Silver(I)-induced anisotropy in the plasmon-driven growth of nanoscale gold

ABSTRACT

The plasmon-mediated synthesis of anisotropic gold nanoparticles (AuNPs) has only recently been investigated and achieved. This process typically utilizes the surface plasmon resonances (SPRs) of the nanoparticles themselves to drive metal deposition and growth. Many of the traditional methods for shape control, including use of functional surfactants and etchants, have yet to be utilized within the context of light-driven synthesis. Here, the underpotential deposition of Ag(I) is utilized as a shape-controlling strategy in a hot electron-driven photochemical synthesis to grow anisotropic gold nanoparticles. The strategy also relies on L-pyroglutamic acid, a natural amino acid metabolite, as a photochemical relay aiding in the transport and localization of plasmon-generated hot electrons. By carefully adjusting reagent concentrations, the morphologies of the resulting nanoparticles can be facilely tuned from spheres to nanostars and nanoflowers. The high extinction in the NIR region of the ‘ideal’ gold nanostars synthesized advocates their use as photothermal therapy agents, supported by a sufficient photothermal conversion efficiency (η = 30.8%) under 808 nm CW laser irradiation. This contribution expands the repertoire of gold nanostructures accessible to visible-light-driven plasmonic photochemistry.

Different gold nanoparticle shapes have been accessed using a plasmon-mediated growth technique. Ag(I) ions induce symmetry breaking, yielding nano-sized gold spheres, stars, and flowers. A specialized photoreactor, equipped with 505 nm LED illumination, facilitates the transfer of hot electrons from a pre-made gold nanocube seed surface. Gold reduction and deposition occur, and anisotropic structures grow with the aid of L-pyroglutamic acid and Triton X-100 as coordinating and shape-directing agents.

GRAPHICAL ABSTRACT

KEYWORDS:

• Gold nanoparticles
• plasmon-mediated
• branched nanostructures
• underpotential deposition
• photothermal therapy

Disclosure statement

No potential conflict of interest was reported by the author(s).