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
15 results
Search Results
Now showing 1 - 10 of 15
Item 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 JosefaIn 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.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.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 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 BODIPYs revealing lipid droplets as valuable targets for photodynamic theragnosis(Chemical Communications, 2019) Tabero, Andrea; García-Garrido, Fernando; Prieto Castañeda, Alejandro; Palao, Eduardo; Rodríguez Agarrabeitia, Antonia; García-Moreno, Inmaculada; Villanueva Valdés, Miguel Ángel; Moya Cerero, Santiago De La; Ortiz, María JoséEndowing BODIPY PDT agents with the ability to probe lipid droplets is demonstrated to boost their phototoxicity, allowing the efficient use of highly fluorescent dyes (poor ROS sensitizers) as phototoxic agents. Conversely, this fact opens the way to the development of highly bright ROS photosensitizers for performing photodynamic theragnosis (fluorescence bioimaging and photodynamic therapy) from a single simple agent. On the other hand, the noticeable capability of some of the reported dyes to probe lipid droplets in different cell lines under different conditions reveals their use as privileged probes for advancing the study of interesting lipid droplets by fluorescence microscopy.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.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.Item 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 JosefaAn 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.