S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group

Autores
Ghosh, Goutam; Belh, Sarah J.; Chiemezie, Callistus; Walalawela, Niluksha; Ghogare, Ashwini A.; Vignoni, Mariana; Thomas, Andrés Héctor; McFarland, Sherri A.; Greer, Edyta M.; Greer, Alexander
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
There is a major need for light-activated materials for the release of sensitizers and drugs. Considering the success of chiral columns for the separation of enantiomer drugs, we synthesized an S,S-chiral linker system covalently attached to silica with a sensitizer ethene near the silica surface. First, the silica surface was modified to be aromatic rich, by replacing 70% of the surface groups with (3-phenoxypropyl)silane. We then synthesized a 3-component conjugate [chlorin sensitizer, S,S-chiral cyclohexane and ethene building blocks] in 5 steps with a 13% yield, and covalently bound the conjugate to the (3-phenoxypropyl)silane-coated silica surface. We hypothesized that the chiral linker would increase exposure of the ethene site for enhanced 1 O2-based sensitizer release. However, the chiral linker caused the sensitizer conjugate to adopt a U shape due to favored 1,2-diaxial substituent orientation; resulting in a reduced efficiency of surface loading. Further accentuating the U shape was p–p stacking between the (3-phenoxypropyl)silane and sensitizer. Semiempirical calculations and singlet oxygen luminescence data provided deeper insight into the sensitizer’s orientation and release. This study has lead to insight on modifications of surfaces for drug photorelease and can help lead to the development of miniaturized photodynamic devices.
Fil: Ghosh, Goutam. City University of New York; Estados Unidos. Acadia University; Canadá
Fil: Belh, Sarah J.. City University of New York; Estados Unidos
Fil: Chiemezie, Callistus. City University of New York; Estados Unidos
Fil: Walalawela, Niluksha. City University of New York; Estados Unidos
Fil: Ghogare, Ashwini A.. City University of New York; Estados Unidos
Fil: Vignoni, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Thomas, Andrés Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: McFarland, Sherri A.. Acadia University; Canadá. University of North Carolina; Estados Unidos
Fil: Greer, Edyta M.. City University of New York; Estados Unidos
Fil: Greer, Alexander. City University of New York; Estados Unidos
Materia
CHIRAL LINKER
SINGLET OXYGEN SENSITIZER
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:11336/118850
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/118850
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene GroupGhosh, GoutamBelh, Sarah J.Chiemezie, CallistusWalalawela, NilukshaGhogare, Ashwini A.Vignoni, MarianaThomas, Andrés HéctorMcFarland, Sherri A.Greer, Edyta M.Greer, AlexanderCHIRAL LINKERSINGLET OXYGEN SENSITIZERhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1There is a major need for light-activated materials for the release of sensitizers and drugs. Considering the success of chiral columns for the separation of enantiomer drugs, we synthesized an S,S-chiral linker system covalently attached to silica with a sensitizer ethene near the silica surface. First, the silica surface was modified to be aromatic rich, by replacing 70% of the surface groups with (3-phenoxypropyl)silane. We then synthesized a 3-component conjugate [chlorin sensitizer, S,S-chiral cyclohexane and ethene building blocks] in 5 steps with a 13% yield, and covalently bound the conjugate to the (3-phenoxypropyl)silane-coated silica surface. We hypothesized that the chiral linker would increase exposure of the ethene site for enhanced 1 O2-based sensitizer release. However, the chiral linker caused the sensitizer conjugate to adopt a U shape due to favored 1,2-diaxial substituent orientation; resulting in a reduced efficiency of surface loading. Further accentuating the U shape was p–p stacking between the (3-phenoxypropyl)silane and sensitizer. Semiempirical calculations and singlet oxygen luminescence data provided deeper insight into the sensitizer’s orientation and release. This study has lead to insight on modifications of surfaces for drug photorelease and can help lead to the development of miniaturized photodynamic devices.Fil: Ghosh, Goutam. City University of New York; Estados Unidos. Acadia University; CanadáFil: Belh, Sarah J.. City University of New York; Estados UnidosFil: Chiemezie, Callistus. City University of New York; Estados UnidosFil: Walalawela, Niluksha. City University of New York; Estados UnidosFil: Ghogare, Ashwini A.. City University of New York; Estados UnidosFil: Vignoni, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Thomas, Andrés Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: McFarland, Sherri A.. Acadia University; Canadá. University of North Carolina; Estados UnidosFil: Greer, Edyta M.. City University of New York; Estados UnidosFil: Greer, Alexander. City University of New York; Estados UnidosWiley Blackwell Publishing, Inc2019-01info: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/11336/118850Ghosh, Goutam; Belh, Sarah J.; Chiemezie, Callistus; Walalawela, Niluksha; Ghogare, Ashwini A.; et al.; S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group; Wiley Blackwell Publishing, Inc; Photochemistry and Photobiology; 95; 1; 1-2019; 293-3050031-8655CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1111/php.13000info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1111/php.13000info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:29:40Zoai:ri.conicet.gov.ar:11336/118850instacron: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 10:29:41.166CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
title S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
spellingShingle S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
Ghosh, Goutam
CHIRAL LINKER
SINGLET OXYGEN SENSITIZER
title_short S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
title_full S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
title_fullStr S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
title_full_unstemmed S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
title_sort S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group
dc.creator.none.fl_str_mv Ghosh, Goutam
Belh, Sarah J.
Chiemezie, Callistus
Walalawela, Niluksha
Ghogare, Ashwini A.
Vignoni, Mariana
Thomas, Andrés Héctor
McFarland, Sherri A.
Greer, Edyta M.
Greer, Alexander
author Ghosh, Goutam
author_facet Ghosh, Goutam
Belh, Sarah J.
Chiemezie, Callistus
Walalawela, Niluksha
Ghogare, Ashwini A.
Vignoni, Mariana
Thomas, Andrés Héctor
McFarland, Sherri A.
Greer, Edyta M.
Greer, Alexander
author_role author
author2 Belh, Sarah J.
Chiemezie, Callistus
Walalawela, Niluksha
Ghogare, Ashwini A.
Vignoni, Mariana
Thomas, Andrés Héctor
McFarland, Sherri A.
Greer, Edyta M.
Greer, Alexander
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv CHIRAL LINKER
SINGLET OXYGEN SENSITIZER
topic CHIRAL LINKER
SINGLET OXYGEN SENSITIZER
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv There is a major need for light-activated materials for the release of sensitizers and drugs. Considering the success of chiral columns for the separation of enantiomer drugs, we synthesized an S,S-chiral linker system covalently attached to silica with a sensitizer ethene near the silica surface. First, the silica surface was modified to be aromatic rich, by replacing 70% of the surface groups with (3-phenoxypropyl)silane. We then synthesized a 3-component conjugate [chlorin sensitizer, S,S-chiral cyclohexane and ethene building blocks] in 5 steps with a 13% yield, and covalently bound the conjugate to the (3-phenoxypropyl)silane-coated silica surface. We hypothesized that the chiral linker would increase exposure of the ethene site for enhanced 1 O2-based sensitizer release. However, the chiral linker caused the sensitizer conjugate to adopt a U shape due to favored 1,2-diaxial substituent orientation; resulting in a reduced efficiency of surface loading. Further accentuating the U shape was p–p stacking between the (3-phenoxypropyl)silane and sensitizer. Semiempirical calculations and singlet oxygen luminescence data provided deeper insight into the sensitizer’s orientation and release. This study has lead to insight on modifications of surfaces for drug photorelease and can help lead to the development of miniaturized photodynamic devices.
Fil: Ghosh, Goutam. City University of New York; Estados Unidos. Acadia University; Canadá
Fil: Belh, Sarah J.. City University of New York; Estados Unidos
Fil: Chiemezie, Callistus. City University of New York; Estados Unidos
Fil: Walalawela, Niluksha. City University of New York; Estados Unidos
Fil: Ghogare, Ashwini A.. City University of New York; Estados Unidos
Fil: Vignoni, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Thomas, Andrés Héctor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: McFarland, Sherri A.. Acadia University; Canadá. University of North Carolina; Estados Unidos
Fil: Greer, Edyta M.. City University of New York; Estados Unidos
Fil: Greer, Alexander. City University of New York; Estados Unidos
description There is a major need for light-activated materials for the release of sensitizers and drugs. Considering the success of chiral columns for the separation of enantiomer drugs, we synthesized an S,S-chiral linker system covalently attached to silica with a sensitizer ethene near the silica surface. First, the silica surface was modified to be aromatic rich, by replacing 70% of the surface groups with (3-phenoxypropyl)silane. We then synthesized a 3-component conjugate [chlorin sensitizer, S,S-chiral cyclohexane and ethene building blocks] in 5 steps with a 13% yield, and covalently bound the conjugate to the (3-phenoxypropyl)silane-coated silica surface. We hypothesized that the chiral linker would increase exposure of the ethene site for enhanced 1 O2-based sensitizer release. However, the chiral linker caused the sensitizer conjugate to adopt a U shape due to favored 1,2-diaxial substituent orientation; resulting in a reduced efficiency of surface loading. Further accentuating the U shape was p–p stacking between the (3-phenoxypropyl)silane and sensitizer. Semiempirical calculations and singlet oxygen luminescence data provided deeper insight into the sensitizer’s orientation and release. This study has lead to insight on modifications of surfaces for drug photorelease and can help lead to the development of miniaturized photodynamic devices.
publishDate 2019
dc.date.none.fl_str_mv 2019-01
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/11336/118850
Ghosh, Goutam; Belh, Sarah J.; Chiemezie, Callistus; Walalawela, Niluksha; Ghogare, Ashwini A.; et al.; S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group; Wiley Blackwell Publishing, Inc; Photochemistry and Photobiology; 95; 1; 1-2019; 293-305
0031-8655
CONICET Digital
CONICET
url http://hdl.handle.net/11336/118850
identifier_str_mv Ghosh, Goutam; Belh, Sarah J.; Chiemezie, Callistus; Walalawela, Niluksha; Ghogare, Ashwini A.; et al.; S,S‐Chiral Linker Induced U Shape with a Syn‐facial Sensitizer and Photocleavable Ethene Group; Wiley Blackwell Publishing, Inc; Photochemistry and Photobiology; 95; 1; 1-2019; 293-305
0031-8655
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1111/php.13000
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1111/php.13000
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 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
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score 13.070432

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