Instituto Universitario Mixto de Tecnologia Química UPV-CSIC, Universitat Politècnica de València, Consejo Superior de Investigaciones Científicas, Avda de los Naranjos s/n, 46022 Valencia, Spain.
Université de Lorraine and CNRS, LPCT UMR 7019, F-54000 Nancy, France.
Org Biomol Chem. 2021 Mar 4;19(8):1752-1759. doi: 10.1039/d0ob02244f.
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.
最近，基于防晒霜的药物光解笼已被引入，以向光活性药物提供紫外线保护，从而提高其光安全性。在这里，我们对基于商业 UVA 滤光剂阿伏苯宗 (AB) 和光致敏非甾体抗炎药酮洛芬 (KP) 的光解笼进行了实验和理论相结合的研究，揭示了光触发释放的光物理过程。特别关注药物和 UV 滤光剂激发态的溶剂稳定化，这分别导致 AB 和 KP 单元的三重态激发态能量之间的切换。值得注意的是，我们表明，乙醇溶液中 AB 三重态激发态的稳定化是光解笼高效的关键要求。相比之下，在非极性溶剂中，特别是己烷中，KP 具有最低的三重态激发态，因此作为能量受体猝灭 AB 三重态系综，从而抑制所需的光反应。
