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    Seeded Growth Synthesis of Gold Nanotriangles: Size Control, SAXS Analysis, and SERS Performance
    (Washington, DC : Soc., 2018) Kuttner, Christian; Mayer, Martin; Dulle, Martin; Moscoso, Ana; López-Romero, Juan Manuel; Förster, Stephan; Fery, Andreas; Pérez-Juste, Jorge; Contreras-Cáceres, Rafael
    We studied the controlled growth of triangular prismatic Au nanoparticles with different beveled sides for surface-enhanced Raman spectroscopy (SERS) applications. First, in a seedless synthesis using 3-butenoic acid (3BA) and benzyldimethylammonium chloride (BDAC), gold nanotriangles (AuNTs) were synthesized in a mixture with gold nanooctahedra (AuNOCs) and separated by depletion-induced flocculation. Here, the influence of temperature, pH, and reducing agent on the reaction kinetics was initially investigated by UV–vis and correlated to the size and yield of AuNT seeds. In a second step, the AuNT size was increased by seed-mediated overgrowth with Au. We show for the first time that preformed 3BA-synthesized AuNT seeds can be overgrown up to a final edge length of 175 nm and a thickness of 80 nm while maintaining their triangular shape and tip sharpness. The NT morphology, including edge length, thickness, and tip rounding, was precisely characterized in dispersion by small-angle X-ray scattering and in dry state by transmission electron microscopy and field-emission scanning electron microscopy. For sensor purposes, we studied the size-dependent SERS performance of AuNTs yielding analytical enhancement factors between 0.9 × 104 and 5.6 × 104 and nanomolar limit of detection (10–8–10–9 M) for 4-mercaptobenzoic acid and BDAC. These results confirm that the 3BA approach allows the fabrication of AuNTs in a whole range of sizes maintaining the NT morphology. This enables tailoring of localized surface plasmon resonances between 590 and 740 nm, even in the near-infrared window of a biological tissue, for use as colloidal SERS sensing agents or for optoelectronic applications.
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    Protein-Assisted Assembly of Modular 3D Plasmonic Raspberry-like Core/Satellite Nanoclusters: Correlation of Structure and Optical Properties
    (Washington, DC : Soc., 2016) Höller, Roland P. M.; Dulle, Martin; Thomä, Sabrina; Mayer, Martin; Steiner, Anja Maria; Förster, Stephan; Fery, Andreas; Kuttner, Christian; Chanana, Munish
    We present a bottom-up assembly route for a large-scale organization of plasmonic nanoparticles (NPs) into three-dimensional (3D) modular assemblies with core/satellite structure. The protein-assisted assembly of small spherical gold or silver NPs with a hydrophilic protein shell (as satellites) onto larger metal NPs (as cores) offers high modularity in sizes and composition at high satellite coverage (close to the jamming limit). The resulting dispersions of metal/metal nanoclusters exhibit high colloidal stability and therefore allow for high concentrations and a precise characterization of the nanocluster architecture in dispersion by small-angle X-ray scattering (SAXS). Strong near-field coupling between the building blocks results in distinct regimes of dominant satellite-to-satellite and core-to-satellite coupling. High robustness against satellite disorder was proved by UV/vis diffuse reflectance (integrating sphere) measurements. Generalized multiparticle Mie theory (GMMT) simulations were employed to describe the electromagnetic coupling within the nanoclusters. The close correlation of structure and optical property allows for the rational design of core/satellite nanoclusters with tailored plasmonics and well-defined near-field enhancement, with perspectives for applications such as surface-enhanced spectroscopies.
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    Mechanotunable Surface Lattice Resonances in the Visible Optical Range by Soft Lithography Templates and Directed Self-Assembly
    (Washington, DC : Soc., 2019) Gupta, Vaibhav; Probst, Patrick T.; Goßler, Fabian R.; Steiner, Anja Maria; Schubert, Jonas; Brasse, Yannic; König, Tobias A.F.; Fery, Andreas
    We demonstrate a novel colloidal self-assembly approach toward obtaining mechanically tunable, cost-efficient, and low-loss plasmonic nanostructures that show pronounced optical anisotropy upon mechanical deformation. Soft lithography and template-assisted colloidal self-assembly are used to fabricate a stretchable periodic square lattice of gold nanoparticles on macroscopic areas. We stress the impact of particle size distribution on the resulting optical properties. To this end, lattices of narrowly distributed particles (∼2% standard deviation in diameter) are compared with those composed of polydisperse ones (∼14% standard deviation). The enhanced particle quality sharpens the collective surface lattice resonances by 40% to achieve a full width at half-maximum as low as 16 nm. This high optical quality approaches the theoretical limit for this system, as revealed by electromagnetic simulations. One hundred stretching cycles demonstrate a reversible transformation from a square to a rectangular lattice, accompanied by polarization-dependent optical properties. On the basis of these findings we envisage the potential applications as strain sensors and mechanically tunable filters. © 2019 American Chemical Society.