Mechanism of oxidative C alpha-C beta cleavage of a lignin model dimer by Phanerochaete chrysosporium ligninase. Stoichiometry and involvement of free radicals.
Identifieur interne : 001053 ( Main/Exploration ); précédent : 001052; suivant : 001054Mechanism of oxidative C alpha-C beta cleavage of a lignin model dimer by Phanerochaete chrysosporium ligninase. Stoichiometry and involvement of free radicals.
Auteurs : K E Hammel ; M. Tien ; B. Kalyanaraman ; T K KirkSource :
- The Journal of biological chemistry [ 0021-9258 ] ; 1985.
Descripteurs français
- KwdFr :
- Basidiomycota (enzymologie), Benzoïne (analogues et dérivés), Benzoïne (métabolisme), Chromatographie en phase liquide à haute performance (MeSH), Cinétique (MeSH), Lignine (analogues et dérivés), Lignine (métabolisme), Oxygénases (métabolisme), Radicaux libres (MeSH), Spectroscopie de résonance de spin électronique (MeSH), Structures macromoléculaires (MeSH).
- MESH :
- analogues et dérivés : Benzoïne, Lignine.
- enzymologie : Basidiomycota.
- métabolisme : Benzoïne, Lignine, Oxygénases.
- Chromatographie en phase liquide à haute performance, Cinétique, Radicaux libres, Spectroscopie de résonance de spin électronique, Structures macromoléculaires.
English descriptors
- KwdEn :
- Basidiomycota (enzymology), Benzoin (analogs & derivatives), Benzoin (metabolism), Chromatography, High Pressure Liquid (MeSH), Electron Spin Resonance Spectroscopy (MeSH), Free Radicals (MeSH), Kinetics (MeSH), Lignin (analogs & derivatives), Lignin (metabolism), Macromolecular Substances (MeSH), Oxygenases (metabolism).
- MESH :
- chemical , analogs & derivatives : Benzoin, Lignin.
- enzymology : Basidiomycota.
- chemical , metabolism : Benzoin, Lignin, Oxygenases.
- Chromatography, High Pressure Liquid, Electron Spin Resonance Spectroscopy, Free Radicals, Kinetics, Macromolecular Substances.
Abstract
The hemoprotein ligninase of Phanerochaete chrysosporium Burds. catalyzes the oxidative cleavage of lignin model dimers between C alpha and C beta of their propyl side chains. The model dimers hitherto used give multiple products and complex stoichiometries upon enzymatic oxidation. Here we present experiments with a new model dimer, 1-(3,4-dimethoxyphenyl)-2-phenylethanediol (dimethoxyhydrobenzoin, DMHB) which is quantitatively cleaved by ligninase in air to give benzaldehyde and veratraldehyde according to the stoichiometry: 2DMHB + O2----2PhCHO + 2Ph(OMe)2CHO. Catalytic amounts of H2O2 are required for this aerobic reaction. Under anaerobic conditions, ligninase uses H2O2 as the oxidant for cleavage: DMHB + H2O2----PhCHO + Ph(OMe)2CHO. Electron spin resonance experiments done in the presence of spin traps, 2-methyl-2-nitrosopropane or 5,5-dimethyl-1-pyrroline-N-oxide, show that C alpha-C beta cleavage yields alpha-hydroxybenzyl radicals as intermediate products. Under anaerobic conditions, these radicals react further to give the final aldehyde products. In air, O2 adds to the carbon-centered radicals, probably giving alpha-hydroxybenzylperoxyl radicals which fragment to yield superoxide, benzaldehyde, and veratraldehyde. These results lead us to propose a mechanism for C alpha-C beta cleavage in which attack by ligninase and H2O2 on the methoxylated ring of DMHB yields a cation radical, which then cleaves to give either benzaldehyde and an alpha-hydroxy(dimethoxybenzyl) radical or veratraldehyde and an alpha-hydroxybenzyl radical (cf. Kersten, P. J., Tien, M., Kalyanaraman, B., and Kirk, T.K. (1985) J. Biol. Chem. 260, 2609-2612; Snook, M. E., and Hamilton, G. A. (1974) J. Am. Chem. Soc. 96, 860-869). Similar mechanisms probably apply to the enzymatic C alpha-C beta cleavage of natural lignin.
PubMed: 2989288
Affiliations:
Links toward previous steps (curation, corpus...)
Le document en format XML
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<author><name sortKey="Kalyanaraman, B" sort="Kalyanaraman, B" uniqKey="Kalyanaraman B" first="B" last="Kalyanaraman">B. Kalyanaraman</name>
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<term>Benzoin (metabolism)</term>
<term>Chromatography, High Pressure Liquid (MeSH)</term>
<term>Electron Spin Resonance Spectroscopy (MeSH)</term>
<term>Free Radicals (MeSH)</term>
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<term>Chromatographie en phase liquide à haute performance (MeSH)</term>
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<term>Lignine (analogues et dérivés)</term>
<term>Lignine (métabolisme)</term>
<term>Oxygénases (métabolisme)</term>
<term>Radicaux libres (MeSH)</term>
<term>Spectroscopie de résonance de spin électronique (MeSH)</term>
<term>Structures macromoléculaires (MeSH)</term>
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<keywords scheme="MESH" qualifier="analogues et dérivés" xml:lang="fr"><term>Benzoïne</term>
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<term>Spectroscopie de résonance de spin électronique</term>
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<front><div type="abstract" xml:lang="en">The hemoprotein ligninase of Phanerochaete chrysosporium Burds. catalyzes the oxidative cleavage of lignin model dimers between C alpha and C beta of their propyl side chains. The model dimers hitherto used give multiple products and complex stoichiometries upon enzymatic oxidation. Here we present experiments with a new model dimer, 1-(3,4-dimethoxyphenyl)-2-phenylethanediol (dimethoxyhydrobenzoin, DMHB) which is quantitatively cleaved by ligninase in air to give benzaldehyde and veratraldehyde according to the stoichiometry: 2DMHB + O2----2PhCHO + 2Ph(OMe)2CHO. Catalytic amounts of H2O2 are required for this aerobic reaction. Under anaerobic conditions, ligninase uses H2O2 as the oxidant for cleavage: DMHB + H2O2----PhCHO + Ph(OMe)2CHO. Electron spin resonance experiments done in the presence of spin traps, 2-methyl-2-nitrosopropane or 5,5-dimethyl-1-pyrroline-N-oxide, show that C alpha-C beta cleavage yields alpha-hydroxybenzyl radicals as intermediate products. Under anaerobic conditions, these radicals react further to give the final aldehyde products. In air, O2 adds to the carbon-centered radicals, probably giving alpha-hydroxybenzylperoxyl radicals which fragment to yield superoxide, benzaldehyde, and veratraldehyde. These results lead us to propose a mechanism for C alpha-C beta cleavage in which attack by ligninase and H2O2 on the methoxylated ring of DMHB yields a cation radical, which then cleaves to give either benzaldehyde and an alpha-hydroxy(dimethoxybenzyl) radical or veratraldehyde and an alpha-hydroxybenzyl radical (cf. Kersten, P. J., Tien, M., Kalyanaraman, B., and Kirk, T.K. (1985) J. Biol. Chem. 260, 2609-2612; Snook, M. E., and Hamilton, G. A. (1974) J. Am. Chem. Soc. 96, 860-869). Similar mechanisms probably apply to the enzymatic C alpha-C beta cleavage of natural lignin.</div>
</front>
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<Abstract><AbstractText>The hemoprotein ligninase of Phanerochaete chrysosporium Burds. catalyzes the oxidative cleavage of lignin model dimers between C alpha and C beta of their propyl side chains. The model dimers hitherto used give multiple products and complex stoichiometries upon enzymatic oxidation. Here we present experiments with a new model dimer, 1-(3,4-dimethoxyphenyl)-2-phenylethanediol (dimethoxyhydrobenzoin, DMHB) which is quantitatively cleaved by ligninase in air to give benzaldehyde and veratraldehyde according to the stoichiometry: 2DMHB + O2----2PhCHO + 2Ph(OMe)2CHO. Catalytic amounts of H2O2 are required for this aerobic reaction. Under anaerobic conditions, ligninase uses H2O2 as the oxidant for cleavage: DMHB + H2O2----PhCHO + Ph(OMe)2CHO. Electron spin resonance experiments done in the presence of spin traps, 2-methyl-2-nitrosopropane or 5,5-dimethyl-1-pyrroline-N-oxide, show that C alpha-C beta cleavage yields alpha-hydroxybenzyl radicals as intermediate products. Under anaerobic conditions, these radicals react further to give the final aldehyde products. In air, O2 adds to the carbon-centered radicals, probably giving alpha-hydroxybenzylperoxyl radicals which fragment to yield superoxide, benzaldehyde, and veratraldehyde. These results lead us to propose a mechanism for C alpha-C beta cleavage in which attack by ligninase and H2O2 on the methoxylated ring of DMHB yields a cation radical, which then cleaves to give either benzaldehyde and an alpha-hydroxy(dimethoxybenzyl) radical or veratraldehyde and an alpha-hydroxybenzyl radical (cf. Kersten, P. J., Tien, M., Kalyanaraman, B., and Kirk, T.K. (1985) J. Biol. Chem. 260, 2609-2612; Snook, M. E., and Hamilton, G. A. (1974) J. Am. Chem. Soc. 96, 860-869). Similar mechanisms probably apply to the enzymatic C alpha-C beta cleavage of natural lignin.</AbstractText>
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