Person:
Rodríguez Agarrabeitia, Antonia

First Name

Antonia

Last Name

Rodríguez Agarrabeitia

URI

https://hdl.handle.net/20.500.14352/79886

Affiliation

Universidad Complutense de Madrid

Faculty / Institute

Óptica y Optometría

Department

Química Orgánica

Area

Química Orgánica

Identifiers

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Now showing 1 - 10 of 10

Circularly Polarized Luminescence by Visible-Light Absorption in a Chiral O-BODIPY Dye: Unprecedented Design of CPL Organic Molecules from Achiral Chromophores
(Journal of the American Chemical Society, 2014) Márquez Sánchez-Carnerero, Esther María; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Ortíz García, María Josefa; Vo, Bryan G.; Muller, Gilles; Moya Cerero, Santiago de la
Circularly polarized luminescence (CPL) in simple (small, nonaggregated, nonpolymeric) O-BODIPYs(R)-1 and (S)-1 by irradiation with visible light is first detected as proof of the ability of a new structural design to achieve CPL from inherently achiral monochromophore systems in simple organic molecules. The measured level of CPL (|glum|) in solution falls into the usual range of that obtained from other simple organic molecules (10−5−10−2range), but the latter having more complex architectures since axially chiral chromophores or multichromophore systems are usually required. The new design is based on chirally perturbing the acting achiral chromophore by orthogonally tethering a single axially chiral 1,1′-binaphtyl moiety to it. The latter does not participate as a chromophore in the light-absorption/emission phenom-enon. This simple design opens up new perspectives for the future development of new small-sized CPL organic dyes (e.g., those based on other highly luminescent achiral chromophores and/or chirally perturbing moieties), as well as for the improvement of the CPL properties of the organic molecules spanning their use in photonic applications.
Tailoring the Molecular Skeleton of Aza-BODIPYs to Design Photostable Red-Light-Emitting Laser Dyes
(ChemPhotoChem, 2018) 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.
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 María
Despite 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.
Spiranic BODIPYs: a ground-breaking design to improve the energy transfer in molecular cassettes
(Chemical Communications, 2014) Márquez Sánchez-Carnerero, Esther María; Gartzia-Rivero, Leire; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Ortiz García, María Josefa; Bañuelos Prieto, Jorge; López Arbeloa, Íñigo María; Moya Cerero, Santiago De La
Boosted excitation energy transfer in spiranic O BODIPY/polyarenecassettes, when compared with the parent non-spiranic (flexible) system, is highlighted as a proof for the ability of a new structural design to improve the energy transfer in molecular cassettes
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, Virginia
Three 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.
Bis(haloBODIPYs) with Labile Helicity: Valuable Simple Organic Molecules That Enable Circularly Polarized Luminescence
(Chemistry: a european journal, 2016) Ray Leiva, César; Márquez Sánchez-Carnerero, Esther María; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Ortiz García, María Josefa; López Arbeloa, Íñigo María; Bañuelos Prieto, Jorge; Cohovi, Komlan D.; Lunkley, jamie L.; Muller, Gilles; Moya Cerero, Santiago De La
Simple organic molecules (SOM) based on bis(haloBODIPY) are shown to enable circularly polarized luminescence (CPL), giving rise to a new structural design for technologically valuable CPL-SOMs. The established design comprises together synthetic accessibility, labile helicity, possibility of reversing the handedness of the circularly polarized emission, and reactive functional groups, making it unique and attractive as advantageous platform for the development of smart CPL-SOMs.
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 La
This 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.
FormylBODIPYs by PCC-Promoted Selective Oxidation of α-MethylBODIPYs. Synthetic Versatility and Applications
(Organic Letters, 2019) 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.
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 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
Halogen-free photosensitizers based on meso-enamine-BODIPYs for bioimaging and photodynamic therapy
(Journal of Materials Chemistry B, 2022) Prieto Montero, Ruth; Díaz Andrés, Aitor; Prieto Castañeda, Alejandro; Tabero Truchado, Andrea; Longarte Aldama, Asier; Rodríguez Agarrabeitia, Antonia; Villanueva Oroquieta, Ángeles; Ortíz García, María Josefa; Montero Santos, Raul; Casanova, David; Martínez Martínez, Virginia
The search for efficient heavy atom free photosensitizers (PSs) for photodynamic therapy (PDT) is a very active field. We describe herein a simple and easily accessible molecular design based on the attachment of an enamine group as an electron-donor moiety at the meso position of the BODIPY core with different alkylation patterns. The effect of the alkylation degree and solvent polarity on the photophysical properties in terms of splitting absorption bands, fluorescence efficiencies and singlet oxygen production is analyzed in depth experimentally using spectroscopic techniques, including femtosecond and nanosecond transient absorption (fs- and ns-TA) and using computational simulations based on time-dependent density functional theory. The correlation between the theoretical/experimental results permits the rationalization of the observed photophysical behavior exhibited by meso-enamine-BODIPY compounds and the determination of mechanistic details, which rule the population of the triplet state manifold. The potential applicability as a theragnostic agent for the most promising compound is demonstrated through in vitro assays in HeLa cells by analyzing the internalization, localization and phototoxic action.