Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas
This Thesis focuses on the synthesis and the study of the optical properties of organometallic luminescent platinum derivatives which incorporate substituted 2-arylbenzothiazole chromophores. It Is divided in a general Introduction, four separate Chapters and an Experimental section. The Pt(II) de...
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Universidad de La Rioja (España)
2021
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This Thesis focuses on the synthesis and the study of the optical properties of organometallic luminescent platinum derivatives which incorporate
substituted 2-arylbenzothiazole chromophores. It Is divided in a general Introduction, four separate Chapters and an Experimental section.
The Pt(II) derivatives incorporate 2-4-(R-phenyl)benzothiazole ligands either with R = alkyne, to obtain trans(bisalkynyl) complexes or R = Br and
Me2N substituents, used to synthesize cyclometalated derivatives. Labile groups (Cl, DMSO), cyanide, C6F5 and bioactive phosphines (having
carboxilic o polyether units) have been used as auxiliary ligands to improve emission efficiencies or their solubility in biological media. Diferent
oxidation reactions have been carried out which have allowed to pobtain luminescent bis(cyclometalated) Pt(IV) derivatives and to observe
unusual reactivity patterns as the reduction of DMSO to SMe2 on the Pt center. The complexes with the basic Me2N-pbt ligand can also act as
pH sensors, changing its spectroscopic properties. All the derivatives have been characterized by NMR and other spectroscopic techniques and,
when possible, their structures have been confirmed by X-ray crystal diffraction.
Most of the derivatives show intense modulable absorption and emission (fluorescence and/or phosphorescence) properties, which have been
studied in different media (solution, solid or doped films at 298 K and 77K), obtaining the quantum yields and lifetimes of the emissions. In
addition, the electronic transitions (absortion and emission), for selected complexes, have been also studied by DFT and TD-DFT theoretical
calculations to support the assignments.
Finally, the potential as anticancer drugs and as biomarkers of selected complexes have been studied in collaboration with the CIBIR. In
particular their cytotoxicity towards cancer and non-tumoral cell lines and citolocatization inside the cells by confocal microscopy has been
examined. Some of the derivatives are very sensible to the presence of molecular oxygen, and, in DMSO solutions, photooxidation of the solvent
is observed enhancing the phosphorescence. Due to this, the potential of one compound as sensitizer in photodynamic therapy towards cancer
cells has been studied, showing promising results. |
| author2 |
Lalinde Peña, Elena (Universidad de La Rioja) |
| author_facet |
Lalinde Peña, Elena (Universidad de La Rioja) Lara Garnica, Rebeca |
| format |
text (thesis) |
| author |
Lara Garnica, Rebeca |
| spellingShingle |
Lara Garnica, Rebeca Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| author_sort |
Lara Garnica, Rebeca |
| title |
Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| title_short |
Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| title_full |
Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| title_fullStr |
Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| title_full_unstemmed |
Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| title_sort |
sistemas de pt(ii) y pt(iv) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicas |
| publisher |
Universidad de La Rioja (España) |
| publishDate |
2021 |
| url |
https://dialnet.unirioja.es/servlet/oaites?codigo=285546 |
| work_keys_str_mv |
AT laragarnicarebeca sistemasdeptiiyptivbasadosencromoforos2arilbenzotiazolpropiedadesopticasyaplicacionesbiologicas |
| _version_ |
1718346692938432512 |
| spelling |
oai-TES00000229812021-02-10Sistemas de Pt(II) y Pt(IV) basados en cromóforos 2-arilbenzotiazol: propiedades ópticas y aplicaciones biológicasLara Garnica, RebecaThis Thesis focuses on the synthesis and the study of the optical properties of organometallic luminescent platinum derivatives which incorporate substituted 2-arylbenzothiazole chromophores. It Is divided in a general Introduction, four separate Chapters and an Experimental section. The Pt(II) derivatives incorporate 2-4-(R-phenyl)benzothiazole ligands either with R = alkyne, to obtain trans(bisalkynyl) complexes or R = Br and Me2N substituents, used to synthesize cyclometalated derivatives. Labile groups (Cl, DMSO), cyanide, C6F5 and bioactive phosphines (having carboxilic o polyether units) have been used as auxiliary ligands to improve emission efficiencies or their solubility in biological media. Diferent oxidation reactions have been carried out which have allowed to pobtain luminescent bis(cyclometalated) Pt(IV) derivatives and to observe unusual reactivity patterns as the reduction of DMSO to SMe2 on the Pt center. The complexes with the basic Me2N-pbt ligand can also act as pH sensors, changing its spectroscopic properties. All the derivatives have been characterized by NMR and other spectroscopic techniques and, when possible, their structures have been confirmed by X-ray crystal diffraction. Most of the derivatives show intense modulable absorption and emission (fluorescence and/or phosphorescence) properties, which have been studied in different media (solution, solid or doped films at 298 K and 77K), obtaining the quantum yields and lifetimes of the emissions. In addition, the electronic transitions (absortion and emission), for selected complexes, have been also studied by DFT and TD-DFT theoretical calculations to support the assignments. Finally, the potential as anticancer drugs and as biomarkers of selected complexes have been studied in collaboration with the CIBIR. In particular their cytotoxicity towards cancer and non-tumoral cell lines and citolocatization inside the cells by confocal microscopy has been examined. Some of the derivatives are very sensible to the presence of molecular oxygen, and, in DMSO solutions, photooxidation of the solvent is observed enhancing the phosphorescence. Due to this, the potential of one compound as sensitizer in photodynamic therapy towards cancer cells has been studied, showing promising results.La Tesis Doctoral se centra en la síntesis y estudio de las propiedades de compuestos de platino luminiscentes que contienen cromóforos derivados del 2-fenilbenzotiazol. Consta de una Introducción general, cuatro capítulos independientes y una sección experimental. Se estudian tanto derivados de Pt(II) con ligandos 2-4-(R-fenil)benzotiazol, ya sea con R = acetileno, para obtener compuestos del tipo trans(bisalquinilo), o con R = Br y Me2N utilizados en la preparación de derivados ciclometalados de Pt(II) . Como coligandos se han usado, ligandos lábiles, cianuro, grupos C6F5 o fosfinas bioactivas (con grupos ácido o polieter), para incrementar la eficiencia de las emisiones o su solubilidad en medios biológicos. Se han estudiado reacciones de oxidación, que han permitido obtener derivados bis(ciclometalados) emisivos de Pt(IV) e inusuales patrones de reactividad como la reducción de DMSO a SMe2 en el centro de Pt. Algunos derivados con el ligando Me2Npbt básico pueden actuar como sensores de ácidos, modificando sus propiedades espectroscópicas. Todos los compuestos se han caracterizado por RMN y otras técnicas espectroscópicas y, de los que ha sido posible, se ha obtenido su estructura cristalina por difracción de rayos-X de monocristal. La mayoría de los derivados presentan propiedades de absorción y emisión (fluorescencia y/o fosforescencia) intensas, con emisiones modulables. Estas propiedades han sido estudiadas en distintos medios (disolución, sólido y films dopados a 298 K y 77 K), obteniendo los rendimientos cuánticos y los tiempos de vida para estas emisiones. Además, se han realizado estudios teóricos mediante cálculos DFT y TDDFT de las estructuras optimizadas de la mayoría de los compuestos, con el objetivo de ayudar a la interpretación de sus propiedades ópticas. Por último, también se ha estudiado el potencial anticancerígeno y como biomarcadores de compuestos seleccionados en colaboración con el CIBIR, donde se ha medido la citotoxicidad frente a líneas celulares cancerígenas y no tumorales y se ha estudiado, mediante microscopía confocal, la emisión en el interior de las células y sus posibles mecanismos de acción. Algunos derivados son sensibles a la presencia de oxígeno, activándose la emisión en disoluciones de DMSO, donde se produce una reacción de fotooxidación del disolvente. Por ello, también se ha estudiado el potencial de uno de los compuestos en terapia fotodinámica frente a células tumorales, dando resultados muy prometedores de citotoxicidad y de selectividad.Universidad de La Rioja (España)Lalinde Peña, Elena (Universidad de La Rioja)Moreno García, María Teresa (Universidad de La Rioja)2021text (thesis)application/pdfhttps://dialnet.unirioja.es/servlet/oaites?codigo=285546spaLICENCIA DE USO: Los documentos a texto completo incluidos en Dialnet son de acceso libre y propiedad de sus autores y/o editores. Por tanto, cualquier acto de reproducción, distribución, comunicación pública y/o transformación total o parcial requiere el consentimiento expreso y escrito de aquéllos. 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