DNA-templated plasmonic Ag/AgCl nanostructures for molecular selective photocatalysis and photocatalytic inactivation of cancer cells†
Silver halide (AgX, X = Cl, Br, I)-based materials represent an emerging class of heterogeneous photocatalysts. Despite progress in the synthesis of carrier-separated AgX-based photocatalysts, a number of issues remain unaddressed, including complicated synthesis, unfavorably large size and therefore poor photocatalytic performance of the resultant structures. Here we show the one-step DNA-programmable synthesis of Ag/AgCl nanostructures that takes only approximately 1 min for photocatalytic application. The optimal DNA-encapsulated structures show DNA sequence-specific sizes down to less than 40 nm with a Ag/AgCl composition ratio of 2 : 1, affording a vastly increased surface area and higher photocatalytic activity than any Ag/AgX nanostructures reported previously by over two orders of magnitude. From a physical standpoint, importantly, the plasmonic nanostructured silver in Ag/AgCl accelerates the photocatalytic reaction in terms of fast electron injection to AgCl, leading to enhanced hole–electron separation and high-performance photocatalysis under visible light. To test the effect of DNA encapsulation on the Ag/AgCl nanostructures, both positively and negatively charged organic compounds serve as the model pollutants to assess their photocatalytic selectivity. Our results show that the photodecomposition of the positively charged compounds obeys a first-order rate law, whereas the negatively charged compound is decomposed with zero-order kinetics. This comparison offers a mechanistic insight into reaction kinetics on the DNA-encapsulated photocatalyst. We further find that the DNA-encapsulated Ag/AgCl photocatalysts are robust and can be recycled. To extend the applicability of the Ag/AgCl nanostructures, their use in the efficient photocatalytic inactivation of cancer cells is also demonstrated for the first time, opening up a new avenue to daylight-based theranostics.