1. Triplet stabilization for enhanced drug photorelease from sunscreen-based photocages
- Author
-
Antonio Monari, Virginie Lhiaubet-Vallet, Mauricio Lineros-Rosa, M. Consuelo Cuquerella, Antonio Francés-Monerris, Miguel A. Miranda, Ministerio de Ciencia e Innovación (España), and Generalitat Valenciana
- Subjects
Drug ,Ultraviolet Rays ,media_common.quotation_subject ,UV filter ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Biochemistry ,chemistry.chemical_compound ,QUIMICA ORGANICA ,Hexanes ,Prodrugs ,Physical and Theoretical Chemistry ,media_common ,Propiophenones ,Quenching (fluorescence) ,Photolysis ,Photosensitizing Agents ,Ethanol ,010405 organic chemistry ,Organic Chemistry ,Anti-Inflammatory Agents, Non-Steroidal ,Acceptor ,0104 chemical sciences ,Hexane ,Solvent ,chemistry ,Models, Chemical ,Ketoprofen ,Excited state ,Solvents ,Avobenzone ,Sunscreening Agents - Abstract
[EN] Recently, sunscreen-based drug photocages have been introduced to provide UV protection to photoactive drugs, thus increasing their photosafety. Here, combined experimental and theoretical studies performed on a photocage based on the commercial UVA filter avobenzone (AB) and on the photosensitizing non-steroidal anti-inflammatory drug ketoprofen (KP) are presented unveiling the photophysical processes responsible for the light-triggered release. Particular attention is paid to solvent stabilization of the drug and UV filter excited states, respectively, which leads to a switching between the triplet excited state energies of the AB and KP units. Most notably, we show that the stabilization of the AB triplet excited state in ethanol solution is the key requirement for an efficient photouncaging. By contrast, in apolar solvents, in particular hexane, KP has the lowest triplet excited state, hence acting as an energy acceptor quenching the AB triplet manifold, thus inhibiting the desired photoreaction., Support from the Universite de Lorraine, CNRS, regional (Prometeo/2017/075) and Spanish Government (PGC2018-096684-B-I00, CTQ2017-87054-C2-2-P) is kindly acknowledged. A. F.-M. is grateful to Generalitat Valenciana and the European Social Fund (postdoctoral contract APOSTD/2019/149 and project GV/2020/226) for financial support. M. L.-R. acknowledges the Universitat Politecnica de Valencia for the FPI grant. All calculations have been performed on the local LPCT computer center and on the Explor regional center in the framework of the project "Dancing under the light".
- Published
- 2021