Harnessing polymer grafting to control the shape of plasmonic nanoparticles

Matrix-free polymer grafted nanoparticles (NPs) are single component polymer nanocomposites (PNCs) for which the often reported severe aggregation of the conventional PNCs can be suppressed. For a given particle core, the size and shape of the polymer grafted nanoparticles can be controlled by the molecular weight of the polymer and its grafting density. However, the degree of homogeneity of one-component PNCs depends on the grafted chain molecular weight and grafting density, as well as on the shape of grafted NPs. Surface plasmon resonance enhanced dynamic light scattering from very dilute solutions, yielding both translational and rotational transport coefficients, complemented by UV–Vis extinction spectra, can detect deviations from spheres. Here, we report that poly(isobutylene)-grafted Ag NPs strongly deviate from the spherical shape and are modeled as prolate spheroids. This NP asphericity, due to inhomogeneous grafting, can impact the structure and properties of plasmonic PNCs in the solid state. Thus, characterizing this behavior is a crucial step prior to the formation of one-component PNCs.Matrix-free polymer grafted nanoparticles (NPs) are single component polymer nanocomposites (PNCs) for which the often reported severe aggregation of the conventional PNCs can be suppressed. For a given particle core, the size and shape of the polymer grafted nanoparticles can be controlled by the molecular weight of the polymer and its grafting density. However, the degree of homogeneity of one-component PNCs depends on the grafted chain molecular weight and grafting density, as well as on the shape of grafted NPs. Surface plasmon resonance enhanced dynamic light scattering from very dilute solutions, yielding both translational and rotational transport coefficients, complemented by UV–Vis extinction spectra, can detect deviations from spheres. Here, we report that poly(isobutylene)-grafted Ag NPs strongly deviate from the spherical shape and are modeled as prolate spheroids. This NP asphericity, due to inhomogeneous grafting, can impact the structure and properties of plasmonic PNCs in the solid state. ...