In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s

Autores
Abraham, Shibu; Ghosh, Indrajit; Nau, Werner M.; Chesta, Carlos Alberto; Pas, Steven J.; Hill, Anita J.; Weiss, Richard G.
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Norrish type 1 reactions of 1-(4-methylphenyl)-3-phenyl-2-propanone (ACOB1) have been used to probe structural and morphological properties of a series of poly(alkyl methacrylate)s (PAMAs, where the alkyl is ethyl, butyl, isobutyl, cyclohexyl, and hexadecyl) below and above their glass transition (or melting) temperatures. The PAMAs investigated cover a wide range of glass transition temperatures and structure types. The ratio of in-cage to the sum of in-cage and out-of-cage recombinations of the triplet benzylic radical-pairs generated upon irradiation of ACOB1 (Fc) have been calculated from relative photoproduct yields at different temperatures and are compared with the free hole volumes within the polymers as calculated from positronium annihilation lifetime spectroscopy. Laser flash photolysis experiments to follow the growth and decay of the radicals have also been conducted in order to correlate the steady-state irradiation results with the radical pair recombination processes (i.e., in-cage and out-of-cage). The changes in Fc as a function of PAMA type and phase (temperature) can be correlated with chain relaxation rates and the nature of the polymer side chains, but not hole free volumes. These results are compared with those from our previous work, conducted in polyethylenes with differing degrees of crystallinity, where hole free volume was the primary factor in controlling Fc.
Fil: Abraham, Shibu. University Of Georgetown; Estados Unidos
Fil: Ghosh, Indrajit. Constructor University Bremen; Alemania
Fil: Nau, Werner M.. Constructor University Bremen; Alemania
Fil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Pas, Steven J.. Monash University; Australia. Commonwealth Scientific And Industrial Research Organization; Australia
Fil: Hill, Anita J.. Monash University; Australia. Commonwealth Scientific And Industrial Research Organization; Australia
Fil: Weiss, Richard G.. University Of Georgetown; Estados Unidos
Materia
Benzylic radical pairs
Glassy and melted states
Polymers
Crystallinity
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/197576
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/197576
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)sAbraham, ShibuGhosh, IndrajitNau, Werner M.Chesta, Carlos AlbertoPas, Steven J.Hill, Anita J.Weiss, Richard G.Benzylic radical pairsGlassy and melted statesPolymersCrystallinityhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Norrish type 1 reactions of 1-(4-methylphenyl)-3-phenyl-2-propanone (ACOB1) have been used to probe structural and morphological properties of a series of poly(alkyl methacrylate)s (PAMAs, where the alkyl is ethyl, butyl, isobutyl, cyclohexyl, and hexadecyl) below and above their glass transition (or melting) temperatures. The PAMAs investigated cover a wide range of glass transition temperatures and structure types. The ratio of in-cage to the sum of in-cage and out-of-cage recombinations of the triplet benzylic radical-pairs generated upon irradiation of ACOB1 (Fc) have been calculated from relative photoproduct yields at different temperatures and are compared with the free hole volumes within the polymers as calculated from positronium annihilation lifetime spectroscopy. Laser flash photolysis experiments to follow the growth and decay of the radicals have also been conducted in order to correlate the steady-state irradiation results with the radical pair recombination processes (i.e., in-cage and out-of-cage). The changes in Fc as a function of PAMA type and phase (temperature) can be correlated with chain relaxation rates and the nature of the polymer side chains, but not hole free volumes. These results are compared with those from our previous work, conducted in polyethylenes with differing degrees of crystallinity, where hole free volume was the primary factor in controlling Fc.Fil: Abraham, Shibu. University Of Georgetown; Estados UnidosFil: Ghosh, Indrajit. Constructor University Bremen; AlemaniaFil: Nau, Werner M.. Constructor University Bremen; AlemaniaFil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Pas, Steven J.. Monash University; Australia. Commonwealth Scientific And Industrial Research Organization; AustraliaFil: Hill, Anita J.. Monash University; Australia. Commonwealth Scientific And Industrial Research Organization; AustraliaFil: Weiss, Richard G.. University Of Georgetown; Estados UnidosRoyal Society of Chemistry2012-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/197576Abraham, Shibu; Ghosh, Indrajit; Nau, Werner M.; Chesta, Carlos Alberto; Pas, Steven J.; et al.; In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 11; 6; 6-2012; 914-9241474-905X1474-9092CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/c1pp05282ainfo:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1039/c1pp05282ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:42:24Zoai:ri.conicet.gov.ar:11336/197576instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:42:24.737CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
title In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
spellingShingle In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
Abraham, Shibu
Benzylic radical pairs
Glassy and melted states
Polymers
Crystallinity
title_short In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
title_full In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
title_fullStr In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
title_full_unstemmed In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
title_sort In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s
dc.creator.none.fl_str_mv Abraham, Shibu
Ghosh, Indrajit
Nau, Werner M.
Chesta, Carlos Alberto
Pas, Steven J.
Hill, Anita J.
Weiss, Richard G.
author Abraham, Shibu
author_facet Abraham, Shibu
Ghosh, Indrajit
Nau, Werner M.
Chesta, Carlos Alberto
Pas, Steven J.
Hill, Anita J.
Weiss, Richard G.
author_role author
author2 Ghosh, Indrajit
Nau, Werner M.
Chesta, Carlos Alberto
Pas, Steven J.
Hill, Anita J.
Weiss, Richard G.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Benzylic radical pairs
Glassy and melted states
Polymers
Crystallinity
topic Benzylic radical pairs
Glassy and melted states
Polymers
Crystallinity
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Norrish type 1 reactions of 1-(4-methylphenyl)-3-phenyl-2-propanone (ACOB1) have been used to probe structural and morphological properties of a series of poly(alkyl methacrylate)s (PAMAs, where the alkyl is ethyl, butyl, isobutyl, cyclohexyl, and hexadecyl) below and above their glass transition (or melting) temperatures. The PAMAs investigated cover a wide range of glass transition temperatures and structure types. The ratio of in-cage to the sum of in-cage and out-of-cage recombinations of the triplet benzylic radical-pairs generated upon irradiation of ACOB1 (Fc) have been calculated from relative photoproduct yields at different temperatures and are compared with the free hole volumes within the polymers as calculated from positronium annihilation lifetime spectroscopy. Laser flash photolysis experiments to follow the growth and decay of the radicals have also been conducted in order to correlate the steady-state irradiation results with the radical pair recombination processes (i.e., in-cage and out-of-cage). The changes in Fc as a function of PAMA type and phase (temperature) can be correlated with chain relaxation rates and the nature of the polymer side chains, but not hole free volumes. These results are compared with those from our previous work, conducted in polyethylenes with differing degrees of crystallinity, where hole free volume was the primary factor in controlling Fc.
Fil: Abraham, Shibu. University Of Georgetown; Estados Unidos
Fil: Ghosh, Indrajit. Constructor University Bremen; Alemania
Fil: Nau, Werner M.. Constructor University Bremen; Alemania
Fil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Pas, Steven J.. Monash University; Australia. Commonwealth Scientific And Industrial Research Organization; Australia
Fil: Hill, Anita J.. Monash University; Australia. Commonwealth Scientific And Industrial Research Organization; Australia
Fil: Weiss, Richard G.. University Of Georgetown; Estados Unidos
description Norrish type 1 reactions of 1-(4-methylphenyl)-3-phenyl-2-propanone (ACOB1) have been used to probe structural and morphological properties of a series of poly(alkyl methacrylate)s (PAMAs, where the alkyl is ethyl, butyl, isobutyl, cyclohexyl, and hexadecyl) below and above their glass transition (or melting) temperatures. The PAMAs investigated cover a wide range of glass transition temperatures and structure types. The ratio of in-cage to the sum of in-cage and out-of-cage recombinations of the triplet benzylic radical-pairs generated upon irradiation of ACOB1 (Fc) have been calculated from relative photoproduct yields at different temperatures and are compared with the free hole volumes within the polymers as calculated from positronium annihilation lifetime spectroscopy. Laser flash photolysis experiments to follow the growth and decay of the radicals have also been conducted in order to correlate the steady-state irradiation results with the radical pair recombination processes (i.e., in-cage and out-of-cage). The changes in Fc as a function of PAMA type and phase (temperature) can be correlated with chain relaxation rates and the nature of the polymer side chains, but not hole free volumes. These results are compared with those from our previous work, conducted in polyethylenes with differing degrees of crystallinity, where hole free volume was the primary factor in controlling Fc.
publishDate 2012
dc.date.none.fl_str_mv 2012-06
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/197576
Abraham, Shibu; Ghosh, Indrajit; Nau, Werner M.; Chesta, Carlos Alberto; Pas, Steven J.; et al.; In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 11; 6; 6-2012; 914-924
1474-905X
1474-9092
CONICET Digital
CONICET
url http://hdl.handle.net/11336/197576
identifier_str_mv Abraham, Shibu; Ghosh, Indrajit; Nau, Werner M.; Chesta, Carlos Alberto; Pas, Steven J.; et al.; In-cage and out-of-cage combinations of benzylic radical pairs in the glassy and melted states of poly(alkyl methacrylate)s; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 11; 6; 6-2012; 914-924
1474-905X
1474-9092
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/c1pp05282a
info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1039/c1pp05282a
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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