If the isotope is placed in the molecule at a position directly involved in the mechanism of the reaction, a kinetic isotope effect is expected.
42.
Such isotope effects are exceedingly common, and so it is well known that deuterium substitution will indeed change the binding constants of molecules to protein receptors.
43.
His basic general equation for the hydrogen / deuterium kinetic isotope effects is given below, neglecting tunnelling contributions which can be introduced as a separate factor.
44.
For isotope effects involving elements other than hydrogen, most of these simplifications are not valid, and may depend largely on some of the neglected factors.
45.
Detectable kinetic isotope effects occur only when solutes exchange hydrogen with the solvent or when there is a specific solute-solvent interaction near the reaction site.
46.
Because kinetic isotope effects typically favor transformation of light isotopes ( e . g ., ), heavy isotopes ( 13C ) become enriched in residues.
47.
In the reaction of methyl bromide and cyanide ( shown in the introduction ), the observed methyl carbon kinetic isotope effect indicates an S N 2 mechanism.
48.
For intermediate cases where both steps have comparable rates, the magnitude of the kinetic isotope effect will depend on the ratio of k 3 and k 2.
49.
At the same time there are significantly large 13 C isotope effects, suggesting rate-limiting C C bond breakage, as expected with the aldol mechanism.
50.
In such a case, transformation mechanisms are identifiable from plots of / versus / parent compound data, reflecting different underlying carbon-and nitrogen-isotope effects.
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