Plasmonic acceleration of a photochemical replicator

The photoinduced decarbonylation of an α-diketone adduct generates 2,6-dimethoxyanthracene in the ground state. The photochemical product can also absorb the incoming photons and transfer its excitation energy to another molecule of the reactant to establish an autocatalytic loop. In the presence of silver nanoparticles, the efficiency of energy transfer increases significantly with a concomitant acceleration of the autocatalytic transformation. In principle, this mechanism to establish kinetic amplification can be extended to any photoactivatable fluorophore, if reactant and product can be engineered to satisfy the spectral requirements necessary for energy transfer. Furthermore, the resulting photochemical replicators can be exploited to monitor the influence of metallic nanostructures on photochemical reactions with convenient fluorescence measurements. In turn, the associated plasmonic effects offer the opportunity to accelerate autocatalysis with nanoscale resolution.