Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents
- Autores
- Caminos, Daniel Alberto; Durantini, Edgardo Néstor
- Año de publicación
- 2005
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Novel asymmetrically meso-substituted porphyrins bearing amino groups have been synthesized as precursors of cationic photodynamic agents. The amphiphilic character of these porphyrins was increased by the presence of a high lipophilic trifluoromethyl group. Different patterns of porphyrin structures were obtained from meso-4-[(3-N,N-dimethylaminopropoxy)phenyl] dipyrromethane 1, which was formed by the condensation of 4-(3-N,N-dimethylaminopropoxy) benzaldehyde with a large excess of pyrrole. This reaction takes place at high temperature with a yield of 59%. This reaction was also attempted under acid-catalyzed condensation at room temperature. However, under these conditions, the amino group reduces the catalyst and the reaction does not take place. To obtain porphyrins, dipyrromethane 1 was condensed with aldehydes in the presence of trifluoroacetic acid (TFA) under different conditions. First, 1 reacted with 4-(3-N,N-dimethylaminopropoxy)benzaldehyde in dichloromethane catalyzed by TFA (~4 times TFA/1 molar ratio) to obtain 6.2% of 5,10,15,20-tetrakis(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A4-porphyrin). Under similar conditions, reaction of 1 with 4-(trifluoromethyl)benzaldehyde produces 5,15-di(4-[3-N,N-dimethylaminopropoxy]phenyl)-10,20- di(4-trifluoromethylphenyl)porphyrin (A2B2-porphyrin) with a 4.8% yield. This procedure also yields a mixture of porphyrins, which were formed due to acidolysis of 1. When a minor amount of TFA was used in acetonitrile, the yield of A2B2-porphyrin was very poor (~0.4%). On the other hand, condensation of 1 with 4-trifluoromethylbenzaldehyde and 4-(3-N,N-dimethylaminopropoxy)benzaldehyde catalyzed by TFA (~2 times TFA/1 molar ratio) in acetonitrile yields 9.3% of 5-(4-trifluoromethylphenyl)-10,15,20- tris(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A3B-porphyrin). A2B2 and A4 porphyrins were also isolated with 6.0 and 2.0%, respectively. Finally, exhaustive methylation of amino porphyrins produces cationic sensitizers (>94% yield). Absorption and fluorescence spectroscopic studies of these sensitizers were compared in N,N-dimethylformamide. In these porphyrins, the cationic centers are isolated from the porphyrin ring by a propoxy bridge. Thus, the cationic charges have minimal influence on the photophysical properties of the sensitizers. In addition, this chain provides a higher mobility of the charge, which could facilitate interaction with the outer membrane of the Gram-negative bacteria. These amphiphilic cationic porphyrins are promising photosensitizers with potential applications in bacterial inactivation by photodynamic therapy.
Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina
Fil: Durantini, Edgardo Néstor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina - Materia
-
Amino porphyrin
Dipyrromethane
Anphiphilic structure
Photosensitizer - 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:11336/241964
Ver los metadatos del registro completo
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oai:ri.conicet.gov.ar:11336/241964 |
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3498 |
network_name_str |
CONICET Digital (CONICET) |
spelling |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agentsCaminos, Daniel AlbertoDurantini, Edgardo NéstorAmino porphyrinDipyrromethaneAnphiphilic structurePhotosensitizerhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Novel asymmetrically meso-substituted porphyrins bearing amino groups have been synthesized as precursors of cationic photodynamic agents. The amphiphilic character of these porphyrins was increased by the presence of a high lipophilic trifluoromethyl group. Different patterns of porphyrin structures were obtained from meso-4-[(3-N,N-dimethylaminopropoxy)phenyl] dipyrromethane 1, which was formed by the condensation of 4-(3-N,N-dimethylaminopropoxy) benzaldehyde with a large excess of pyrrole. This reaction takes place at high temperature with a yield of 59%. This reaction was also attempted under acid-catalyzed condensation at room temperature. However, under these conditions, the amino group reduces the catalyst and the reaction does not take place. To obtain porphyrins, dipyrromethane 1 was condensed with aldehydes in the presence of trifluoroacetic acid (TFA) under different conditions. First, 1 reacted with 4-(3-N,N-dimethylaminopropoxy)benzaldehyde in dichloromethane catalyzed by TFA (~4 times TFA/1 molar ratio) to obtain 6.2% of 5,10,15,20-tetrakis(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A4-porphyrin). Under similar conditions, reaction of 1 with 4-(trifluoromethyl)benzaldehyde produces 5,15-di(4-[3-N,N-dimethylaminopropoxy]phenyl)-10,20- di(4-trifluoromethylphenyl)porphyrin (A2B2-porphyrin) with a 4.8% yield. This procedure also yields a mixture of porphyrins, which were formed due to acidolysis of 1. When a minor amount of TFA was used in acetonitrile, the yield of A2B2-porphyrin was very poor (~0.4%). On the other hand, condensation of 1 with 4-trifluoromethylbenzaldehyde and 4-(3-N,N-dimethylaminopropoxy)benzaldehyde catalyzed by TFA (~2 times TFA/1 molar ratio) in acetonitrile yields 9.3% of 5-(4-trifluoromethylphenyl)-10,15,20- tris(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A3B-porphyrin). A2B2 and A4 porphyrins were also isolated with 6.0 and 2.0%, respectively. Finally, exhaustive methylation of amino porphyrins produces cationic sensitizers (>94% yield). Absorption and fluorescence spectroscopic studies of these sensitizers were compared in N,N-dimethylformamide. In these porphyrins, the cationic centers are isolated from the porphyrin ring by a propoxy bridge. Thus, the cationic charges have minimal influence on the photophysical properties of the sensitizers. In addition, this chain provides a higher mobility of the charge, which could facilitate interaction with the outer membrane of the Gram-negative bacteria. These amphiphilic cationic porphyrins are promising photosensitizers with potential applications in bacterial inactivation by photodynamic therapy.Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Durantini, Edgardo Néstor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaWorld Sci Publ Co Inc2005-02info: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/11336/241964Caminos, Daniel Alberto; Durantini, Edgardo Néstor; Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents; World Sci Publ Co Inc; Journal Of Porphyrins And Phthalocyanines; 09; 05; 2-2005; 334-3421088-4246CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.worldscientific.com/doi/abs/10.1142/S1088424605000423info:eu-repo/semantics/altIdentifier/doi/10.1142/S1088424605000423info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:21:54Zoai:ri.conicet.gov.ar:11336/241964instacron: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 10:21:54.623CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
title |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
spellingShingle |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents Caminos, Daniel Alberto Amino porphyrin Dipyrromethane Anphiphilic structure Photosensitizer |
title_short |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
title_full |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
title_fullStr |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
title_full_unstemmed |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
title_sort |
Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents |
dc.creator.none.fl_str_mv |
Caminos, Daniel Alberto Durantini, Edgardo Néstor |
author |
Caminos, Daniel Alberto |
author_facet |
Caminos, Daniel Alberto Durantini, Edgardo Néstor |
author_role |
author |
author2 |
Durantini, Edgardo Néstor |
author2_role |
author |
dc.subject.none.fl_str_mv |
Amino porphyrin Dipyrromethane Anphiphilic structure Photosensitizer |
topic |
Amino porphyrin Dipyrromethane Anphiphilic structure Photosensitizer |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
Novel asymmetrically meso-substituted porphyrins bearing amino groups have been synthesized as precursors of cationic photodynamic agents. The amphiphilic character of these porphyrins was increased by the presence of a high lipophilic trifluoromethyl group. Different patterns of porphyrin structures were obtained from meso-4-[(3-N,N-dimethylaminopropoxy)phenyl] dipyrromethane 1, which was formed by the condensation of 4-(3-N,N-dimethylaminopropoxy) benzaldehyde with a large excess of pyrrole. This reaction takes place at high temperature with a yield of 59%. This reaction was also attempted under acid-catalyzed condensation at room temperature. However, under these conditions, the amino group reduces the catalyst and the reaction does not take place. To obtain porphyrins, dipyrromethane 1 was condensed with aldehydes in the presence of trifluoroacetic acid (TFA) under different conditions. First, 1 reacted with 4-(3-N,N-dimethylaminopropoxy)benzaldehyde in dichloromethane catalyzed by TFA (~4 times TFA/1 molar ratio) to obtain 6.2% of 5,10,15,20-tetrakis(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A4-porphyrin). Under similar conditions, reaction of 1 with 4-(trifluoromethyl)benzaldehyde produces 5,15-di(4-[3-N,N-dimethylaminopropoxy]phenyl)-10,20- di(4-trifluoromethylphenyl)porphyrin (A2B2-porphyrin) with a 4.8% yield. This procedure also yields a mixture of porphyrins, which were formed due to acidolysis of 1. When a minor amount of TFA was used in acetonitrile, the yield of A2B2-porphyrin was very poor (~0.4%). On the other hand, condensation of 1 with 4-trifluoromethylbenzaldehyde and 4-(3-N,N-dimethylaminopropoxy)benzaldehyde catalyzed by TFA (~2 times TFA/1 molar ratio) in acetonitrile yields 9.3% of 5-(4-trifluoromethylphenyl)-10,15,20- tris(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A3B-porphyrin). A2B2 and A4 porphyrins were also isolated with 6.0 and 2.0%, respectively. Finally, exhaustive methylation of amino porphyrins produces cationic sensitizers (>94% yield). Absorption and fluorescence spectroscopic studies of these sensitizers were compared in N,N-dimethylformamide. In these porphyrins, the cationic centers are isolated from the porphyrin ring by a propoxy bridge. Thus, the cationic charges have minimal influence on the photophysical properties of the sensitizers. In addition, this chain provides a higher mobility of the charge, which could facilitate interaction with the outer membrane of the Gram-negative bacteria. These amphiphilic cationic porphyrins are promising photosensitizers with potential applications in bacterial inactivation by photodynamic therapy. Fil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina Fil: Durantini, Edgardo Néstor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina |
description |
Novel asymmetrically meso-substituted porphyrins bearing amino groups have been synthesized as precursors of cationic photodynamic agents. The amphiphilic character of these porphyrins was increased by the presence of a high lipophilic trifluoromethyl group. Different patterns of porphyrin structures were obtained from meso-4-[(3-N,N-dimethylaminopropoxy)phenyl] dipyrromethane 1, which was formed by the condensation of 4-(3-N,N-dimethylaminopropoxy) benzaldehyde with a large excess of pyrrole. This reaction takes place at high temperature with a yield of 59%. This reaction was also attempted under acid-catalyzed condensation at room temperature. However, under these conditions, the amino group reduces the catalyst and the reaction does not take place. To obtain porphyrins, dipyrromethane 1 was condensed with aldehydes in the presence of trifluoroacetic acid (TFA) under different conditions. First, 1 reacted with 4-(3-N,N-dimethylaminopropoxy)benzaldehyde in dichloromethane catalyzed by TFA (~4 times TFA/1 molar ratio) to obtain 6.2% of 5,10,15,20-tetrakis(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A4-porphyrin). Under similar conditions, reaction of 1 with 4-(trifluoromethyl)benzaldehyde produces 5,15-di(4-[3-N,N-dimethylaminopropoxy]phenyl)-10,20- di(4-trifluoromethylphenyl)porphyrin (A2B2-porphyrin) with a 4.8% yield. This procedure also yields a mixture of porphyrins, which were formed due to acidolysis of 1. When a minor amount of TFA was used in acetonitrile, the yield of A2B2-porphyrin was very poor (~0.4%). On the other hand, condensation of 1 with 4-trifluoromethylbenzaldehyde and 4-(3-N,N-dimethylaminopropoxy)benzaldehyde catalyzed by TFA (~2 times TFA/1 molar ratio) in acetonitrile yields 9.3% of 5-(4-trifluoromethylphenyl)-10,15,20- tris(4-[3-N,N-dimethylaminopropoxy]phenyl)porphyrin (A3B-porphyrin). A2B2 and A4 porphyrins were also isolated with 6.0 and 2.0%, respectively. Finally, exhaustive methylation of amino porphyrins produces cationic sensitizers (>94% yield). Absorption and fluorescence spectroscopic studies of these sensitizers were compared in N,N-dimethylformamide. In these porphyrins, the cationic centers are isolated from the porphyrin ring by a propoxy bridge. Thus, the cationic charges have minimal influence on the photophysical properties of the sensitizers. In addition, this chain provides a higher mobility of the charge, which could facilitate interaction with the outer membrane of the Gram-negative bacteria. These amphiphilic cationic porphyrins are promising photosensitizers with potential applications in bacterial inactivation by photodynamic therapy. |
publishDate |
2005 |
dc.date.none.fl_str_mv |
2005-02 |
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/11336/241964 Caminos, Daniel Alberto; Durantini, Edgardo Néstor; Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents; World Sci Publ Co Inc; Journal Of Porphyrins And Phthalocyanines; 09; 05; 2-2005; 334-342 1088-4246 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/241964 |
identifier_str_mv |
Caminos, Daniel Alberto; Durantini, Edgardo Néstor; Synthesis of asymmetrically meso -substituted porphyrins bearing amino groups as potential cationic photodynamic agents; World Sci Publ Co Inc; Journal Of Porphyrins And Phthalocyanines; 09; 05; 2-2005; 334-342 1088-4246 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/https://www.worldscientific.com/doi/abs/10.1142/S1088424605000423 info:eu-repo/semantics/altIdentifier/doi/10.1142/S1088424605000423 |
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 |
World Sci Publ Co Inc |
publisher.none.fl_str_mv |
World Sci Publ Co 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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1844614209514504192 |
score |
13.070432 |