title: Hydrogen tunneling in peptidylglycine alpha-hydroxylating monooxygenase.
abstract: The temperature dependence of the primary and secondary intrinsic isotope effects for the C-H bond cleavage catalyzed by peptidylglycine alpha-hydroxylating monooxygenase has been determined. Analysis of the magnitude and Arrhenius behavior of the intrinsic isotope effects provides strong evidence for the use of tunneling as a primary catalytic strategy for this enzyme. Modeling of the isotope effect data allows for a comparison to the hydrogen transfer catalyzed by soybean lipoxygenase in terms of environmental reorganization energy and frequency of the protein vibration that controls the hydrogen transfer.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
authors.forename: Wilson A
authors.initials: WA
authors.lastname: Francisco
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Knapp
authors.forename: Ninian J
authors.initials: NJ
authors.lastname: Blackburn
authors.forename: Judith P
authors.initials: JP
authors.lastname: Klinman
mesh_terms: D003903:Deuterium / Q000737:chemistry / Q000378:metabolism; D005998:Glycine / Q000737:chemistry / Q000378:metabolism; D006859:Hydrogen / Q000737:chemistry* / Q000378:metabolism; D007700:Kinetics; D006899:Mixed Function Oxygenases / Q000737:chemistry* / Q000378:metabolism; D009097:Multienzyme Complexes / Q000737:chemistry* / Q000378:metabolism; D013696:Temperature; D013816:Thermodynamics
chemical_list: D009097:Multienzyme Complexes; D006859:Hydrogen; D003903:Deuterium; D006899:Mixed Function Oxygenases; C035189:peptidylglycine monooxygenase; D005998:Glycine