Kinetic study and intermediates identification of noradrenaline oxidation by tyrosinase. 1984

M Jimenez, and F Garcia-Canovas, and F Garcia-Carmona, and J A Lozano, and J L Iborra

Characterization of intermediates formed in the noradrenaline oxidation by mushroom tyrosinase and sodium periodate has been performed by rapid scanning spectrophotometry and graphical analysis of obtained spectra. In a pH range from 5.0 to 6.0, it has been possible to detect o-noradrenalinequinone-H+ as the first intermediate in these oxidations. The following steps for noradrenaline transformation into noradrenochrome would be: noradrenaline----o-noradrenalinequinone-H+----o- noradrenalinequinone----leukonoradrenochrome----noradreno chrome. It has been also verified that o-noradrenalinequinone-H+ is transformed into noradrenochrome at a constant ratio. The stoichiometry for this converstion followed the equation: 2-noradrenalinequinone-H+----noradrenaline + noradrenochrome. The pathway between noradrenaline and noradrenochrome has been studied as a system of various chemical reactions coupled to an enzymatic reaction. We have denominated this type of mechanism as an enzymatic-chemical-chemical mechanism, (E2CC). Whole rate constants for the implicated chemical steps at different pH and temperature values have been evaluated from measurement of the lag period arising from the accumulation of noradrenochrome that takes place when noradrenaline was oxidized at pH 5-6. The lag period was independent on enzyme concentration, but was increased when pH and/or temperature were increased. Rate constants pH independent for the deprotonation of noradrenalinequinone-H+ into noradrenalinequinone and for the internal cyclization of noradrenalinequinone into leukonoradrenochrome have been obtained. We conclude that this minor pathway of noradrenaline oxidation by tyrosinase follows a scheme similar to that established for L-dopa.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008433 Mathematics The deductive study of shape, quantity, and dependence. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Mathematic
D009638 Norepinephrine Precursor of epinephrine that is secreted by the ADRENAL MEDULLA and is a widespread central and autonomic neurotransmitter. Norepinephrine is the principal transmitter of most postganglionic sympathetic fibers, and of the diffuse projection system in the brain that arises from the LOCUS CERULEUS. It is also found in plants and is used pharmacologically as a sympathomimetic. Levarterenol,Levonorepinephrine,Noradrenaline,Arterenol,Levonor,Levophed,Levophed Bitartrate,Noradrenaline Bitartrate,Noradrénaline tartrate renaudin,Norepinephrin d-Tartrate (1:1),Norepinephrine Bitartrate,Norepinephrine Hydrochloride,Norepinephrine Hydrochloride, (+)-Isomer,Norepinephrine Hydrochloride, (+,-)-Isomer,Norepinephrine d-Tartrate (1:1),Norepinephrine l-Tartrate (1:1),Norepinephrine l-Tartrate (1:1), (+,-)-Isomer,Norepinephrine l-Tartrate (1:1), Monohydrate,Norepinephrine l-Tartrate (1:1), Monohydrate, (+)-Isomer,Norepinephrine l-Tartrate (1:2),Norepinephrine l-Tartrate, (+)-Isomer,Norepinephrine, (+)-Isomer,Norepinephrine, (+,-)-Isomer
D004156 Catechol Oxidase An enzyme of the oxidoreductase class that catalyzes the reaction between catechol and oxygen to yield benzoquinone and water. It is a complex of copper-containing proteins that acts also on a variety of substituted catechols. EC 1.10.3.1. Diphenol Oxidases,Diphenol Oxidase,Polyphenol Oxidase,Polyphenoloxidase,Oxidase, Catechol,Oxidase, Diphenol,Oxidase, Polyphenol,Oxidases, Diphenol
D004837 Epinephrine The active sympathomimetic hormone from the ADRENAL MEDULLA. It stimulates both the alpha- and beta- adrenergic systems, causes systemic VASOCONSTRICTION and gastrointestinal relaxation, stimulates the HEART, and dilates BRONCHI and cerebral vessels. It is used in ASTHMA and CARDIAC FAILURE and to delay absorption of local ANESTHETICS. Adrenaline,4-(1-Hydroxy-2-(methylamino)ethyl)-1,2-benzenediol,Adrenaline Acid Tartrate,Adrenaline Bitartrate,Adrenaline Hydrochloride,Epifrin,Epinephrine Acetate,Epinephrine Bitartrate,Epinephrine Hydrochloride,Epinephrine Hydrogen Tartrate,Epitrate,Lyophrin,Medihaler-Epi,Acetate, Epinephrine
D006863 Hydrogen-Ion Concentration The normality of a solution with respect to HYDROGEN ions; H+. It is related to acidity measurements in most cases by pH pH,Concentration, Hydrogen-Ion,Concentrations, Hydrogen-Ion,Hydrogen Ion Concentration,Hydrogen-Ion Concentrations
D001487 Basidiomycota A phylum of fungi that produce their sexual spores (basidiospores) on the outside of the basidium. It includes forms commonly known as mushrooms, boletes, puffballs, earthstars, stinkhorns, bird's-nest fungi, jelly fungi, bracket or shelf fungi, and rust and smut fungi. Basidiomycetes,Basidiomycete,Basidiomycotas
D014442 Monophenol Monooxygenase An enzyme of the oxidoreductase class that catalyzes the reaction between L-tyrosine, L-dopa, and oxygen to yield L-dopa, dopaquinone, and water. It is a copper protein that acts also on catechols, catalyzing some of the same reactions as CATECHOL OXIDASE. EC 1.14.18.1. Dopa Oxidase,Phenoloxidase,Tyrosinase,Cresolase,Phenol Oxidase,Phenoloxidase A,Phenoloxidase B,Monooxygenase, Monophenol,Oxidase, Dopa,Oxidase, Phenol

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