Projects per year
DFT calculations for methyl cation complexed within a constrained cage of water molecules permit the controlled manipulation of the “axial” donor/acceptor distance and the “equatorial” distance to hydrogen-bond acceptors. The kinetic isotope effect k(CH3)/k(CT3) for methyl transfer within a cage with a short axial distance becomes less inverse for shorter equatorial C⋅⋅⋅O distances: a decrease of 0.5 Å results in a 3 % increase at 298 K. Kinetic isotope effects in AdoMet-dependent methyltransferases may be m∧odulated by CH⋅⋅⋅O hydrogen bonding, and factors other than axial compression may contribute, at least partially, to recently reported isotope-effect variations for catechol-O-methyltransferase and its mutant structures.
|Early online date||28 Jan 2016|
|Publication status||Published - 24 Feb 2016|
FingerprintDive into the research topics of 'Influence of equatorial CH⋅⋅⋅O interactions on secondary kinetic isotope effects for methyl transfer'. Together they form a unique fingerprint.
- 1 Finished
A COMPUTATIONAL FRAMEWORK FOR INTERPRETATION OF KINETIC ISOT OPE EFFECTS FOR ORGANIC REACTIONS IN SOLUTION
Engineering and Physical Sciences Research Council
1/12/06 → 30/11/09
Project: Research council
High Performance Computing (HPC) Facility
Steven Chapman (Manager)University of Bath