Dual-Fuel Driven Dissipative Self-Assembly of Gold Nanoparticles Enables Transient Conductivity

Inspired by the dynamic behavior of natural systems, which rely on a constant supply of energy to maintain structure and function, we have developed a synthetic platform that mimics such nonequilibrium behavior. Our system employs a chemically fueled mechanism to control the reversible assembly of gold nanoparticles in methanol. Central to this strategy is a dual-fuel approach involving 9-fluorenylmethoxycarbonyl chloride (Fmoc-Cl) and triethylamine (Et3N), both of which serve as activators, while Et3N subsequently functions as a deactivator. In this process, Fmoc groups are transiently attached to ligands on the AuNP surfaces, reducing polarity and inducing aggregation via solvophobic interactions. Meanwhile, Et3N facilitates a carbonate-forming reaction that gradually removes the hydrophobic Fmoc groups, restoring the system to its original dispersed state. A crucial design feature is that the fuel-driven attachment reaction occurs significantly faster than the cleavage, enabling precise temporal control over the assembly process across multiple cycles. Importantly, the extent of nanoparticle aggregation directly influences the electrical conductivity of the system, providing a chemically driven route to responsive, energy-dissipative nanomaterials with transient conductivity reminiscent of neuronal behavior. These findings lay the groundwork for the development of transient electronic devices, bioinspired memory, and smart materials that operate far from equilibrium–much like systems in nature.