Adenosine Triphosphate Harnessed Transient Aggregations of Nanoparticles for Efficient Nanoreactors in Water

Living cells utilize diverse biochemical reactions occurring in microcompartments to regulate important biological functions. Although transient nanoreactors mediated by diverse fuels are achieved in discrete nanoassemblies of synthetic building blocks, the slow diffusion of substrates in and out of these solvent-dispersed nanoassemblies greatly compromises the reaction efficiency. Herein, we report adenosine triphosphate (ATP)-driven transient aggregation of nanoreactors that enable the acceleration of nucleophilic aromatic substitution (S_NAr) in an aqueous solution. This system is composed of nanoparticles self-assembled from an amphiphilic molecule containing an ATP receptor, ATP, and potato apyrase (PA). The sequential addition of ATP and PA results in a reversible aggregation and disaggregation of the nanoparticles, which serve as smart nanoreactors to accelerate the S_NAr reaction on demand. Notably, this reaction is temporally regulated by the autonomous aggregation and disaggregation of the nanoparticles. Furthermore, the azobenzene moiety in amphiphilic molecules allows the further modulation of the S_NAr reaction in the nanoreactors using ultraviolet light.