Haloperoxidase reactions catalyzed by lignin peroxidase, an extracellular enzyme from the basidiomycete Phanerochaete chrysosporium
Lignin peroxidase (ligninase, LiP) an H/sub 2/O/sub 2/-dependent lignin-degrading heme enzyme from the basidiomycetous fungus Phanerochaete chrysosporium, catalyzes the oxidation of a variety of lignin model compounds. In this paper the authors examine the haloperoxidase reactions of LiP. In the presence of H/sub 2/O/sub 2/, homogeneous LiP oxidized bromide and iodide but not chloride. Halide oxidation was measured by the halogenation of monochlorodimedone (MCD) and a variety of other aromatic compounds. Bromination of MCD produced monochloromonobromodimedone. The pH optimum for the bromination of MCD was 3.5. Both chloride and fluoride inhibited the bromination reaction. LiP binds halides to produce characteristic optical difference spectra. From these spectra apparent dissociation constants for fluoride and chloride were determined to be 0.3 and 20 mM, respectively. Incubation of LiP with bromide and H/sub 2/O/sub 2/ in the absence of organic substrate led to the bleaching of the heme as measured by a decrease in Soret maximum. LiP brominated a variety of aromatic substrates including 3,4-dimethoxybenzyl alcohol (veratryl alcohol) to produce 6-bromoveratryl alcohol (VII). LiP hydrobrominated cinnamic acid (IV) to produce 2-bromo-3-hydroxy-3-phenylpropionic acid (XII). In an analogous reaction LiP hydrobrominated 1-(4-ethoxy-3-methoxyphenyl)propene (II) to produce 2-bromo-1-(4-ethoxy-3-methoxyphenyl)-1-hydroxypropane (XIII). Finally, with 3,4-dimethoxycinnamic acid as the substrate, three bromination products were identified: trans-2-bromo-1-(3,4-dimethoxyphenyl)ethylene (IX), 2,2-dibromo-1-(3,4-dimethoxyphenyl)-1-hydroxyethane (X), and 2-bromo-3-(3,4-dimethoxyphenyl)-3-hydroxypropionic acid (XI).
- Research Organization:
- Oregon Graduate Center, Beaverton
- DOE Contract Number:
- FG06-86ER13550
- OSTI ID:
- 5879517
- Journal Information:
- Biochemistry; (United States), Vol. 26:16
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
PEROXIDASES
BIOCHEMICAL REACTION KINETICS
PHANEROCHAETE
BIOCHEMISTRY
BROMIDES
BROMINATION
CHLORIDES
LIGNIN
PH VALUE
BROMINE COMPOUNDS
CARBOHYDRATES
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE COMPOUNDS
ENZYMES
FUNGI
HALIDES
HALOGEN COMPOUNDS
HALOGENATION
KINETICS
ORGANIC COMPOUNDS
OXIDOREDUCTASES
PLANTS
POLYSACCHARIDES
REACTION KINETICS
SACCHARIDES
550200* - Biochemistry