- and tetraloop calix[4]arenes cannot form dimers due to overlapping loops. However, they readily form heterodimers with open-chain tetraureas, as long as their urea residues can pass thr…
The mechanism of formamide hydrolysis in water from ab initio calculations and simulations.
2005
The neutral hydrolysis of formamide in water is a suitable reference to quantify the efficiency of proteolytic enzymes. However, experimental data for this reaction has only very recently been obtained and the kinetic constant determined experimentally is significantly higher than that predicted by previous theoretical estimations. In this work, we have investigated in detail the possible mechanisms of this reaction. Several solvent models have been considered that represent a considerable improvement on those used in previous studies. Density functional and ab initio calculations have been carried out on a system which explicitly includes the first solvation shell of the formamide molecule…
Fluoride-induced modulation of ionic transport in asymmetric nanopores functionalized with “caged” fluorescein moieties
2016
[EN] We demonstrate experimentally and theoretically a nanofluidic fluoride sensing device based on a single conical pore functionalized with "caged" fluorescein moieties. The nanopore functionalization is based on an amine-terminated fluorescein whose phenolic hydroxyl groups are protected with tert-butyldiphenylsilyl (TBDPS) moieties. The protected fluorescein (Fcn-TBDPS-NH2) molecules are then immobilized on the nanopore surface via carbodiimide coupling chemistry. Exposure to fluoride ions removes the uncharged TBDPS moieties due to the fluoride-promoted cleavage of the silicon-oxygen bond, leading to the generation of negatively charged groups on the fluorescein moieties immobilized on…
Molecular dynamics simulations of elementary chemical processes in liquid water using combined density functional and molecular mechanics potentials.…
1997
A new approach to carry out molecular dynamics simulations of chemical reactions in solution using combined density functional theory/molecular mechanics potentials is presented. We focus our attention on the analysis of reactive trajectories, dynamic solvent effects and transmission coefficient rather than on the evaluation of free energy which is another important topic that will be examined elsewhere. In a previous paper we have described the generalities of this hybrid molecular dynamics method and it has been employed to investigate low energy barrier proton transfer process in water. The study of processes with activation energies larger than a few kT requires the use of specific tech…
Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
2021
Efficiency of the electrochemical N2 reduction reaction (NRR) to ammonia is seriously limited by the competing hydrogen evolution reaction (HER) but our current atomic-scale insight on the factors controlling HER/NRR competition are unknown. Herein we unveil the elementary mechanism, thermodynamics, and kinetics determining the HER/NRR selectivity on the state-of-the-art NRR electrocatalyst, Ru-N4 using constant potential density functional theory calculations (DFT). The calculations show that NRR and HER intermediates coadsorb on the catalyst where HER is greatly suppressed by the NRR intermediates. The first reaction step leading to either *NNH or *H determines the selectivity towards NRR…
A Lotka-type model for oscillations in surface reactions
1997
In this paper we introduce a reaction model on a lattice which leads to oscillations. The model consists of two monomolecular and one bimolecular reaction step and is related to the Lotka model. Despite the simple evolution rules, the model shows a complex behaviour (i.e. the appearance of oscillations). This offers us the opportunity to test different types of stochastic approximations and compare them with the results of a Monte Carlo simulation. The simulation is performed on a large lattice (L = 1024) in order to take long-range correlations into account. Comparing the results of this simulation with the stochastic approaches shows that only advanced numerical approximations are able to…
Fast synthesis of single-phased 110 K bismuth superconductor by freeze-drying of acetic precursors. Kinetic role of calcium and copper oxides
1993
Abstract Although the usefulness of solution procedures to improve the synthesis of bismuth HTSC has been argued, an adequate control of the procedural variables has allowed us to isolate the 110 K phase as the only superconducting phase after such a short sintering time as 22 h. The precursors used have been freeze-dried powders resulting from acetic solutions containing excess Ca and Cu. TGA-DTA and XRD experiments have been performed to follow the subsequent solid-state reaction processes. The initial formation of a mixed bismuth-lead oxoacetate, as intermediate to (Bi 1− y Pb y ) 2 CuO 4 , and the presence of an excess of Ca 2 CuO 3 in the last reaction step are two of the main factors …