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
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/241964

id CONICETDig_5831e9abef3167159dfd562ede4dbe83
oai_identifier_str oai:ri.conicet.gov.ar:11336/241964
network_acronym_str CONICETDig
repository_id_str 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
_version_ 1844614209514504192
score 13.070432