ABSTRACT

I. Introduction ...................................................................................................................... 645

II. Instrumentation................................................................................................................. 646

III. Equilibrium Isotope Effects ............................................................................................. 648

IV. Applications...................................................................................................................... 650

A. Glucose Oxidase....................................................................................................... 650

B. Tyrosine Hydroxylase .............................................................................................. 653

C. Soybean Lipoxygenase ............................................................................................ 655

D. Methane Monooxygenase ........................................................................................ 657

E. Cytochrome P-450 ................................................................................................... 658

F. Dopamine b-Monooxygenase and Peptidylglycine

a-Hydroxylating Monooxygenase ........................................................................... 660

G. Copper Amine Oxidases .......................................................................................... 662

V. Overview and Perspectives for the Future ...................................................................... 665

References..................................................................................................................................... 666

With the exception of specialized ecological niches, life on planet Earth is inextricably linked to the

chemistry of molecular oxygen. The range of enzymes that uses O

as cosubstrate is exhaustive and

includes those which activate and transform organic substrates through the direct insertion of one or

both oxygen atoms from O

,

those which bind recyclable cofactors that use O

as a two-electron

sink and generate hydrogen peroxide

and those which interconvert O

among its variously reduced

forms

:

O

O

O

O

H

O

O

OH

þ H

O O

H

O ð24:1Þ

Regarding cellular physiology, the most central of the enzymes in the latter class is cytochrome

C oxidase, the terminal electron acceptor in aerobic cells that couples the four-electron reduction of

O

to water for the generation of the cellular fuel, ATP.