Dihalogenation of alkenes to the high-added value vicinal dihalides is a prominent process in modern synthetic chemistry. However, their effective conversion still requires the use of expensive and hazardous agents, sacrificial half-reaction coupling or primary energy input. Here, we show a photocatalytically assisted shuttle (p-shuttle) strategy for redox-neutral and reversible vicinal dihalogenation using low-cost and stable 1,2-dihaloethane under visible light illumination. Energetic hot electrons from metal-halide perovskite QDs enable the challenging photocatalytic reactions. Ultrafast laser transient absorption spectroscopy have unveiled the energy matching of the hot electrons with the high reduction potential of 1,2-dihaloethane, via two consecutive photoexcitation process. Powered by the sustainable energy as the only energy input, our new catalytic system using metal-halide perovskite QDs for dibromination, dichlorination and even unexplored hetero-dihalogenation, shows good tolerance with a wide range of alkenes at room temperature. In contrast to homogeneous photocatalysts, chalcogenide QDs and other semiconductor catalysts, perovskite QDs deliver previously unattainable performance in photoredox shuttle vicinal dihalogenation with the turnover number over 120,000. This work provides new opportunities in visible-light-driven heterogeneous catalysis for unlocking novel chemical transformations.
In this work, Arg-Gly-Asp (RGD) peptide-coupled polydopamine-modified mesoporous platinum nanoparticles (mPt@PDA-RGD NPs) were developed for targeted photothermal therapy (PTT) and migration inhibition of SKOV-3 cells. mPt@PDA-RGD NPs with obvious core/shell structure demonstrated high photothermal performance under 808-nm near-infrared (NIR) laser irradiation. mPt@PDA-RGD NPs with favorable biocompatibility exhibited remarkable SKOV-3 inhibition ability under NIR laser irradiation. Moreover, compared to mPt@PDA NPs, the RGD-functionalized NPs achieved more tumor uptake and PTT performance, which was attributed to the specific interaction between RGD of NPs and αvβ3 integrin overexpressed by SKOV-3. Importantly, cell scratch experiments indicated that the photothermal effect of mPt@PDA-RGD NPs can effectively inhibit the migration of surviving SKOV-3 cells, which was assigned to disturbance of the actin cytoskeleton of SKOV-3. Thus, mPt@PDA-RGD NPs presented great potential for targeted tumor photothermal ablation and migration inhibition.
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