Catalytic and molecular properties of rabbit liver carboxylesterase acting on 1,8-cineole derivatives.
Rabbit liver carboxylesterase (rCE) was evaluated as the catalyst for the enantioselective hydrolysis of (+/-)-3-endo-acetyloxy-1 ,8-cineole [(+/-)-4], which yields (1S,3S,4R)-(+)-3-acetyloxy-1,8-cineole [(+)-4] and (1R,3R,4S)-(-)-3-hydroxy-1,8-cineole [(-)-3]. Enantioselective asymmetrization of meso-3,5-diacetoxy-1,8-cineol (5) gives (1S,3S,4R,5R)-(-)-3-acetyloxy-5-hydroxy-1,8-cineole (6), with high enantioselectivity. rCE has been chosen to perform both experiments and molecular modeling simulations. Docking simulations combined with molecular dynamics calculations were used to study rCE-catalyzed enantioselective hydrolysis of cineol derivatives. Both compounds were found to bind with their acetyl groups stabilized by hydrogen bond interactions between their oxygen atoms and Ser221.
Instituto de Quimica Orgánica, Facultad de Bioquímica Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, S. M de Tucumán, T4000INI, Argentina.
María H
MH
del Loandos
Ana C
AC
Muro
Margarita B
MB
Villecco
Marcelo F
MF
Masman
Paul G M
PG
Luiten
Sebastian A
SA
Andujar
Fernando D
FD
Suvirec
Ricardo D
RD
Enriz
D000818:Animals; D055162:Biocatalysis; D043182:Carboxylesterase / Q000737:chemistry / Q000378:metabolism*; D003511:Cyclohexanols / Q000737:chemistry*; D000077591:Eucalyptol; D006868:Hydrolysis; D008099:Liver / Q000201:enzymology*; D008958:Models, Molecular; D039821:Monoterpenes / Q000737:chemistry*; D011817:Rabbits; D013237:Stereoisomerism
D003511:Cyclohexanols; D039821:Monoterpenes; D043182:Carboxylesterase; D000077591:Eucalyptol