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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/118850
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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 Técnicas2025-09-03T10:06:19Zoai: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:34982025-09-03 10:06:19.553CONICET 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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1842269953406795776 |
score |
13.13397 |