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 : 001050 ( Main/Curation ); précédent : 001049; suivant : 001051Mechanism 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
Links toward previous steps (curation, corpus...)
- to stream Main, to step Corpus: Pour aller vers cette notice dans l'étape Curation :001050
Links to Exploration step
pubmed:2989288Le document en format XML
<record><TEI><teiHeader><fileDesc><titleStmt><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>
</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>
</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>
</record>
Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Bois/explor/PhanerochaeteV1/Data/Main/Curation
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 001050 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Main/Curation/biblio.hfd -nk 001050 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien |wiki= Bois |area= PhanerochaeteV1 |flux= Main |étape= Curation |type= RBID |clé= pubmed:2989288 |texte= Mechanism of oxidative C alpha-C beta cleavage of a lignin model dimer by Phanerochaete chrysosporium ligninase. Stoichiometry and involvement of free radicals. }}
Pour générer des pages wiki
HfdIndexSelect -h $EXPLOR_AREA/Data/Main/Curation/RBID.i -Sk "pubmed:2989288" \ | HfdSelect -Kh $EXPLOR_AREA/Data/Main/Curation/biblio.hfd \ | NlmPubMed2Wicri -a PhanerochaeteV1
This area was generated with Dilib version V0.6.37. |