One-electron reduction of ferrideuteroporphyrin IX and reaction of the oxidized and reduced forms with chlorinated methyl radicals

Journal Article · Mon Jun 30 04:00:00 EDT 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00523a018· OSTI ID:5439812

Brault, D ^[1]; Bizet, C; Morliere, P; Rougee, M; Land, E J; Santus, R; Swallow, A J

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1. Museum National d'Histoire Naturelle, Paris, France

..cap alpha..-hydroxyisopropyl radicals prepared by fast electron irradiation of aqueous solutions containing 2-propanol and acetone were found to reduce monomeric ferrideuteroporphyrin to ferrodeuteroporphyrin with a rate constant of 3.7 x 10/sup 8/ M/sup -1/s/sup -1/. Relaxation of the coordination sphere is found to proceed with a rate constant k greater than or equal to 5 x 10/sup 5/s/sup -1/. Irradiation of such solutions in the added presence of various concentrations of CCl/sub 4/, CHCl/sub 3/, or CH/sub 2/Cl/sub 2/ enabled studies to be made of the reactions of ferri- and ferrodeuteroporphyrin with chlorinated methyl radicals. No reaction of ferrideuteroporphyrin with .CCl/sub 3/ could be detected (k less than or equal to 10/sup 6/ M/sup -1/s/sup -1/). For ferrodeuteroporphyrin it appears that a rapid reaction (k = (2 +- 1) x 10/sup 9/ M/sup -1/s-/sup 1/) gives a complex (DPFe/sup II/-CH/sub 3-n/Cl/sub n/) which undergoes further reaction as shown by transient spectral modifications. These results suggest that ferrous cytochrome P450 is likely to react rapidly with chlorinated radicals. A model for the toxicity and detoxification of CCl/sub 4/ is proposed. 38 references, 6 figures.

• OSTI ID: 5439812
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:3; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ACETONE
ALCOHOLS
AQUEOUS SOLUTIONS
BIOLOGICAL EFFECTS
CARBON TETRACHLORIDE
CARBOXYLIC ACIDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
CHLOROFORM
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
DATA FORMS
DECOMPOSITION
DEUTERIUM COMPOUNDS
DISPERSIONS
DOSE RATES
EXPERIMENTAL DATA
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
IRON COMPLEXES
IRRADIATION
ISOLATED VALUES
KETONES
KINETICS
MIXTURES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PH VALUE
PORPHYRINS
PROPANOLS
PULSED IRRADIATION
QUANTITY RATIO
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
REDUCTION
SOLUTIONS
SPECTRA
TIME DEPENDENCE
TRANSITION ELEMENT COMPLEXES
VISIBLE SPECTRA