Search results for "Kinetic isotope effect"
showing 10 items of 55 documents
Deuterium isotope effect on the induction period of the cerium catalyzed Belousov-Zhabotinsky reaction
2009
Abstract In this work we present results about the deuterium isotopic effect on the global kinetics of a cerium catalyzed Belousov–Zhabotinsky reaction. A nonlinear dependence of the induction period upon the percentage of deuterated reactants was found in batch conditions. In order to understand this result, we investigated two reaction pathways responsible for the length of the induction period, namely: (a) the reaction between the enolic form of the malonic acid with molecular bromine and (b) the oxidation of malonic acid by the Ce(IV) ion. In both cases we obtained a linear dependence of the kinetic constants on the percentage of deuterated reactants. Nevertheless, by inserting the expe…
Synthesis, X-ray crystal structure, NMR characterization and theoretical calculations on [Cp2Ta(η2-H2)(CO)]+, the first thermally stable group 5 dihy…
2001
Protonation of Cp2TaH(CO) (Cp = C5H5, 1a; C5H4But, 1b) by HBF4·Et2O at −78 °C in CH2Cl2 affords [Cp2TaH2(CO)]BF4 (2, 3) as mixtures of 2 isomers. The minor ones (2a, 2b) contain the known trans-dihydride [Cp2TaH2(CO)]+ cations whereas the major ones (3a, 3b) are [Cp2Ta(η2-H2)(CO)]BF4, the first group 5 dihydrogen complexes. The crystal structure of the analogous complex 3a·BArf4 recorded at 120 K confirms the presence of the coordinated dihydrogen ligand, which displays an H–H separation of 1.09(2) A in agreement with distances calculated from NMR data. Protonation of Cp2TaH2(SiMe2Ph) by (Et2O)2 ·HBArf4 does not lead to an analogous silane derivative but to the new dinuclear complex [(Cp2…
Extending Limits of Chlorine Kinetic Isotope Effects
2012
Chlorine kinetic isotope effects exceeding semiclassical limits were observed in enzyme-catalyzed reactions, but their source has not been yet identified. Herein we show that unusually large chlorine kinetic isotope effects are associated with reactions in which chlorine is the central atom that is being passed between two heavy atoms. The origin of these large values is the ratio of imaginary frequencies for light-to-heavy species (the so-called temperature-independent factor).
Pressure measurements of TO-phonon anharmonicity in isotopic ZnS
2004
We have measured the dependence on pressure of the line-widths of the TO and LO Raman phonons of β-ZnS. In order to enhance the phenomena observed, and to eliminate possible effects of isotopic disorder, we have measured a nearly isotopically pure crystal, 68 Zn 32 S. The strongly structured pressure effects observed are interpreted on the basis of anharmonic decay and the corresponding two-phonon density of states.
In situ measurement of elastic properties of PdH , PdD , and PdT
2003
Abstract The Young’s modulus E of palladium hydride PdH x , deuteride PdD x and tritide PdT x were measured for studying the effect of both hydrogen stoichiometry x and isotope nature. A special technique based on optical detection of flexural modes of a palladium cylindrical microcantilever was adapted to in situ measurements to guarantee the sample homogeneity during the hydriding process. A 10% decrease in E was found between pure polycrystalline palladium and hydride phases. The non linear dependence observed with the H content was discussed in terms of lattice expansion, phonons and electronic properties. Sensitivity of the technique enables to distinguish an isotope effect on E .
Computing kinetic isotope effects for chorismate mutase with high accuracy. A new DFT/MM strategy.
2006
A novel procedure has been applied to compute experimentally unobserved intrinsic kinetic isotope effects upon the rearrangement of chorismate to prephenate catalyzed by B. subtilis chorismate mutase. In this modified QM/MM approach, the "low-level" QM description of the quantum region is corrected during the optimization procedure by means of a "high-level" calculation in vacuo, keeping the QM-MM interaction contribution at a quantum "low-level". This allows computation of energies, gradients, and Hessians including the polarization of the QM subsystem and its interaction with the MM environment, both terms calculated using the low-level method at a reasonable computational cost. New infor…
Isotope shift and hyperfine structure of stable platinum isotopes
1987
Isotope shift (IS) and hyperfine structure (hfs) measurements have been performed on seven lines of the platinum I spectrum with interference as well as laser fluorescence spectroscopy. In the latter case a frequency-doubled single-mode cw dye laser was applied. The IS of190Pt with a natural abundance of only 0.01% was determined to beδν 190, 192=−38.65(8) mK in theλ306.47 nm transition. The IS parameters and the effective hfs integrals in the configuration (5d+6s)10 were determined in intermediate coupling by a least squares fit of the IS and hfs data with eigenvectors obtained from the platinum fine structure (fs). The results are compared with theoretical values and yield improvedδ〈r 2〉 …
Isotope effects on the dynamics of a supercooled van der Waals liquid
2000
Deuteron magnetic resonance was used to study three differently isotope-labeled species of the fragile glass-forming liquid ortho-terphenyl. The calorimetric glass transition of the isotope deuterated only at the central phenyl ring is significantly lower than that of the perdeuterated one. It is shown that while the ortho-terphenyl molecule is not as rigid as previously often assumed, its overall reorientation geometry is independent of deuteration. The characteristic jump angles are found to increase with temperature, thus resolving an apparent discrepancy previously noted when comparing typical jump sizes from NMR with other data.
Raman studies of isotope effects in Si and GaAs
1999
Abstract We have measured by Raman scattering changes of the optic phonon energy and line width in Si and GaAs with isotopic composition. The phonon energies of isotopically pure samples show the expected dependence on the average atomic mass in Si and the reduced mass in GaAs, respectively, as well as small anharmonic contributions. In isotopically disordered samples we find frequency shifts of 1.15(20) cm−1 for 28Si0.530Si0.5 and 0.31(20) cm−1 for the TO phonon of natGaAs, induced by mass disorder which also contributes to the line broadening. We give theoretical estimates of these effects.
Role of Solvent on Nonenzymatic Peptide Bond Formation Mechanisms and Kinetic Isotope Effects
2013
Based on the hypothesis that similar mechanisms are involved in the peptide bond formation in aqueous solution and in the ribosome, the aminolysis of esters in aqueous solution has been the subject of numerous studies as the reference reaction for the catalyzed process. The mechanisms proposed in the literature have been explored in the present paper by hybrid QM/MM molecular dynamics simulations. The free energy profiles have been computed with the QM region of the system described at semiempirical AM1 level and by DFT within the M06-2X functional. According to the results, the formation of adduct zwitterion species is a preliminary step required for all possible mechanisms. Then, from dif…