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:
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Kalyanaraman</name></author><author><name sortKey="Kirk, T K" sort="Kirk, T K" uniqKey="Kirk T" first="T K" last="Kirk">T K Kirk</name></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="1985">1985</date><idno type="RBID">pubmed:2989288</idno><idno type="pmid">2989288</idno><idno type="wicri:Area/Main/Corpus">001050</idno><idno type="wicri:explorRef" wicri:stream="Main" wicri:step="Corpus" wicri:corpus="PubMed">001050</idno><idno type="wicri:Area/Main/Curation">001050</idno><idno type="wicri:explorRef" wicri:stream="Main" wicri:step="Curation">001050</idno><idno type="wicri:Area/Main/Exploration">001050</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Mechanism of oxidative C alpha-C beta cleavage of a lignin model dimer by Phanerochaete chrysosporium ligninase. Stoichiometry and involvement of free radicals.</title><author><name sortKey="Hammel, K E" sort="Hammel, K E" uniqKey="Hammel K" first="K E" last="Hammel">K E Hammel</name></author><author><name sortKey="Tien, M" sort="Tien, M" uniqKey="Tien M" first="M" last="Tien">M. Tien</name></author><author><name sortKey="Kalyanaraman, B" sort="Kalyanaraman, B" uniqKey="Kalyanaraman B" first="B" last="Kalyanaraman">B. Kalyanaraman</name></author><author><name sortKey="Kirk, T K" sort="Kirk, T K" uniqKey="Kirk T" first="T K" last="Kirk">T K Kirk</name></author></analytic><series><title level="j">The Journal of biological chemistry</title><idno type="ISSN">0021-9258</idno><imprint><date when="1985" type="published">1985</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Basidiomycota (enzymology)</term><term>Benzoin (analogs & derivatives)</term><term>Benzoin (metabolism)</term><term>Chromatography, High Pressure Liquid (MeSH)</term><term>Electron Spin Resonance Spectroscopy (MeSH)</term><term>Free Radicals (MeSH)</term><term>Kinetics (MeSH)</term><term>Lignin (analogs & derivatives)</term><term>Lignin (metabolism)</term><term>Macromolecular Substances (MeSH)</term><term>Oxygenases (metabolism)</term></keywords><keywords scheme="KwdFr" xml:lang="fr"><term>Basidiomycota (enzymologie)</term><term>Benzoïne (analogues et dérivés)</term><term>Benzoïne (métabolisme)</term><term>Chromatographie en phase liquide à haute performance (MeSH)</term><term>Cinétique (MeSH)</term><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></keywords><keywords scheme="MESH" type="chemical" qualifier="analogs & derivatives" xml:lang="en"><term>Benzoin</term><term>Lignin</term></keywords><keywords scheme="MESH" qualifier="analogues et dérivés" xml:lang="fr"><term>Benzoïne</term><term>Lignine</term></keywords><keywords scheme="MESH" qualifier="enzymologie" xml:lang="fr"><term>Basidiomycota</term></keywords><keywords scheme="MESH" qualifier="enzymology" xml:lang="en"><term>Basidiomycota</term></keywords><keywords scheme="MESH" type="chemical" qualifier="metabolism" xml:lang="en"><term>Benzoin</term><term>Lignin</term><term>Oxygenases</term></keywords><keywords scheme="MESH" qualifier="métabolisme" xml:lang="fr"><term>Benzoïne</term><term>Lignine</term><term>Oxygénases</term></keywords><keywords scheme="MESH" xml:lang="en"><term>Chromatography, High Pressure Liquid</term><term>Electron Spin Resonance Spectroscopy</term><term>Free Radicals</term><term>Kinetics</term><term>Macromolecular Substances</term></keywords><keywords scheme="MESH" xml:lang="fr"><term>Chromatographie en phase liquide à haute performance</term><term>Cinétique</term><term>Radicaux libres</term><term>Spectroscopie de résonance de spin électronique</term><term>Structures macromoléculaires</term></keywords></textClass></profileDesc></teiHeader><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></TEI><pubmed><MedlineCitation Status="MEDLINE" Owner="NLM"><PMID Version="1">2989288</PMID><DateCompleted><Year>1985</Year><Month>08</Month><Day>16</Day></DateCompleted><DateRevised><Year>2013</Year><Month>11</Month><Day>21</Day></DateRevised><Article PubModel="Print"><Journal><ISSN IssnType="Print">0021-9258</ISSN><JournalIssue CitedMedium="Print"><Volume>260</Volume><Issue>14</Issue><PubDate><Year>1985</Year><Month>Jul</Month><Day>15</Day></PubDate></JournalIssue><Title>The Journal of biological chemistry</Title><ISOAbbreviation>J Biol Chem</ISOAbbreviation></Journal><ArticleTitle>Mechanism of oxidative C alpha-C beta cleavage of a lignin model dimer by Phanerochaete chrysosporium ligninase. Stoichiometry and involvement of free radicals.</ArticleTitle><Pagination><MedlinePgn>8348-53</MedlinePgn></Pagination><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></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Hammel</LastName><ForeName>K E</ForeName><Initials>KE</Initials></Author><Author ValidYN="Y"><LastName>Tien</LastName><ForeName>M</ForeName><Initials>M</Initials></Author><Author ValidYN="Y"><LastName>Kalyanaraman</LastName><ForeName>B</ForeName><Initials>B</Initials></Author><Author ValidYN="Y"><LastName>Kirk</LastName><ForeName>T K</ForeName><Initials>TK</Initials></Author></AuthorList><Language>eng</Language><GrantList CompleteYN="Y"><Grant><GrantID>GM-29035</GrantID><Acronym>GM</Acronym><Agency>NIGMS NIH HHS</Agency><Country>United States</Country></Grant><Grant><GrantID>RR-01008</GrantID><Acronym>RR</Acronym><Agency>NCRR NIH HHS</Agency><Country>United States</Country></Grant></GrantList><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType><PublicationType UI="D013486">Research Support, U.S. Gov't, Non-P.H.S.</PublicationType><PublicationType UI="D013487">Research Support, U.S. Gov't, P.H.S.</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>J Biol Chem</MedlineTA><NlmUniqueID>2985121R</NlmUniqueID><ISSNLinking>0021-9258</ISSNLinking></MedlineJournalInfo><ChemicalList><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance UI="D005609">Free Radicals</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance UI="D046911">Macromolecular Substances</NameOfSubstance></Chemical><Chemical><RegistryNumber>9005-53-2</RegistryNumber><NameOfSubstance UI="D008031">Lignin</NameOfSubstance></Chemical><Chemical><RegistryNumber>98094-77-0</RegistryNumber><NameOfSubstance UI="C046020">1-(3,4-dimethoxyphenyl)-2-phenylethanediol</NameOfSubstance></Chemical><Chemical><RegistryNumber>EC 1.13.-</RegistryNumber><NameOfSubstance UI="D010105">Oxygenases</NameOfSubstance></Chemical><Chemical><RegistryNumber>EC 1.14.99.-</RegistryNumber><NameOfSubstance UI="C044391">ligninase</NameOfSubstance></Chemical><Chemical><RegistryNumber>L7J6A1NE81</RegistryNumber><NameOfSubstance UI="D001573">Benzoin</NameOfSubstance></Chemical></ChemicalList><CitationSubset>IM</CitationSubset><MeshHeadingList><MeshHeading><DescriptorName UI="D001487" MajorTopicYN="N">Basidiomycota</DescriptorName><QualifierName UI="Q000201" MajorTopicYN="Y">enzymology</QualifierName></MeshHeading><MeshHeading><DescriptorName UI="D001573" MajorTopicYN="N">Benzoin</DescriptorName><QualifierName UI="Q000031" MajorTopicYN="N">analogs & derivatives</QualifierName><QualifierName UI="Q000378" MajorTopicYN="N">metabolism</QualifierName></MeshHeading><MeshHeading><DescriptorName UI="D002851" MajorTopicYN="N">Chromatography, High Pressure Liquid</DescriptorName></MeshHeading><MeshHeading><DescriptorName UI="D004578" MajorTopicYN="N">Electron Spin Resonance Spectroscopy</DescriptorName></MeshHeading><MeshHeading><DescriptorName UI="D005609" MajorTopicYN="N">Free Radicals</DescriptorName></MeshHeading><MeshHeading><DescriptorName UI="D007700" MajorTopicYN="N">Kinetics</DescriptorName></MeshHeading><MeshHeading><DescriptorName UI="D008031" MajorTopicYN="N">Lignin</DescriptorName><QualifierName UI="Q000031" MajorTopicYN="N">analogs & derivatives</QualifierName><QualifierName UI="Q000378" MajorTopicYN="Y">metabolism</QualifierName></MeshHeading><MeshHeading><DescriptorName UI="D046911" MajorTopicYN="N">Macromolecular Substances</DescriptorName></MeshHeading><MeshHeading><DescriptorName UI="D010105" MajorTopicYN="N">Oxygenases</DescriptorName><QualifierName UI="Q000378" MajorTopicYN="Y">metabolism</QualifierName></MeshHeading></MeshHeadingList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="pubmed"><Year>1985</Year><Month>7</Month><Day>15</Day></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>1985</Year><Month>7</Month><Day>15</Day><Hour>0</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>1985</Year><Month>7</Month><Day>15</Day><Hour>0</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">2989288</ArticleId></ArticleIdList></PubmedData></pubmed><affiliations><list></list><tree><noCountry><name sortKey="Hammel, K E" sort="Hammel, K E" uniqKey="Hammel K" first="K E" last="Hammel">K E Hammel</name><name sortKey="Kalyanaraman, B" sort="Kalyanaraman, B" uniqKey="Kalyanaraman B" first="B" last="Kalyanaraman">B. Kalyanaraman</name><name sortKey="Kirk, T K" sort="Kirk, T K" uniqKey="Kirk T" first="T K" last="Kirk">T K Kirk</name><name sortKey="Tien, M" sort="Tien, M" uniqKey="Tien M" first="M" last="Tien">M. Tien</name></noCountry></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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