Rodríguez Agarrabeitia, Antonia

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First Name
Last Name
Rodríguez Agarrabeitia
Universidad Complutense de Madrid
Faculty / Institute
Óptica y Optometría
Química Orgánica
Química Orgánica
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Now showing 1 - 10 of 20
  • Publication
    Mitochondria selective trackers for long-term imaging based on readily accessible neutral BODIPYs
    (RSC, 2021-05-28) 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 Josefa
    We 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.
  • Publication
    Exploring BODIPY Derivatives as Singlet Oxygen Photosensitizers for PDT
    (Wiley / American Society of Photobiology, 2020-04-20) 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, Virginia
    This 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.
  • Publication
    First Lanthanide Complex for de Novo Phasing in Native Protein Crystallography at 1 Å Radiation
    (American Chemical Society (ACS), 2021-04-29) 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.
  • Publication
    Exploring the Application of the Negishi Reaction of HaloBODIPYs: Generality, Regioselectivity, and Synthetic Utility in the Development of BODIPY Laser Dyes
    (ACS, 2016-05-06) Palao Utiel, Eduardo; Durán Sampedro, Gonzalo; Moya Cerero, Santiago de la; Madrid, Miriam; García López, Carmen; Rodríguez Agarrabeitia, Antonia; Verbelen, Bram; Dehaen, Wim; Boens, Nöel; Ortíz García, María Josefa
    The generality of the palladium-catalyzed C–C coupling Negishi reaction when applied to haloBODIPYs is demonstrated on the basis of selected starting BODIPYs, including polyhalogenated and/or asymmetrical systems, and organozinc reagents. This reaction is an interesting synthetic tool in BODIPY chemistry, mainly because it allows a valuable regioselective postfunctionalization of BODIPY chromophores with different functional groups. In this way, functional patterns that are difficult to obtain by other procedures (e.g., asymmetrically functionalized BODIPYs involving halogenated positions) can now be made. The regioselectivity is achieved by controlling the reaction conditions and is based on almost-general reactivity preferences, and the nature of the involved halogens and their positions. This ability is exemplified by the preparation of a series of new BODIPY dyes with unprecedented substitution patterns allowing noticeable lasing properties.
  • Publication
    C*-BODIPYs: Exploring a New Strategy to Transfer Chirality towards BODIPY Chiroptics
    (MDPI, 2020-01-20) Jiménez González, Josué; Sánchez Camacho, Juan; Moreno Jiménez, Florencio; Rodríguez Agarrabeitia, Antonia; Arbeloa, Teresa; Cabreros, Trevor A.; Muller, Gilles; Bañuelos, Jorge; Maroto, Beatriz Lora; Moya Cerero, Santiago de la
    C*-BODIPYs, that is, boron dipyrromethenes (BODIPYs) which have chiral carbons attached directly to the boron center, are introduced for the first time. These novel chiral BODIPYs mean a new strategy for the chiral perturbation of the inherently achiral BODIPY chromophore that is directed to enable chiroptical properties. Their preparation is very simple and only implies the complexation of a dipyrrin with an enantiopure dialkylborane having boron bonded to chiral carbons.
  • Publication
    AcetylacetonateBODIPY-Biscyclometalated Iridium(III) Complexes: Effective Strategy towards Smarter Fluorescent Photosensitizer Agents
    (Wiley, 2017-07-26) 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 Josefa
    Biscyclometalated 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, Weinheim
  • Publication
    FormylBODIPYs by PCC-Promoted Selective Oxidation of α-MethylBODIPYs. Synthetic Versatility and Applications
    (ACS (American Chemical Society), 2019-06) Ramos Torres, Ágata; Avellanal Zaballa, Edurne; Prieto Castañeda, Alejandro; García Garrido, Fernando; Bañuelos Prieto, Jorge; Rodríguez Agarrabeitia, Antonia; Ortíz García, María Josefa
    An efficient synthesis of formylBODIPYs has been established based on an oxidation with PCC of 3-methylBODIPYs. It has been demonstrated that this reagent can oxidize methyl groups at such position of the BODIPY core, regardless of its substitution pattern. Moreover, through this procedure it is possible to synthesize 8-aryl-3,5-diformylBODIPYs, which are otherwise difficult to obtain. These precursors have been functionalized to develop fluorescent sensors of amino acids or photosensitizers for singlet oxygen generation.
  • Publication
    Tailoring the Molecular Skeleton of Aza-BODIPYs to Design Photostable Red-Light-Emitting Laser Dyes
    (Wiley-VCH Verlag, 2018-11-28) Prieto Castañeda, Alejandro; Avellanal Zaballa, Edurne; Gartzia Rivero, Leire; Cerdán Pedraza, Luis; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; Bañuelos Prieto, Jorge; Ortíz García, María Josefa
    In this article the design and characterization of a set of novel red‐light‐emitting laser aza‐BODIPY dyes is reported. The applied synthetic method allows an exhaustive and versatile functionalization of both the dipyrrin core and the boron bridge. From the analysis of the photophysical and laser signatures, we determine the suitable modifications of the chromophoric backbone necessary to modulate the emission spectral region, efficiency and photostability under a strong irradiation regime. These dyes are endowed with efficient fluorescence and laser emission, and are particularly outstanding in terms of their high photostability, a key parameter to guarantee long‐lasting emission in any (bio)technological application. The herein‐reported results support, for the first time, the viability of aza‐BODIPYs as tunable red laser dyes. In fact, the laser performances of some of the tested aza‐BODIPYs surpass those of commercially available laser dyes in the same spectral region.
  • Publication
    Rational molecular design enhancing the photonic performance of red-emitting perylene bisimide dyes
    (Royal Society of Chemistry, 2017-04-25) Avellanal Zaballa, Edurne; Durán Sampedro, Gonzalo; Prieto Castañeda, Alejandro; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; López Arbeloa, Íñigo María; Bañuelos Prieto, Jorge; Ortíz García, María Josefa
    We 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.
  • Publication
    Generation of multiple triplet states in an orthogonal bodipy dimer: a breakthrough spectroscopic and theoretical approach
    (Royal Society of Chemistry, 2022-02-14) García Moreno, Inmaculada; Postils, Verónica; Rebollar, Esther; Ortíz García, María Josefa; Rodríguez Agarrabeitia, Antonia; Casanova, David
    Generation 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.