Singlet-oxygen reactions sensitized on solid surfaces of lignin or titanium dioxide: Product studies from hindered secondary amines and from lipid peroxidation
Product analyses and kinetic methods were used to determine the role of singlet oxygen in lignin-catalyzed oxidations of organic substrates. Method A used the ESR analysis of nitroxide radicals formed by singlet oxygen (Type II) on 2,2,6,6-tetramethylpiperidine, 1 , or tetramethylpiperidone, 2 . Met...
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| Veröffentlicht in: | Canadian journal of chemistry 2003-06, Vol.81 (6), p.457-467 |
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| creator | Barclay, L RC Basque, M -C Vinqvist, M R |
| description | Product analyses and kinetic methods were used to determine the role of singlet oxygen in lignin-catalyzed oxidations of organic substrates. Method
A
used the ESR analysis of nitroxide radicals formed by singlet oxygen (Type II) on 2,2,6,6-tetramethylpiperidine,
1
, or tetramethylpiperidone,
2
. Method
B
used HPLC analysis of the 9- and 13-linoleate chain hydroperoxides formed on oxidation of methyl linoleate to distinguish free-radical peroxidation (Type I) from singlet-oxygen oxidation (Type II) on the basis of different cis,trans (kinetic) to trans,trans (thermodynamic) product ratios. Applications of method
A
to solid dispersions of lignin or titanium dioxide (TiO
2
, a known singlet-oxygen sensitizer) indicated singlet-oxygen reactions. In addition to the nitroxide triplet, irradiation of lignin produces a persistent broad signal in the solid attributed to phenoxyl radicals. Benzophenone and 3,5-di-tert-butyl-ortho-benzoquinone,
5
, coated on silica gel were used as models to compare the effects of irradiating such compounds on the products and kinetics of methyl linoleate oxidation. Benzophenone acted as an initiator, giving free-radical peroxidation, whereas
5
or lignin coated with methyl linoleate acted as singlet-oxygen sensitizers, according to both product studies (method
B
) and the kinetic order in oxygen consumption during UV photolysis. Photolysis of phase-separated sensitizer (TiO
2
or lignin) and substrate (methyl linoleate) resulted in typical singlet-oxygen products. These results indicate that singlet oxygen plays a significant role in the photo-yellowing of high-lignin-content wood pulps.
Key words: lignin, singlet oxygen, mechanism, peroxidation, products. |
| doi_str_mv | 10.1139/v02-199 |
| format | Article |
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A
used the ESR analysis of nitroxide radicals formed by singlet oxygen (Type II) on 2,2,6,6-tetramethylpiperidine,
1
, or tetramethylpiperidone,
2
. Method
B
used HPLC analysis of the 9- and 13-linoleate chain hydroperoxides formed on oxidation of methyl linoleate to distinguish free-radical peroxidation (Type I) from singlet-oxygen oxidation (Type II) on the basis of different cis,trans (kinetic) to trans,trans (thermodynamic) product ratios. Applications of method
A
to solid dispersions of lignin or titanium dioxide (TiO
2
, a known singlet-oxygen sensitizer) indicated singlet-oxygen reactions. In addition to the nitroxide triplet, irradiation of lignin produces a persistent broad signal in the solid attributed to phenoxyl radicals. Benzophenone and 3,5-di-tert-butyl-ortho-benzoquinone,
5
, coated on silica gel were used as models to compare the effects of irradiating such compounds on the products and kinetics of methyl linoleate oxidation. Benzophenone acted as an initiator, giving free-radical peroxidation, whereas
5
or lignin coated with methyl linoleate acted as singlet-oxygen sensitizers, according to both product studies (method
B
) and the kinetic order in oxygen consumption during UV photolysis. Photolysis of phase-separated sensitizer (TiO
2
or lignin) and substrate (methyl linoleate) resulted in typical singlet-oxygen products. These results indicate that singlet oxygen plays a significant role in the photo-yellowing of high-lignin-content wood pulps.
Key words: lignin, singlet oxygen, mechanism, peroxidation, products.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v02-199</identifier><identifier>CODEN: CJCHAG</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><subject>Amines ; Chemical reactions ; Irradiation ; Kinetics ; Light intensity ; Lignin ; Lipid peroxidation ; Liquid chromatography ; Organic compounds ; Oxidation ; Oxygen ; Oxygen consumption ; Peroxidation ; Peroxides ; Photochemistry ; Photolysis ; Photooxidation ; Pulp bleaching ; Silica ; Substrates ; Titanium dioxide ; Titanium oxides</subject><ispartof>Canadian journal of chemistry, 2003-06, Vol.81 (6), p.457-467</ispartof><rights>Copyright National Research Council of Canada Jun 2003</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c316t-764ee0b11b30a7c51df729c4ead36cb3c1f933a649291bdf1b25cb7c6d311d1d3</citedby><cites>FETCH-LOGICAL-c316t-764ee0b11b30a7c51df729c4ead36cb3c1f933a649291bdf1b25cb7c6d311d1d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27923,27924</link.rule.ids></links><search><creatorcontrib>Barclay, L RC</creatorcontrib><creatorcontrib>Basque, M -C</creatorcontrib><creatorcontrib>Vinqvist, M R</creatorcontrib><title>Singlet-oxygen reactions sensitized on solid surfaces of lignin or titanium dioxide: Product studies from hindered secondary amines and from lipid peroxidation</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>Product analyses and kinetic methods were used to determine the role of singlet oxygen in lignin-catalyzed oxidations of organic substrates. Method
A
used the ESR analysis of nitroxide radicals formed by singlet oxygen (Type II) on 2,2,6,6-tetramethylpiperidine,
1
, or tetramethylpiperidone,
2
. Method
B
used HPLC analysis of the 9- and 13-linoleate chain hydroperoxides formed on oxidation of methyl linoleate to distinguish free-radical peroxidation (Type I) from singlet-oxygen oxidation (Type II) on the basis of different cis,trans (kinetic) to trans,trans (thermodynamic) product ratios. Applications of method
A
to solid dispersions of lignin or titanium dioxide (TiO
2
, a known singlet-oxygen sensitizer) indicated singlet-oxygen reactions. In addition to the nitroxide triplet, irradiation of lignin produces a persistent broad signal in the solid attributed to phenoxyl radicals. Benzophenone and 3,5-di-tert-butyl-ortho-benzoquinone,
5
, coated on silica gel were used as models to compare the effects of irradiating such compounds on the products and kinetics of methyl linoleate oxidation. Benzophenone acted as an initiator, giving free-radical peroxidation, whereas
5
or lignin coated with methyl linoleate acted as singlet-oxygen sensitizers, according to both product studies (method
B
) and the kinetic order in oxygen consumption during UV photolysis. Photolysis of phase-separated sensitizer (TiO
2
or lignin) and substrate (methyl linoleate) resulted in typical singlet-oxygen products. These results indicate that singlet oxygen plays a significant role in the photo-yellowing of high-lignin-content wood pulps.
Key words: lignin, singlet oxygen, mechanism, peroxidation, products.</description><subject>Amines</subject><subject>Chemical reactions</subject><subject>Irradiation</subject><subject>Kinetics</subject><subject>Light intensity</subject><subject>Lignin</subject><subject>Lipid peroxidation</subject><subject>Liquid chromatography</subject><subject>Organic compounds</subject><subject>Oxidation</subject><subject>Oxygen</subject><subject>Oxygen consumption</subject><subject>Peroxidation</subject><subject>Peroxides</subject><subject>Photochemistry</subject><subject>Photolysis</subject><subject>Photooxidation</subject><subject>Pulp bleaching</subject><subject>Silica</subject><subject>Substrates</subject><subject>Titanium dioxide</subject><subject>Titanium oxides</subject><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><sourceid>8G5</sourceid><sourceid>ABUWG</sourceid><sourceid>AFKRA</sourceid><sourceid>AZQEC</sourceid><sourceid>BENPR</sourceid><sourceid>CCPQU</sourceid><sourceid>DWQXO</sourceid><sourceid>GNUQQ</sourceid><sourceid>GUQSH</sourceid><sourceid>M2O</sourceid><recordid>eNp10N9KwzAUBvAgCs4pvkLwQkGo5jRdu3on4j8YKKjXJU1OZqRLapLK9GV8VTM2vBC8CiE_vpPzEXII7AyA1-cfLM-grrfICIopy3hewzYZMcamWcGKfJfshfCWrhXLJyPy_WTsvMOYueXnHC31KGQ0zgYa0AYTzRcq6iwNrjOKhsFrITFQp2ln5tZY6jyNJgprhgVVxi2Nwgv66J0aZKQhDsokrr1b0FdjFfoUF1A6q4T_pGJhbHoWVq1JZ_o0pUe_yhGrf-yTHS26gAebc0xebq6fr-6y2cPt_dXlLJMcyphVZYHIWoCWM1HJCShd5bUsUCheypZL0DXnoizqVEerNLT5RLaVLBUHUKD4mBytc3vv3gcMsXlzg7dpZJPDtJxMOWMJnayR9C4Ej7rpvVmkRRpgzar8JpXfpPKTPF5L66XHgMLL11-8QU2vdIKn_8O_qT9FDpcT</recordid><startdate>20030601</startdate><enddate>20030601</enddate><creator>Barclay, L RC</creator><creator>Basque, M -C</creator><creator>Vinqvist, M R</creator><general>NRC Research Press</general><general>Canadian Science Publishing NRC Research Press</general><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7XB</scope><scope>88I</scope><scope>8AF</scope><scope>8AO</scope><scope>8FE</scope><scope>8FG</scope><scope>8FK</scope><scope>8FQ</scope><scope>8FV</scope><scope>8G5</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AEUYN</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>BHPHI</scope><scope>BKSAR</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>GNUQQ</scope><scope>GUQSH</scope><scope>HCIFZ</scope><scope>KB.</scope><scope>M2O</scope><scope>M2P</scope><scope>M3G</scope><scope>MBDVC</scope><scope>PADUT</scope><scope>PCBAR</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>Q9U</scope></search><sort><creationdate>20030601</creationdate><title>Singlet-oxygen reactions sensitized on solid surfaces of lignin or titanium dioxide: Product studies from hindered secondary amines and from lipid peroxidation</title><author>Barclay, L RC ; Basque, M -C ; Vinqvist, M R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c316t-764ee0b11b30a7c51df729c4ead36cb3c1f933a649291bdf1b25cb7c6d311d1d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><topic>Amines</topic><topic>Chemical reactions</topic><topic>Irradiation</topic><topic>Kinetics</topic><topic>Light intensity</topic><topic>Lignin</topic><topic>Lipid peroxidation</topic><topic>Liquid chromatography</topic><topic>Organic compounds</topic><topic>Oxidation</topic><topic>Oxygen</topic><topic>Oxygen consumption</topic><topic>Peroxidation</topic><topic>Peroxides</topic><topic>Photochemistry</topic><topic>Photolysis</topic><topic>Photooxidation</topic><topic>Pulp bleaching</topic><topic>Silica</topic><topic>Substrates</topic><topic>Titanium dioxide</topic><topic>Titanium oxides</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Barclay, L RC</creatorcontrib><creatorcontrib>Basque, M -C</creatorcontrib><creatorcontrib>Vinqvist, M R</creatorcontrib><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Science Database (Alumni Edition)</collection><collection>STEM Database</collection><collection>ProQuest Pharma Collection</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Canadian Business & Current Affairs Database</collection><collection>Canadian Business & Current Affairs Database (Alumni Edition)</collection><collection>Research Library (Alumni Edition)</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest One Sustainability</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>Natural Science Collection</collection><collection>Earth, Atmospheric & Aquatic Science Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>ProQuest Central Student</collection><collection>Research Library Prep</collection><collection>SciTech Premium Collection</collection><collection>Materials Science Database</collection><collection>Research Library</collection><collection>Science Database</collection><collection>CBCA Reference & Current Events</collection><collection>Research Library (Corporate)</collection><collection>Research Library China</collection><collection>Earth, Atmospheric & Aquatic Science Database</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>ProQuest Central Basic</collection><jtitle>Canadian journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Barclay, L RC</au><au>Basque, M -C</au><au>Vinqvist, M R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Singlet-oxygen reactions sensitized on solid surfaces of lignin or titanium dioxide: Product studies from hindered secondary amines and from lipid peroxidation</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>2003-06-01</date><risdate>2003</risdate><volume>81</volume><issue>6</issue><spage>457</spage><epage>467</epage><pages>457-467</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><coden>CJCHAG</coden><abstract>Product analyses and kinetic methods were used to determine the role of singlet oxygen in lignin-catalyzed oxidations of organic substrates. Method
A
used the ESR analysis of nitroxide radicals formed by singlet oxygen (Type II) on 2,2,6,6-tetramethylpiperidine,
1
, or tetramethylpiperidone,
2
. Method
B
used HPLC analysis of the 9- and 13-linoleate chain hydroperoxides formed on oxidation of methyl linoleate to distinguish free-radical peroxidation (Type I) from singlet-oxygen oxidation (Type II) on the basis of different cis,trans (kinetic) to trans,trans (thermodynamic) product ratios. Applications of method
A
to solid dispersions of lignin or titanium dioxide (TiO
2
, a known singlet-oxygen sensitizer) indicated singlet-oxygen reactions. In addition to the nitroxide triplet, irradiation of lignin produces a persistent broad signal in the solid attributed to phenoxyl radicals. Benzophenone and 3,5-di-tert-butyl-ortho-benzoquinone,
5
, coated on silica gel were used as models to compare the effects of irradiating such compounds on the products and kinetics of methyl linoleate oxidation. Benzophenone acted as an initiator, giving free-radical peroxidation, whereas
5
or lignin coated with methyl linoleate acted as singlet-oxygen sensitizers, according to both product studies (method
B
) and the kinetic order in oxygen consumption during UV photolysis. Photolysis of phase-separated sensitizer (TiO
2
or lignin) and substrate (methyl linoleate) resulted in typical singlet-oxygen products. These results indicate that singlet oxygen plays a significant role in the photo-yellowing of high-lignin-content wood pulps.
Key words: lignin, singlet oxygen, mechanism, peroxidation, products.</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v02-199</doi><tpages>11</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0008-4042 |
| ispartof | Canadian journal of chemistry, 2003-06, Vol.81 (6), p.457-467 |
| issn | 0008-4042 1480-3291 |
| language | eng |
| recordid | cdi_crossref_primary_10_1139_v02_199 |
| source | Free Full-Text Journals in Chemistry |
| subjects | Amines Chemical reactions Irradiation Kinetics Light intensity Lignin Lipid peroxidation Liquid chromatography Organic compounds Oxidation Oxygen Oxygen consumption Peroxidation Peroxides Photochemistry Photolysis Photooxidation Pulp bleaching Silica Substrates Titanium dioxide Titanium oxides |
| title | Singlet-oxygen reactions sensitized on solid surfaces of lignin or titanium dioxide: Product studies from hindered secondary amines and from lipid peroxidation |
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