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
39 results
Search Results
Now showing 1 - 10 of 39
Item Carboxylates versus Fluorines: Boosting the Emission Properties of Commercial BODIPYs in Liquid and Solid Media(Advanced Functional Materials, 2013) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Cerdán, Luis; Pérez Ojeda, María Eugenia; Costela, Angel; García‐Moreno, Inmaculada; Esnal, Ixone; Bañuelos, Jorge; López Arbeloa, Iñigo; Ortiz García, María JosefaA new and facile strategy for the development of photonic materials is presented that fufi lls the conditions of being effi cient, stable, and tunable laser emitters over the visible region of spectrum, with the possibility of being easily processable and cost-effective. This approach uses poly(methyl methacrylate) (PMMA) as a host for new dyes with improved effi ciency and photostability synthesized. Using a simple protocol, fl uorine atoms in the commercial (4,4-difl uoro-4-bora-3a,4a-diaza-s-indacene) ( F -BODIPY) by carboxylate groups. The new O -BODIPYs exhibit enhanced optical properties and laser behavior both in the liquid and solid phases compared to their commercial analogues. Lasing effi ciencies up to 2.6 times higher than those recorded for the commercial dyes are registered with high photostabilities since the laser output remain at 80% of the initial value after 100 000 pump pulses in the same position of the sample at a repetition rate of 30 Hz; the corresponding commercial dye entirely loses its laser action after only 12 000 pump pulses. Distributed feedback laser emission is demonstrated with organic fi lms incorporating new O -BODIPYs deposited onto quartz substrates engraved with appropriated periodical structures. These dyes exhibit laser thresholds up to two times lower than those of the corresponding parent dyes with lasing intensities up to one order of magnitude higher.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 Coumarin–BODIPY hybrids by heteroatom linkage: versatile, tunable and photostable dye lasers for UV irradiation(Physical Chemistry Chemical Physics, 2015) Esnal, Ixone; Duran-Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Bañuelos, Jorge; García-Moreno, Inmaculada; Macías, Maria Ángeles ; Peña-Cabrera, Eduardo; López-Arbeloa, Iñigo; De la Moya, Santiago; Ortiz, Maria JoséLinking amino and hydroxycoumarins to BODIPYs through the amino or hydroxyl group lets the easy construction of unprecedented photostable coumarin–BODIPY hybrids with broadened and enhanced absorption in the UV spectral region, and outstanding wavelength-tunable laser action within the green-to-red spectral region (∼520–680 nm). These laser dyes allow the generation of a valuable tunable UV (∼260–350 nm) laser source by frequency doubling, which is essential to study accurately the photochemistry of biological molecules under solar irradiation. The tunability is achieved by selecting the substitution pattern of the hybrid. Key factors are the linking heteroatom (nitrogen vs. oxygen), the number of coumarin units joined to the BODIPY framework and the involved linking positions.Item Circularly Polarized Luminescence from Simple Organic Molecules(Chemistry: a european journal, 2015) Márquez Sánchez-Carnerero, Esther María; Rodríguez Agarrabeitia, Antonia; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Muller, Gilles; Ortiz García, María Josefa; Moya Cerero, Santiago De LaThis article aims to show the identity of “circularly polarized luminescent active simple organic molecules” as a new concept in organic chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and non-aggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.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; Ortiz 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.- Project number: 175
Item Del laboratorio al aula virtual en las prácticas de Química Orgánica(2021) Lora Maroto, Beatriz; Martínez Ruiz, María Paloma; Ortiz 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 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; Ortiz 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 A BODIPY-Based Fluorescent Sensor for Amino Acids Bearing Thiol(Proceedings, 2019) Avellanal-Zaballa, Edurne; Ramos Torres, Ágata; Prieto Castañeda, Alejandro; García Garrido, Fernando; Bañuelos, Jorge; Rodríguez Agarrabeitia, Antonia; Ortiz García, María JosefaHerein, we describe the synthetic route to access a red-emitting BODIPY from its α-diformylated precursor. The photophysical signatures of this dye are sensitive to the presence of thiol-containing amino acids (like cysteine, homocysteine, and glutathione) in the surrounding environment. This sensor provides up to three detection channels to monitor and quantify these biomolecules, even at low concentrations (down to micromolar). Moreover, owing to the pronounced splitting of the spectral band profile induced by these amino acids, the detection can be visualized following just the evolution of the fluorescence color by the naked eye.Item 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; Ortiz 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).Item Increased laser action in commercial dyes from fluorination regardless of their skeleton(Laser Physics Letters, 2014) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Arbeloa Lopez, Teresa; Bañuelos, Jorge; López Arbeloa, Iñigo; Chiara, José Luis; Garcia Moreno, Inmaculada; Ortiz García, María JosefaThe direct and simple fluorination of representative organic laser dyes with emission covering the entire visible spectrum, from blue to red, including Coumarin 460, Pyrromethene 546, Rhodamine 6G and Perylene Red, enhances laser efficiencies by a factor up to 1.8 with respect to the corresponding non-fluorinated parent dyes. More importantly, fluorination also significantly enhances the photostability of the dyes, even under drastic laser pumping conditions.