Person:
Moya Cerero, Santiago De La

First Name

Santiago De La

Last Name

Moya Cerero

URI

https://hdl.handle.net/20.500.14352/76266

Affiliation

Universidad Complutense de Madrid

Faculty / Institute

Ciencias Químicas

Department

Química Orgánica

Area

Química Orgánica

Identifiers

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Now showing 1 - 10 of 13

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, 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.
Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry
(Physical Chemistry Chemical Physics, 2023) García Martínez, Antonio; Siehl, Hans-Ulrich; Moya Cerero, Santiago De La; Gómez Calzada, Pedro Carlos
An expeditious procedure for the challenging computation of the free energy barriers (DGa) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)// PCM method, and it allows the easy, accurate and inexpensive prediction of these barriers for carbocations of very different stability. This method was validated by the fair mean absolute error (ca. 1.5 kcal mol1 ) achieved in the prediction of 19 known experimental barriers covering a range of ca. 50 kcal mol1 . Interestingly, the new procedure also uses an original method for the calculation of the required inner reorganization energy (Li ) and free energy of reaction (DG). This procedure should pave the way to face computationally the pivotal issue of carbocation chemistry and could be easily extended to any bimolecular organic reaction.
A Computational-Experimental Approach to Unravel the Excited State Landscape in Heavy-Atom Free BODIPY-Related Dyes
(Molecules, 2022) Rebollar, Esther; Bañuelos, Jorge; Moya Cerero, Santiago De La; Eng, Julien; Penfold, Thomas; Garcia-Moreno, Inmaculada
We performed a time-gated laser-spectroscopy study in a set of heavy-atom free single BODIPY fluorophores, supported by accurate, excited-state computational simulations of the key low-lying excited states in these chromophores. Despite the strong fluorescence of these emitters, we observed a significant fraction of time-delayed (microseconds scale) emission associated with processes that involved passage through the triplet manifold. The accuracy of the predictions of the energy arrangement and electronic nature of the low-lying singlet and triplet excited states meant that an unambiguous assignment of the main deactivation pathways, including thermally activated delayed fluorescence and/or room temperature phosphorescence, was possible. The observation of triplet state formation indicates a breakthrough in the “classic” interpretation of the photophysical properties of the renowned BODIPY and its derivatives.
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 Josefa
We 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.
Unprecedented induced axial chirality in a molecular BODIPY dye: strongly bisignated electronic circular dichroism in the visible region
(Chemical Communications, 2013) Márquez Sánchez-Carnerero, Esther María; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Bañuelos Prieto, Jorge; Arbeloa, Teresa; López Arbeloa, Íñigo María; Ortiz García, María Josefa; Moya Cerero, Santiago De La
Enantiomeric bis(BODIPYs) 1a and 1b exhibit strong bisignated ECD due to the formation of a stable helical conformation with induced axial chirality, which allows efficient excito coupling of the BODIPY chromophores in the Vis region.
Dissimilar-at-boron N-BODIPYs: from light-harvesting multichromophoric arrays to CPL-bright chiral-at-boron BODIPYs
(Organic Chemistry Frontiers, 2023) Ray, César; Avellanal-Zaballa, Edurne; Muñoz Úbeda, Mónica; Colligan, Jessica; Moreno Jiménez, Florencio; Muller, Gilles ; López Montero, Iván; Bañuelos, Jorge; Lora Maroto, Beatriz; Moya Cerero, Santiago De La
We report a workable and easy approach for the direct post-multifunctionalization of common BODIPYs (F-BODIPYs) with minimal interference to the starting photophysical behavior. It entails the easy transformation of an F-BODIPY into the corresponding N-BODIPY by using a dissimilarly-N,N′-disubstituted bis(sulfonamide), which is easily obtained from ethane-1,2-diamine. This approach is exemplified by the rapid synthesis of a selected battery of unprecedented dissimilar-at-boron N-BODIPYs, which are rationally designed to act as efficient multichromophoric arrays for light harvesting by excitation energy transfer, as specific bioprobes for fluorescent imaging, or as efficient chiroptical dyes exhibiting visible circular dichroism and circularly polarized luminescence. Noticeably, this approach has led to the synthesis of the first CPL-bright chiral-at-boron BODIPYs, a significant novelty in BODIPY chemistry and CPL emitters
Manipulating Charge-TransferStates in BODIPYs: A ModelStrategy to Rapidly Develop Photodynamic Theragnostic Agents
(Chemistry: a european journal, 2020) Jiménez González, Josué; Prieto Montero, Ruth; Lora Maroto, Beatriz; Moreno Jiménez, Florencio; Ortiz García, María Josefa; Oliden Sánchez, Ainhoa; López Arbeloa, Íñigo María; Martínez Martínez, Virginia; Moya Cerero, Santiago De La
On the basis of a family of BINOL (1,1′-bi-2-naphthol)-based O-BODIPY (dioxyboron dipyrromethene) dyes, it is demonstrated that chemical manipulation of the chromophoric push–pull character, by playing with the electron-donating capability of the BINOL moiety (BINOL versus 3,3'-dibromoBINOL) and with the electron-acceptor ability of the BODIPY core (alkyl substitution degree), is a workable strategy to finely balance fluorescence (singlet-state emitting action) versus the capability to photogenerate cytotoxic reactive oxygen species (triplet-state photosensitizing action). It is also shown that the promotion of a suitable charge-transfer character in the involved chromophore upon excitation enhances the probability of an intersystem crossing phenomenon, which is required to populate the triple state enabling singlet oxygen production. The reported strategy opens up new perspectives for rapid development of smarter agents for photodynamic theragnosis, including heavy-atom-free agents, from a selected organic fluorophore precursor.
Electron ionization-induced fragmentation of bridgehead-substituted norbornan-2-ones derived from fenchone
(International journal of mass spectrometry, 2012) Teso Vilar, Enrique; García Martínez, Antonio; García Fraile, Amelia; Moya Cerero, Santiago De La; Martínez Ruiz, María Paloma; Moreno Jiménez, Florencio
Camphor- and fenchone-based bridgehead-substituted norbornan-2-ones constitute an interesting class of chiral synthons with applications in stereoselective synthesis, due to the wide variety of stereo-controlled transformations which they can undergo. Despite their synthetic value, few mass spectral studies have been realized for these compounds due to the lack of general procedures for their preparation. In this paper we have carried out an electron ionization (EI) mass spectral study of a series of heteroatomically bridgehead-substituted 7,7-dimethylnorbornan-2-ones. Their cleavage mechanisms have been rationalized on the basis of the substituent shifts, as well as on the identification of relevant peaks through accurate mass measurements and collision-induced dissociation (CID) tandem mass-spectrometric experiments. The driving force for the main fragmentation pathways of C(1)-O- and C(1)-N-substituted 7,7-dimethylnorbornan-2-ones is the alpha-cleavage of the C(1) C(2) bond directed by the bridgehead substituent. Further rearrangements and fragmentations of the distonic ions initially formed lead to the major ions in the spectra of all the compounds. A comparison with the known behaviour of their isomeric 3,3-dimethylnorbornan-2-ones reveals that the key bridgehead heteroatom effect controlling the fragmentation pathways can be modulated by the position of the gem-dimethyl group. As a consequence, the corresponding fragmentation patterns of both isomeric series are very different. In contrast, the fragmentation patterns of 7,7-dimethyl-2-oxo-norbornanesulphonamides, whose main fragmentation pathway involves homolytic S N bond cleavage, are almost identical to those displayed by their 3,3-dimethylated isomers
An asymmetric BODIPY triad with panchromatic absorption for high-performance red-edge laser emission
(Chemmical Communications, 2015) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Garcia-Moreno, Inmaculada ; Gartzia-Rivero, Leire; Bañuelos, Jorge; López-Arbeloa, Ínigo; Ortiz García, María Josefa; Moya Cerero, Santiago De La
A rational design of an unprecedented asym. cassette triad based entirely on BODIPY chromophores allows efficient light harvesting over the UV-vis spectral region, leading to a bright and stable red-edge laser emission via efficient energy-transfer processes.
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.