Activating water: efficient intramolecular general base catalysis of the hydrolysis of a phosphate triester.
We have identified the first highly efficient intramolecular general base catalysis (IGBC) of a hydrolysis reaction, in a system where two general bases are available to assist the attack of the same nucleophilic water molecule. The suggested mechanism, available uniquely to a phosphate triester model, is readily available in enzyme active sites, and the results suggest a possible solution to the long-unsolved question of how enzymes are able to activate a water molecule to be a highly effective nucleophile.
Kirby
Anthony J
AJ
University Chemical Laboratory, Cambridge CB2 1EW (UK).
Medeiros
Michelle
M
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900 (Brazil).
Oliveira
Pedro S M
PSM
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900 (Brazil).
Brandão
Tiago A S
TAS
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900 (Brazil).
Nome
Faruk
F
Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900 (Brazil).
D002384:Catalysis; D018360:Crystallography, X-Ray; D004789:Enzyme Activation; D004952:Esters; D006868:Hydrolysis; D007700:Kinetics; D008958:Models, Molecular; D010710:Phosphates / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D004952:Esters; D010710:Phosphates; D014867:Water