Formylation as a Chemical Tool to Modulate the Performance of Photosensitizers Based on Boron Dipyrromethene Dimers.
Carolina Díaz-NorambuenaEdurne Avellanal-ZaballaAlejandro Prieto-CastañedaJorge BañuelosSantiago de la MoyaAntonia R AgarrabeitiaMaria J OrtizPublished in: International journal of molecular sciences (2023)
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.
Keyphrases
- photodynamic therapy
- living cells
- single molecule
- fluorescent probe
- energy transfer
- quantum dots
- fluorescence imaging
- induced apoptosis
- radiation therapy
- oxidative stress
- mass spectrometry
- gene expression
- electron transfer
- hepatitis c virus
- genome wide
- cell death
- men who have sex with men
- endoplasmic reticulum stress
- pi k akt