Intramolecular catalysis of phosphodiester hydrolysis by two imidazoles.
Two imidazole groups act together to catalyze the hydrolysis of the phosphodiester bis(2-(1-methyl-1H-imidazolyl)phenyl) phosphate (BMIPP). A full investigation involving searching computational and electrospray ionization (ESI-MS-/MS) and ultra mass spectrometry (LTQ-FT) experiments made possible a choice between two kinetically equivalent mechanisms. The preferred pathway, involving intramolecular nucleophilic catalysis by imidazole, assisted by intramolecular general acid catalysis by the imidazolium group, offers the first simple model for the mechanism used by the extensive phospholipase D superfamily.
Orth
Elisa S
ES
INCT-Catálise, Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, Santa Catarina 88040-900, Brazil.
Brandão
Tiago A S
TA
Souza
Bruno S
BS
Pliego
Josefredo R
JR
Vaz
Boniek G
BG
Eberlin
Marcos N
MN
Kirby
Anthony J
AJ
Nome
Faruk
F
D002021:Buffers; D002384:Catalysis; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007093:Imidazoles / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D009943:Organophosphorus Compounds; D010710:Phosphates / Q000737:chemistry*; D011789:Quantum Theory; D021241:Spectrometry, Mass, Electrospray Ionization; D013816:Thermodynamics
D002021:Buffers; D007093:Imidazoles; D009943:Organophosphorus Compounds; D010710:Phosphates; C527956:bis(2-(1-methyl-1H-imidazolyl)phenyl)phosphate