Deuterium kinetic isotope effect
WebDeuterium Isotope Effects for Probing Aspects of the Interaction of H–H and C–H Bonds with Transition Metals Introduction. It is well known that the measurement of kinetic deuterium isotope effects (i.e. k H / k D) … WebMay 17, 2016 · One of the most significant impacts of deuteration is manifested by the so-called deuterium kinetic isotope effect (DKIE), where cleavage of a C-2 H bond can be many times slower than for the C-1 ...
Deuterium kinetic isotope effect
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WebFeb 28, 2014 · The initial hydrogen-transfer was recently concluded to be a rate-limiting step in cyclooxygenase catalysis based on the observed intrinsic deuterium kinetic isotope effect values (D k cat). In the present study, we have found that D k cat values of both PGHS-1 and -2 show an unusual increase with temperatures in the range of 288–310 K ... WebAbstract. Cytochrome P450 (P450) enzymes account for ~75% of the metabolism of drugs. Most of the reactions catalyzed by P450s are mixed-function oxidations, and a C-H bond is (usually) broken. The rate-limiting nature of this step can be analyzed using the kinetic isotope effect (KIE) approach.
Webwhen the H-tunneling effect is large, use of deuterium and tritium transfers is of course helpful, although tunneling has frequently and understandably dominated the discussions. A functional form is suggested for the dependence of the deuterium kinetic isotope effect KIE on G° and a different form for the 13C KIE. WebNote that when deuterium is used the kinetic isotope effect (KIE) is referred to as the deuterium isotope effect. A $\ce{\sf{C–H}}$ bond is about 5 kJ/mol weaker than a …
WebRate versus selectivity determining: The measurement of a kinetic isotope effect (KIE) can provide valuable information about the mechanism of a reaction, but care must be taken in the design and interpretation of KIE … http://www.columbia.edu/cu/chemistry/groups/parkin/isotope.html
WebJan 1, 2024 · The concept and theory of the kinetic isotope effect (KIE) are long-established and treated elsewhere in this monograph. This chapter will be restricted to …
WebJan 1, 2024 · The kinetic deuterium isotope effect on the reaction of the side chain labeled with H (k EH) and with D (k ED) is related to the product isotope effect by the … theotagomotoWebIn this work, we have attempted to improve on the in vivo pharmacokinetics of [11C]Cou by using the deuterium kinetic isotope effect (KIE) to slow the MAO-B-mediated oxidation … theotaki asproWebAbstract. Cytochrome P450 (P450) enzymes account for ~75% of the metabolism of drugs. Most of the reactions catalyzed by P450s are mixed-function oxidations, and a C-H bond … theo takWebJul 24, 2024 · Large primary deuterium kinetic isotope effects (1° DKIEs) on enzyme-catalyzed hydride transfer may be observed when the transferred hydride tunnels … theotakuThe theoretical treatment of isotope effects relies heavily on transition state theory, which assumes a single potential energy surface for the reaction, and a barrier between the reactants and the products on this surface, on top of which resides the transition state. The kinetic isotope effect arises largely from the changes to vibrational ground states produced by the isotopic perturbation alo… the otago dailyWebThe hydrogen/deuterium primary kinetic isotope effect provides useful information about the degradation mechanism of OLED host materials. Thus, replacement of labile C–H bonds in the host with C–D bonds increases the device lifetime by a factor of five without loss of efficiency, and replacement with C–C bonds by a factor of 22.5. theotakumarket.comWebFeb 5, 2003 · A previous report of an inverse kinetic isotope effect of 0.76 for C-H reductive coupling in the [Tp]Pt(CH(3))H(2) system is shown to be erroneous. Finally, a computational study provides evidence that the reductive coupling of [Me(2)Si(C(5)Me(4))(2)]W(Ph)H proceeds via the initial formation of a benzene sigma … shubhra ranjan international relations notes