87861-95-8Relevant academic research and scientific papers
Structure Sensitivity of the Marcus λ for Hydride Transfer between NAD+ Analogues
Kreevoy, Maurice M.,Ostovic, Drazen,Lee, In-Sook Han,Binder, David A.,King, Gary W.
, p. 524 - 530 (2007/10/02)
Thirty-five rate constants, kij, for transfer of hydride between various pyridinium, quinilinium, acridinium, and phenantridinium ions spanning a range of over 10E11 in their equilibrium constants Kij and over 10E6 in kij
Hydride Transfer and Oxyanion Addition Equilibria of NAD+ Analogues
Ostovic, Drazen,Lee, In-Sook Han,Roberts, Roger M. G.,Kreevoy, Maurice M.
, p. 4206 - 4211 (2007/10/02)
Equilibrium constants, K, have been determined for the reduction of 10-methylacridinium ion by 15 N-heterocyclic hydride donors: acridine, quinoline, pyridine, and phenanthridine derivatives.The solvent was a mixture of 2-propanol and water in the ratio 4 : 1 by volume.Reduction potentials have been estimated for the corresponding cations in aqueous solution by assuming that the K's would be the same and accepting -361 mV as the reduction potential of the 3-(aminocarbonyl)-1-benzylpyridinium ion.These reduction potentials span 430 mV.Values of pKR have also been determined for six of the cations in the same solvent.For derivatives of the same ring system, -ΔlogK is approximately equal to ΔpKR, but a 4 log unit discrepancy appears when phenanthridine derivatives are compared with the 9-methylacridinium ion.
Isotope Effects on Hydride Transfer between NAD+ Analogues
Ostovic, Drazen,Roberts, Roger M. G.,Kreevoy, Mourice M.
, p. 7629 - 7631 (2007/10/02)
Primary kinetic hydrogen isotope effects (KIE's) for hydride transfer between NAD+ analogues are between 6 and 4, for reactions with equilibrium constants ranging from 0.7 to 1016.There is no sign of the sharp change in KIE which would signal the change of a rate-limiting step in a multistep mechanism, and other evidence also indicates a one-step mechanism. 2 The secondary KIE produced by changing the hydrogen already attached at the acceptor site from H to D is about 10percent smaller when the transferred atom is D than when it is H.These results, combined with the values of the primary KIE's, strongly suggest some nuclear tunneling in the reaction coordinate.
