Alessandri Ivano
Sustainable Chemistry and Materials Group, Department of Information Engineering, University of Brescia, Italy.
INSTM, Consorzio Nazionale per la Scienza e Tecnologia dei Materiali, RU Brescia, via Branze 38, 25123, Brescia, Italy.
Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202205013. doi: 10.1002/anie.202205013. Epub 2022 May 19.
The photodimerization of 4-aminothiophenol (PATP) into 4,4'-dimercaptobenzene (DMAB) has been extensively utilized as a paradigm reaction to probe the role of surface plasmons in nanoparticle-mediated light-driven processes. Here I report the first observation of the PATP-to-DMAB photoreaction in the absence of any plasmonic mediators. The reaction was observed to occur with different kinetics either for PATP adsorbed on non-plasmonic nanoparticles (TiO , ZnO, SiO ) or deposited as macroscopic droplets. Confocal microRaman spectroscopy enabled to investigate the reaction progress in different plasmon-free contexts, either aerobic or anaerobic, suggesting a new interpretation of the photodimerization process, based on direct laser-induced activation of singlet oxygen species. These results provide new insights in light-driven redox processes, elucidating the role of sample morphology, light and oxygen.
4-氨基硫酚（PATP）光二聚化为4,4'-二巯基苯（DMAB）已被广泛用作范例反应，以探究表面等离子体激元在纳米颗粒介导的光驱动过程中的作用。在此，我报告了在没有任何等离子体激元介质的情况下首次观察到PATP到DMAB的光反应。观察到，无论是吸附在非等离子体激元纳米颗粒（TiO、ZnO、SiO）上的PATP，还是以宏观液滴形式沉积的PATP，反应都以不同的动力学发生。共焦显微拉曼光谱能够研究在有氧或无氧的不同无等离子体激元环境中的反应进程，这表明基于单重态氧物种的直接激光诱导活化，对光二聚化过程有了新的解释。这些结果为光驱动的氧化还原过程提供了新的见解，阐明了样品形态、光和氧的作用。
