A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins

Autores
Biasutti, Maria Alicia; Posadaz, Ariana; García, N. A.
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Kinetic aspects of the sensitized photooxidation of a- and b-chymotrypsins have been studied at pH 6 and 8. The sensitization, employing classical O2(1Dg)-photogenerators, such as xanthene dyes, is a kinetically intricate process because of the presence of ground state dye?protein associations and to the simultaneous participation of superoxide ion and singlet molecular oxygen [O2(1Dg)].Both proteins, that possess the same distribution pattern of photooxidizable amino acids, suffer a pure O2(1Dg)- mediated photodynamic attack, using the carbonylic sensitizer Perinaphthenone. Overall and reactive rate constants for the O2(1Dg)-quenching (in the order of 108 and 107/M/s, respectively), and rates of oxygen consumption determined by time-resolved, spectroscopic and polarographic methods indicate that a- and b-chymotrypsins are less photooxidizable at pH 6, as a result of an enhancement of the O2(1Dg)-physical quenching component. In general terms, b-chymotrypsin exhibits the greater overall proclivity to interact with O2(1Dg), whereas structural factors, possibly evidenced by a higher exposure of the reactive tryptophan residues, impart an increased photooxidation degree to the proteins at pH 8, specially to the a-chymotrypsin.
Fil: Biasutti, Maria Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto; Argentina
Fil: Posadaz, Ariana. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina
Fil: García, N. A.. Universidad Nacional de Río Cuarto; Argentina
Materia
chymotrypsin
photodynamic effect
singlet molecular oxygen
photodynamic effect
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:11336/240804
Acceder
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network_name_str CONICET Digital (CONICET)
spelling A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsinsBiasutti, Maria AliciaPosadaz, ArianaGarcía, N. A.chymotrypsinphotodynamic effectsinglet molecular oxygenphotodynamic effecthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Kinetic aspects of the sensitized photooxidation of a- and b-chymotrypsins have been studied at pH 6 and 8. The sensitization, employing classical O2(1Dg)-photogenerators, such as xanthene dyes, is a kinetically intricate process because of the presence of ground state dye?protein associations and to the simultaneous participation of superoxide ion and singlet molecular oxygen [O2(1Dg)].Both proteins, that possess the same distribution pattern of photooxidizable amino acids, suffer a pure O2(1Dg)- mediated photodynamic attack, using the carbonylic sensitizer Perinaphthenone. Overall and reactive rate constants for the O2(1Dg)-quenching (in the order of 108 and 107/M/s, respectively), and rates of oxygen consumption determined by time-resolved, spectroscopic and polarographic methods indicate that a- and b-chymotrypsins are less photooxidizable at pH 6, as a result of an enhancement of the O2(1Dg)-physical quenching component. In general terms, b-chymotrypsin exhibits the greater overall proclivity to interact with O2(1Dg), whereas structural factors, possibly evidenced by a higher exposure of the reactive tryptophan residues, impart an increased photooxidation degree to the proteins at pH 8, specially to the a-chymotrypsin.Fil: Biasutti, Maria Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto; ArgentinaFil: Posadaz, Ariana. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: García, N. A.. Universidad Nacional de Río Cuarto; ArgentinaWiley Blackwell Publishing, Inc2008-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/240804Biasutti, Maria Alicia; Posadaz, Ariana; García, N. A.; A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins; Wiley Blackwell Publishing, Inc; Journal Of Peptide Research; 62; 1; 12-2008; 11-181397-002XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1034/j.1399-3011.2003.00064.xinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:05:13Zoai:ri.conicet.gov.ar:11336/240804instacron: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:34982025-09-03 10:05:13.349CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
title A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
spellingShingle A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
Biasutti, Maria Alicia
chymotrypsin
photodynamic effect
singlet molecular oxygen
photodynamic effect
title_short A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
title_full A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
title_fullStr A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
title_full_unstemmed A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
title_sort A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins
dc.creator.none.fl_str_mv Biasutti, Maria Alicia
Posadaz, Ariana
García, N. A.
author Biasutti, Maria Alicia
author_facet Biasutti, Maria Alicia
Posadaz, Ariana
García, N. A.
author_role author
author2 Posadaz, Ariana
García, N. A.
author2_role author
author
dc.subject.none.fl_str_mv chymotrypsin
photodynamic effect
singlet molecular oxygen
photodynamic effect
topic chymotrypsin
photodynamic effect
singlet molecular oxygen
photodynamic effect
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Kinetic aspects of the sensitized photooxidation of a- and b-chymotrypsins have been studied at pH 6 and 8. The sensitization, employing classical O2(1Dg)-photogenerators, such as xanthene dyes, is a kinetically intricate process because of the presence of ground state dye?protein associations and to the simultaneous participation of superoxide ion and singlet molecular oxygen [O2(1Dg)].Both proteins, that possess the same distribution pattern of photooxidizable amino acids, suffer a pure O2(1Dg)- mediated photodynamic attack, using the carbonylic sensitizer Perinaphthenone. Overall and reactive rate constants for the O2(1Dg)-quenching (in the order of 108 and 107/M/s, respectively), and rates of oxygen consumption determined by time-resolved, spectroscopic and polarographic methods indicate that a- and b-chymotrypsins are less photooxidizable at pH 6, as a result of an enhancement of the O2(1Dg)-physical quenching component. In general terms, b-chymotrypsin exhibits the greater overall proclivity to interact with O2(1Dg), whereas structural factors, possibly evidenced by a higher exposure of the reactive tryptophan residues, impart an increased photooxidation degree to the proteins at pH 8, specially to the a-chymotrypsin.
Fil: Biasutti, Maria Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto; Argentina
Fil: Posadaz, Ariana. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina
Fil: García, N. A.. Universidad Nacional de Río Cuarto; Argentina
description Kinetic aspects of the sensitized photooxidation of a- and b-chymotrypsins have been studied at pH 6 and 8. The sensitization, employing classical O2(1Dg)-photogenerators, such as xanthene dyes, is a kinetically intricate process because of the presence of ground state dye?protein associations and to the simultaneous participation of superoxide ion and singlet molecular oxygen [O2(1Dg)].Both proteins, that possess the same distribution pattern of photooxidizable amino acids, suffer a pure O2(1Dg)- mediated photodynamic attack, using the carbonylic sensitizer Perinaphthenone. Overall and reactive rate constants for the O2(1Dg)-quenching (in the order of 108 and 107/M/s, respectively), and rates of oxygen consumption determined by time-resolved, spectroscopic and polarographic methods indicate that a- and b-chymotrypsins are less photooxidizable at pH 6, as a result of an enhancement of the O2(1Dg)-physical quenching component. In general terms, b-chymotrypsin exhibits the greater overall proclivity to interact with O2(1Dg), whereas structural factors, possibly evidenced by a higher exposure of the reactive tryptophan residues, impart an increased photooxidation degree to the proteins at pH 8, specially to the a-chymotrypsin.
publishDate 2008
dc.date.none.fl_str_mv 2008-12
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/11336/240804
Biasutti, Maria Alicia; Posadaz, Ariana; García, N. A.; A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins; Wiley Blackwell Publishing, Inc; Journal Of Peptide Research; 62; 1; 12-2008; 11-18
1397-002X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/240804
identifier_str_mv Biasutti, Maria Alicia; Posadaz, Ariana; García, N. A.; A comparative kinetic study on the singlet molecular oxygen‐mediated photoxidation of α‐ and β‐chymotrypsins; Wiley Blackwell Publishing, Inc; Journal Of Peptide Research; 62; 1; 12-2008; 11-18
1397-002X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1034/j.1399-3011.2003.00064.x
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
dc.publisher.none.fl_str_mv Wiley Blackwell Publishing, Inc
publisher.none.fl_str_mv Wiley Blackwell Publishing, Inc
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
_version_ 1842269899674615808
score 13.13397

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