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Plasmonic nanoparticles (NPs) have garnered excitement over the past several decades stemming from their unique optoelectronic properties, leading to their use in various sensing applications and theranostics. Symmetry dictates the properties of many nanomaterials, and nanostructures with low, but still defined symmetries, often display markedly different properties compared to their higher symmetry counterparts. While numerous methods are available to manipulate symmetry, surface protecting groups such as polymers are finding use due to their ability to achieve regioselective modification of NP seeds, which can be removed after overgrowth as shown here. Specifically, poly(styrene- b -polyacrylic acid) (PSPAA) is used to asymmetrically passivate cubic Au seeds through competition with hexadecyltrimethylammonium bromide (CTAB) ligands. The asymmetric passivation via collapsed PSPAA causes only select vertices and faces of the Au cubes to be available for deposition of new material ( i.e. , Au, Au–Ag alloy, and Au–Pd alloy) during seeded overgrowth. At low metal precursor concentrations, deposition follows observations from unpassivated seeds but with new material growing from only the exposed seed portions. At high metal precursor concentrations, nanobowl-like structures form from interaction between the depositing phase and the passivating PSPAA. Through experiment and simulation, the optoelectronic properties of these nanobowls were probed, finding that the interiors and exteriors of the nanobowls can be functionalized selectively as revealed by surface enhanced Raman spectroscopy (SERS). 

Bimetallic gold–palladium particles were originally proposed as catalysts with tunable reaction rates. Following the development of synthesis routes that offer better control on the morphology and composition of the particles, novel optical sensing functionalities were more recently proposed. Since temperature is a fundamental parameter that interplays with every other proposed application, we studied the light-to-heat conversion ability of Au/Pd bimetallic nanoparticles with a regular octapodal shape. Both compositional (Au-to-Pd ratio) and structural (diagonal tip-to-tip distance and tip width) characteristics were screened and found to be essential control parameters to promote light absorption and efficient conversion into heat. Electromagnetic simulations reveal that the Pd content, and specifically its distribution inside the branched particle geometry, has a profound impact on the optical properties and is an essential criterion for efficient heating. Notably, the optical and photothermal responses are shown to remain stable throughout extended illumination, with no noticeable structural changes to the branched nanocrystals due to heat generation.