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Published online by Cambridge University Press: 04 February 2014
Hydrogen atom H (≡ proton + electron) transfer (HAT), is the most common reaction that involves the transfer of two elementary particles, a proton and an electron. Antioxidant, proton-coupled electron transfer (PCET) reactions involve also the transfer of two elementary particles, a proton and an electron. These constitute the fundamental step in a wide range of processes, chemical energy technologies, which rely on e–/H+ transfer from combustion and aerobic oxidations, to enzymatic catalysis and the destructive effects of reactive oxygen species in vivo. Here we describe a novel phenomenon, plasmonically-enhanced PCET, using nanothin silica-coated plasmonic Ag nanoparticles, functionalized with gallic acid, a natural antioxidant molecule, that is able to perform PCET. These nanoparticles can transfer rapidly electrons and protons to stable radicals. The kinetics and yield of these PCET reactions can be enhanced by plasmonic resonance modes excited by low-power, near-Infrared (785nm) laser irradiation. The demonstration that these plasmonic nanoparticles can enhance the HAT rates for both electrons and protons expands the traditional view of interfacial PCET. The occurrence of interfacial plasmon-enhancement of PCET brings together so far unrelated domains of nanoplasmonics, electron/proton translocation with significant impact on a variety of applications and most notably in theranostics.