Anisotropic Gold Nanomaterial Synthesis Using Peptide Facet Specificity and Timed Intervention.

ABSTRACT

Thin metal particles with two-dimensional (2D) symmetry are attractive for multiple applications but are difficult to synthesize in a reproducible manner. Although molecules that selectively adsorb to facets have been used to control nanoparticle shape, there is still limited research into the temporal control of growth processes to control these structural outcomes. Moreover, much of the current research into the growth of thin 2D particles lacks mechanistic details. In this work, we study why the substitution of isoleucine for methionine in a gold-binding peptide (Z2, RMRMKMK) results in an increase in gold nanoparticle anisotropy. Nanoplatelet growth in the presence of Z2M246I (RIRIKIK) is characterized using in situ small-angle X-ray scattering (SAXS) and UV-vis spectroscopy. Fitting time-resolved SAXS profiles reveal that 10 nm-thick particles with 2D symmetry are formed within the first few minutes of the reaction. Next, through a combination of electron diffraction and molecular dynamics simulations, we show that substitution of methionine for isoleucine increases the (111) facet selectivity in Z2M246I, and we conclude that this is key to the growth of nanoplatelets. However, the potential application of nanoplatelets formed using Z2M246I is limited due to their uncontrolled lateral growth, aggregation, and rapid sedimentation. Therefore, we use a liquid-handling robot to perform temporally controlled synthesis and dynamic intervention through the addition of Z2 to nanoplatelets grown in the presence of Z2M246I at different times. UV-vis spectroscopy, dynamic light scattering, and electron microscopy show that dynamic intervention results in control over the mean size and stability of plate-like particles. Finally, we use in situ UV-vis spectroscopy to study plate-like particle growth at different times of intervention. Our results demonstrate that both the selectivity and magnitude of binding free energy toward lattices are important for controlling nanoparticle growth pathways.