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
6 results
Search Results
Now showing 1 - 6 of 6
Item A versatile fluorescent molecular probe endowed with singlet oxygen generation under white-light photosensitization(Dyes and Pigments, 2017) Durán Sampedro, Gonzalo; Epelde Elezcano, Nerea; Martínez Martínez, Virginia; Esnal Martínez, Ixone; Bañuelos Prieto, Jorge; García Moreno, Inmaculada; Rodríguez Agarrabeitia, Antonia; Moya Cerero, Santiago de la; Tabero Truchado, Andrea; Lázaro Carrillo, Ana; Villanueva Oroquieta, Ángeles; Ortíz García, María Josefa; López Arbeloa, Íñigo MaríaDespite fluorescent photodynamic therapy (fluorescent-PDT) dyes are promising theranostic agents, current approaches unfortunately involve crucial shortcomings (such as, narrow absorption bands, high cost, low bio-compatibility and specificity, low dual efficiency) making difficult their clinical translation. Particularly, efficient fluorescent-PDT agents triggered under white-light, with potential application in topic solar treatments, are scarce. Here, we describe the rational development of a novel fluorescent-PDT molecular biomaterial based on BODIPY building blocks able to sustain, simultaneously, synthetic accessibility, high fluorescence and phototoxicity within a broad spectral window, biocompatibility, including low dark toxicity and high cell permeability with selective accumulation in lysosomes and, what is more important, excellent efficient activity triggered under white light. These all-in-one combined properties make the new dye a valuable ground platform for the development of future smarter theranostic agents.Item Singlet Fission Mediated Photophysics of BODIPY Dimers(Journal of physical chemistry letters, 2018) Montero, Raul; Martínez Martínez, Virginia; Longarte, Asier; Epelde Elezcano, Nerea; Palao Utiel, Eduardo; Lamas, Iker; Manzano, Hegoi; Rodríguez Agarrabeitia, Antonia; López Arbeloa, Íñigo María; Ortíz García, María Josefa; García Moreno, InmaculadaThe photodynamics of an orthogonal BODIPY dimer, particularly the formation of triplet states, has been explored by femtosecond and nanosecond transient absorption measurements. The short time scale data show the appearance of transient features of triplet character that, according to quantitative analysis of their intensities, account for more than 100% of the initially excited molecules, which reveals the occurrence of a singlet fission process in the isolated dimers. The formation rate of the triplet correlated state 1(TT) is found to depend on the solvent polarity, pointing to the mediation of a charge transfer character state. The dissociation of the 1(TT) state into pairs of individual triplets determines the triplet yield measured in the long time scales. The kinetic model derived from the results provides a comprehensive view of the photodynamics of BODIPY dimers and permits rationalization of the photophysical parameters of these systems.Item Rational molecular design enhancing the photonic performance of red-emitting perylene bisimide dyes(Physical Chemistry Chemical Physics, 2017) Avellanal Zaballa, Edurne; Durán Sampedro, Gonzalo; Prieto Castañeda, Alejandro; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; López Arbeloa, Íñigo María; Bañuelos Prieto, Jorge; Ortiz García, María JosefaWe report the synthesis of novel multichromophoric organic architectures, where perylene red is decorated with BODIPY and/or hydroxycoumarin dyes acting as light harvesters and energy donors. The computationally-aided photophysical study of these molecular assemblies reveals a broadband absorption which, regardless of the excitation wavelength, leads solely to a bright red-edge emission from perylene bisimide after efficient intramolecular energy transfer hops. The increase of the absorbance of these molecular antennas at key pumping wavelengths enhances the laser action of the commercial perylene red. The herein applied strategy based on energy transfer dye lasers should boost the use of perylene-based dyes as active media for red-emitting lasers.Item Controlling Vilsmeier-Haack processes in meso-methylBODIPYs: A new way to modulate finely photophysical properties in boron dipyrromethenes(Dyes and Pigments, 2017) Palao Utiel, Eduardo; Montalvillo Jiménez, Laura; Esnal Martínez, Ixone; Prieto Montero, Ruth; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; Bañuelos Prieto, Jorge; López Arbeloa, Íñigo María; Moya Cerero, Santiago De La; Ortiz García, María JosefaIn the herein work we report the fine and selective control of competitive processes when submitting meso-methylBODIPYs to Vilsmeier-Haack reaction conditions. These competitive processes generate BODIPYs with opposed photophysical properties, from highly fluorescent dyes enabling laser emission, to non-fluorescent singlet-oxygen photosensitizers. The synthetic control is exerted on the basis of the structure of the starting BODIPY, as well as the electrophilic character (hard or soft) of the formylating reagent.Item AcetylacetonateBODIPY-Biscyclometalated Iridium(III) Complexes: Effective Strategy towards Smarter Fluorescent Photosensitizer Agents(Chemistry: a european journal, 2017) Palao Utiel, Eduardo; Sola Llano, Rebeca; Tabero Truchado, Andrea; Manzano, Hegoi; Rodríguez Agarrabeitia, Antonia; Villanueva Oroquieta, Ángeles; López Arbeloa, Íñigo María; Martínez Martínez, Virginia; Ortíz García, María JosefaBiscyclometalated IrIII complexes involving boron-dipyrromethene (BODIPY)-based ancillary ligands, where the BODIPY unit is grafted to different chelating cores (acetylacetonate for Ir-1 and Ir-2, and bipyridine for Ir-3) by the BODIPY meso position, have been synthesized and characterized. Complexes with the BODIPY moiety directly grafted to acetylacetonate (Ir-1 and Ir-2) exhibit higher absorption coefficients (ϵ≈4.46×104 m−1 cm−1 and 3.38×104 m−1 cm−1 at 517 nm and 594 nm, respectively), higher moderate fluorescence emission (φfl≈0.08 and 0.22 at 528 nm and 652 nm, respectively) and, in particular, more efficient singlet oxygen generation upon visible-light irradiation (φΔ≈0.86 and 0.59, respectively) than that exhibited by Ir-3 (φΔ≈0.51, but only under UV light). Phosphorescence emission, nanosecond time-resolved transient absorption, and DFT calculations suggest that BODIPY-localized long-lived 3IL states are populated for Ir-1 and Ir-2. In vitro photodynamic therapy (PDT) activity studied for Ir-1 and Ir-2 in HeLa cells shows that such complexes are efficiently internalized into the cells, exhibiting low dark- and high photocytoxicity, even at significantly low complex concentration, making them potentially suitable as theranostic agents. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimItem Rational Design of Advanced Photosensitizers Based on Orthogonal BODIPY Dimers to Finely Modulate Singlet Oxygen Generation(Chemistry: a european journal, 2017) Epelde Elezcano, Nerea; Palao Utiel, Eduardo; Manzano, Hegoi; Prieto Castañeda, Alejandro; Rodríguez Agarrabeitia, Antonia; Tabero Truchado, Andrea; Villanueva Oroquieta, Ángeles; Moya Cerero, Santiago de la; López Arbeloa, Íñigo María; Martínez Martínez, Virginia; Ortíz García, María JosefaThe synthesis, photophysical characterization, and modeling of a new library of halogen-free photosensitizers (PS) based on orthogonal boron dipyrromethene (BODIPY) dimers are reported. Herein we establish key structural factors in order to enhance singlet oxygen generation by judiciously choosing the substitution patterns according to key electronic effects and synthetic accessibility factors. The photosensitization mechanism of orthogonal BODIPY dimers is demonstrated to be strongly related to their intrinsic intramolecular charge transfer (ICT) character through the spin-orbit charge-transfer intersystem crossing (SOCT-ISC) mechanism. Thus, singlet oxygen generation can be effectively modulated through the solvent polarity and the presence of electron-donating or withdrawing groups in one of the BODIPY units. The photodynamic therapy (PDT) activity is demonstrated by in vitro experiments, showing that selected photosensitizers are efficiently internalized into HeLa cells, exhibiting low dark toxicity and high phototoxicity, even at low PS concentration (0.05–5×10−6 m).