kinetic isotope effect

Thus, the magnitude of the kinetic isotope effect can be used to elucidate the reaction mechanism.

His work on the magnitude of kinetic isotope effects is still the basis of understanding in the field.

As a result, very large kinetic isotope effects are observed that can not be accounted for by differences in zero point energies.

Second, the analysis of C and deuterium kinetic isotope effects points toward the aldol mechanism.

The kinetic isotope effect is trapped in a single molecule within a membrane-based nanoreactor.

This kinetic isotope effect can be used to study reaction mechanisms by analyzing how the differently-massed atom is involved in the process.

This mechanism was suggested from studies investigating kinetic isotope effects in conjunction with competitive inhibition and active site mutagenesis.

Kinetic isotope effect studies have shown that C-H bond cleavage is involved in the rate-determining step.

A stepwise or a largely asynchronous mechanism has been proposed for the catalyzed reaction based on kinetic isotope effect studies.

This assertion has also been supported by the observation of unusually large kinetic isotope effects (KIE).

The kinetic isotope effect leads to a specific distribution of deuterium isotopes in natural products, depending on the route they were synthesized in nature.

His 118-page thesis is entitled "Kinetic Isotope Effects of Thymidine Phosphorylase".

Reaction mechanisms are routinely elucidated using the kinetic isotope effect, e.g. the halogenation of toluene:

This large kinetic isotope effect shows that the C-H (or C-D) bond breaks in the rate-determining step.

This mechanism (figure below) takes into account experimentally determined second order kinetics for the aldehyde and a substantial kinetic isotope effect for the enone alpha-proton.

As a proof of concept orthogonal deprotection is demonstrated in a photochemical transesterification by trimethylsilyldiazomethane utilizing the kinetic isotope effect:

In one study the kinetic isotope effect (KIE) was determined for the gas phase reaction of several alkyl halides with the chlorate ion.

The secondary kinetic isotope effect (SKIE) arises in cases where the isotopic substitution is remote from the bond being broken.

The kinetic isotope effect (KIE) is the ratio of reaction rates of two different isotopically labeled molecules in a chemical reaction.

Utilization of kinetic isotope effects for the concentration of tritium, GM Brown, TJ Meyer et al., 2001.

The Swain equation relates the kinetic isotope effect for the protium/tritium combination with that of the protium/deuterium combination according to:

The HDO may be separated from regular water by distillation or electrolysis and also by various chemical exchange processes, all of which exploit a kinetic isotope effect.

Reactions are known where the deuterated species reacts faster than the undeuterated analogue, and these cases are said to exhibit inverse kinetic isotope effects (IKIE).

The main exception to this is the kinetic isotope effect: due to their larger masses, heavier isotopes tend to react somewhat more slowly than lighter isotopes of the same element.

The kinetic isotope effect is the difference in the rate of a chemical reaction when an atom in one of the reactants is replaced by one of its isotopes.