Person: Rodríguez Agarrabeitia, Antonia
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First Name
Antonia
Last Name
Rodríguez Agarrabeitia
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Óptica y Optometría
Department
Química Orgánica
Area
Química Orgánica
Identifiers
14 results
Search Results
Now showing 1 - 10 of 14
Item Generation of multiple triplet states in an orthogonal bodipy dimer: a breakthrough spectroscopic and theoretical approach(Physical chemistry chemical physics, 2022) García Moreno, Inmaculada; Postils, Verónica; Rebollar, Esther; Ortíz García, María Josefa; Rodríguez Agarrabeitia, Antonia; Casanova, DavidGeneration of triplet states in assemblies of organic chromophores is extremely appealing for their potential use in optoelectronic applications. In this work, we investigate the intricacies of triplet state generation in an orthogonal BODIPY dimer by combining delayed photoemission techniques with electronic structure calculations. Our analysis provides a deep understanding of the electronic states involved, and describes different competing deactivation channels beyond prompt radiative decay. In particular, we identify charge-transfer (CT) mediated intersystem crossing (ISC) as the most likely mechanism for the triplet state generation in this system. The different emission bands at long times can be associated with delayed fluorescence, CT emission and phosphorescence from multiple low-energy triplets. Interestingly, the dependence of the yield of triplet state population and emission profiles with the solvent polarity evidences the decisive role of the CT configuration in the fate of the photoactivated dimer, controlling the relative ISC, reverse ISC, and internal conversion efficiencies. Overall, the present results provide a rather complete description of the delayed photophysics in the BODIPY dimer, but are not able to fully rationalize the unexpected photoluminescence recorded at long wavelengths (≥ 900 nm). We hypothesize that the origin of this emission, not present in BODIPY monomers, emerges from intermonomer interactions triggered by intramolecular distortions opening up a new vision in the controverted mechanism driving the photophysical behavior from orthogonally linked organic monomers.Item First Lanthanide Complex for de Novo Phasing in Native Protein Crystallography at 1 Å Radiation(ACS Applied Bio Materials, 2021) Prieto Castañeda, Alejandro; Martínez Caballero, Siseth; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; Moya Cerero, Santiago de la; Ortíz García, María Josefa; Hermoso, Juan A.Phasing agents enabling de novo protein structure determination at ca. 1 Å, the wavelength corresponding to the maximum intensity of the synchrotron facilities applied in biomacromolecular crystallography, have been long sought-after. The first phasing agent designed for solving native protein structures at 0.97934 Å is described herein. The agent consists of a neutral ytterbium(III)-caged complex that exhibits higher anomalous signals at shorter wavelengths when compared to the best, currently applied lanthanide-based phasing agents, all of them based on gadolinium or terbium. As a proof of principle, the complex allows determining the 3D structure of a 36 kDa protein without setting the incident beam wavelength at the metal absorption edge, the strategy followed to date to gain the strongest anomalous signal even at the expense of crystallographic resolution. The agent becomes nondisruptive to the diffraction quality of the marked crystals and allows determining accurate phases, both leading to high-quality electron-density maps that enable the full tracing of the protein structure only with one agent unit bound to the protein. The high phasing power, efficient binding to the protein, low metal−macromolecule ratio, and easy handling support the developed Yb(III) complex as the best phasing agent for X-ray crystallography of a complex biomacromolecule without using modified analogues.Item Mitochondria selective trackers for long-term imaging based on readily accessible neutral BODIPYs(Chemical Communications, 2021) Ramos Torres, Ágata; Avellanal Zaballa, Edurne; García Garrido, Fernando; Fernández Martínez, Ana B.; Prieto Castañeda, Alejandro; Rodríguez Agarrabeitia, Antonia; Bañuelos Prieto, Jorge; García Moreno, Inmaculada; Lucio Cazaña, Francisco Javier; Ortíz García, María JosefaWe report the design of a new model based on a small neutral 8-aryl-3-formylBODIPY and its suitability to develop privileged highly bright and photostable fluorescent probes for selective and, more importantly, covalent staining of mitochondria.- Project number: 77
Item Adaptación de las prácticas de laboratorio de Materiales en Óptica Oftálmica y Lentes de contacto a metodologías de aprendizaje activo basado en la experimentación(2023) Orden Hernández, María Ulagares De La; Escobar Peña, Ana Andrea; Jiménez García, Inmaculada; Lasagabaster Latorre, Aurora; Macicior Michelena, Jon; Martín-Fontecha Corrales, María Del Mar; Molina Santos, Marina Mercedes; Marinov, Lyuboslav Nikolaev; Ortiz García, María Josefa; Rodríguez Agarrabeitia, AntoniaEste proyecto pretende rediseñar las prácticas de Materiales Ópticos y adaptarlas a los principios del Aprendizaje Activo Basado en la Experimentación (ABE) implementando herramientas de Aula Invertida y Aprendizaje Cooperativo Item Red haloBODIPYs as theragnostic agents: The role of the substitution at meso position(Dyes and Pigments, 2021) Prieto Montero, Ruth; Prieto Castañeda, Alejandro; Katsumiti, Alberto; Sola Llano, Rebeca; Rodríguez Agarrabeitia, Antonia; Cajaraville, Miren P.; Ortiz García, María Josefa; Martínez Martínez, VirginiaThree different molecular designs based on BODIPY dye have been proposed as photosensitizers (PSs) for photodynamic therapy (PDT) by the inclusion of halogen atoms (Iodine) at 2,6-positions and with extended conjugation at 3, 5-positions and varying the substitution at meso position. The synthesis is described and their main photophysical features including singlet oxygen production and triplet states were characterized by absorption and fluorescence spectroscopy (steady-state and time-correlated) and nanosecond transient absorption spectroscopy. The results were compared with the commercial Chlorin e6. The three new red-halogen-BODIPYs showed a great balance between singlet oxygen generation (ΦΔ≥0.40) and fluorescence (Φfl≥0.22) for potential application on PDT, and particularly in theragnosis. In vitro experiments in HeLa cells were done to study their performance and to elucidate the best potential candidate for PDT.Item Development of Geometry-Controlled All-Orthogonal BODIPY Trimers for Photodynamic Therapy and Phototheragnosis(Organic Letters, 2022) Prieto Castañeda, Alejandro; García Garrido, Fernando; Díaz Norambuena, Carolina; Escriche Navarro, Blanca; García Fernández, Alba; Bañuelos, Jorge; Rebollar, Esther; García Moreno, Inmaculada; Martínez Máñez, Ramón; Moya Cerero, Santiago De La; Rodríguez Agarrabeitia, Antonia; Ortiz García, María JosefaWe have established an easy synthetic protocol for selectively developing all-orthogonal BODIPY trimers with unprecedented geometries on the basis of selecting methyl oxidation versus electrophilic formylation of key dimeric precursors. Photophysical characterization together with biological assays unraveled the most suitable BODIPY−BODIPY geometrical arrangements within the trimer, forcing them to serve as molecular platforms for the development of new, advanced heavy-atom-free photosensitizers for photodynamic therapy and phototheragnosis.Item Formylation as a Chemical Tool to Modulate the Performance of Photosensitizers Based on Boron Dipyrromethene Dimers(International Journal of Molecular Sciences, 2023) Díaz Norambuena, Carolina; Avellanal Zaballa, Edurne; Prieto Castañeda, Alejandro; Bañuelos, Jorge; de la Moya, Santiago; Rodríguez Agarrabeitia, Antonia; Moya Cerero, Santiago De La; Ortiz, María J.Heavy-atom-free photosensitizers are envisioned as the next generation of photoactive molecules for photo-theragnosis. In this approach, and after suitable irradiation, a single molecular scaffold is able to visualize and kill tumour cells by fluorescence signalling and photodynamic therapy (PDT), respectively, with minimal side effects. In this regard, BODIPY-based orthogonal dimers have irrupted as suitable candidates for this aim. Herein, we analyse the photophysical properties of a set of formyl-functionalized BODIPY dimers to ascertain their suitability as fluorescent photosensitizers. The conducted computationally aided spectroscopic study determined that the fluorescence/singlet oxygen generation dual performance of these valuable BODIPY dimers not only depends on the BODIPY-BODIPY linkage and the steric hindrance around it, but also can be modulated by proper formyl functionalization at specific chromophoric positions. Thus, we propose regioselective formylation as an effective tool to modulate such a delicate photonic balance in BODIPY-based dimeric photosensitizers. The taming of the excited-state dynamics, in particular intramolecular charge transfer as the key underlying process mediating fluorescence deactivation vs. intersystem crossing increasing, could serve to increase fluorescence for brighter bioimaging, enhance the generation of singlet oxygen for killing activity, or balance both for photo-theragnosis.Item Functionalization of photosensitized silica nanoparticles for advanced photodynamic therapy of cancer(International Journal of Molecular Sciences, 2021) Prieto Montero, Ruth; Prieto Castañeda, Alejandro; Katsumiti, Alberto; Cajaraville, Miren P.; Rodríguez Agarrabeitia, Antonia; Ortiz García, María Josefa; Martínez Martínez, VirginiaBODIPY dyes have recently attracted attention as potential photosensitizers. In this work, commercial and novel photosensitizers (PSs) based on BODIPY chromophores (haloBODIPYs and orthogonal dimers strategically designed with intense bands in the blue, green or red region of the visible spectra and high singlet oxygen production) were covalently linked to mesoporous silica nanoparticles (MSNs) further functionalized with PEG and folic acid (FA). MSNs approximately 50 nm in size with different functional groups were synthesized to allow multiple alternatives of PS-PEG-FA decoration of their external surface. Different combinations varying the type of PS (commercial Rose Bengal, Thionine and Chlorine e6 or custom-made BODIPY-based), the linkage design, and the length of PEG are detailed. All the nanosystems were physicochemically characterized (morphology, diameter, size distribution and PS loaded amount) and photophysically studied (absorption capacity, fluorescence efficiency, and singlet oxygen production) in suspension. For the most promising PS-PEG-FA silica nanoplatforms, the biocompatibility in dark conditions and the phototoxicity under suitable irradiation wavelengths (blue, green, or red) at regulated light doses (10–15 J/cm2) were compared with PSs free in solution in HeLa cells in vitro.- Project number: 175
Item Del laboratorio al aula virtual en las prácticas de Química Orgánica(2021) Lora Maroto, Beatriz; Martínez Ruiz, María Paloma; Ortíz García, María Josefa; Osío Barcina, José de Jesús; Rodríguez Agarrabeitia, Antonia; Ray Leiva, César; Schad Alburquerque, Cristobal MartínEste proyecto surge de la necesidad de proporcionar a los estudiantes la posibilidad de adquirir las competencias asociadas a las prácticas de laboratorio de Química Orgánica, también en aquellas situaciones en las que no es posible la docencia presencial. Un claro ejemplo de ello ha sido el año 2020 con la situación del COVID-19 y el obligado confinamiento, que ha hecho imposible proporcionar a los estudiantes docencia práctica en el laboratorio. Pero esta no es la única situación en la que la posibilidad de recibir docencia práctica online se hace necesaria. Pueden existir casos de estudiantes que no puedan asistir presencialmente al laboratorio, por ejemplo, por motivos médicos, psicológicos, por discapacidad, cuando no se dispone de un laboratorio convenientemente adaptado, etc. La docencia online tiene la ventaja, frente a la docencia presencial, que se puede recibir desde cualquier lugar, de manera no necesariamente síncrona. Esto facilita que los estudiantes puedan organizar su docencia adaptada a su situación y necesidades. Así, en este proyecto se proporcionan las herramientas para posibilitar que todos los estudiantes puedan recibir esta docencia en cualquier situación, momento y lugar. Es evidente el reto que supone adaptar una docencia práctica de laboratorio a la docencia online, donde no es posible la manipulación de reactivos y material que se trabaja en un laboratorio de prácticas. Por ello, en este proyecto se han diseñado las actividades online que han de sustituir a la docencia presencial en el laboratorio, de manera que se logre la adquisición de las competencias asociadas a las prácticas por parte de la totalidad de los estudiantes, así como su correcta evaluación. Item Exploring BODIPY Derivatives as Singlet Oxygen Photosensitizers for PDT(Photochemistry and Photobiology, 2020) Prieto Moreno, Ruth; Prieto Castañeda, Alejandro; Sola Llano, Rebeca; Rodríguez Agarrabeitia, Antonia; García Fresnadillo, David; López Arbeloa, Íñigo María; Villanueva Oroquieta, Ángeles; Ortíz García, María Josefa; Moya Cerero, Santiago de la; Martínez Martínez, VirginiaThis minireview is devoted to honoring the memory of Dr. Thomas Dougherty, a pioneer of modern photodynamic therapy (PDT). It compiles the most important inputs made by our research group since 2012 in the development of new photosensitizers based on BODIPY chromophore which, thanks to the rich BODIPY chemistry, allows a finely tuned design of the photophysical properties of this family of dyes to serve as efficient photosensitizers for the generation of singlet oxygen. These two factors, photophysical tuning and workable chemistry, have turned BODIPY chromophore as one of the most promising dyes for the development of improved photosensitizers for PDT. In this line, this minireview is mainly related to the establishment of chemical methods and structural designs for enabling efficient singlet oxygen generation in BODIPYs. The approaches include the incorporation of heavy atoms, such as halogens (iodine or bromine) in different number and positions on the BODIPY scaffold, and also transition metal atoms, by their complexation with Ir(III) center, for instance. On the other hand, low‐toxicity approaches, without involving heavy metals, have been developed by preparing several orthogonal BODIPY dimers with different substitution patterns. The advantages and drawbacks of all these diverse molecular designs based on BODIPY structural framework are described.