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The assembly of plasmonic nanoparticles with precise spatial and orientational order may lead to structures with new electromagnetic properties at optical frequencies. The directed self-assembly method presented controls the interparticle-spacing and symmetry of the resulting nanometer-sized elements in solution. The self-assembly of three-dimensional (3D), icosahedral plasmonic nanosclusters (NCs) with resonances at visible wavelengths is demonstrated experimentally. The ideal NCs consist of twelve gold (Au) nanospheres (NSs) attached to thiol groups at predefined locations on the surface of a genetically engineered cowpea mosaic virus with icosahedral symmetry. In situ dynamic light scattering (DLS) measurements confirm the NSs assembly on the virus. Transmission electron micrographs (TEM) demonstrate the ability of the self-assembly method to control the nanoscopic symmetry of the bound NSs, which reflects the icosahedral symmetry of the virus. Both, TEM and DLS show that the NCs comprise of a distribution of capsids mostly covered (i.e., 6-12 NS/capsid) with NSs. 3D finite-element simulations of aqueous suspensions of NCs reproduce the experimental bulk absorbance measurements and major features of the spectra. Simulations results show that the fully assembled NCs give rise to a 10-fold surface-averaged enhancement of the local electromagnetic field., (© 2014 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We demonstrate aqueous hydrogel-based microcontact printing of amine ligands into solvent-templated nanocavities of chloromethylphenyl-based siloxane or thin polymer films. Migration of pyridine ligands within films following printing, which can compromise pattern fidelity, is eliminated by heat treatment of the substrate. Gentle heating (e.g., 50 degrees C, 5 min) leads to the efficient alkylation of mobile pyridine adsorbate by the C-Cl bonds of the film, covalently tethering the adsorbate to the surface as a pyridinium salt. Subsequent binding of a Pd-based colloid to surface pyridinium (and remaining strongly bound and immobile pyridine ligand) sites permits selective electroless metal deposition and fabrication of patterned metal films.

We describe and characterize a simple process for the fabrication of patterned materials on polychloromethylstyrene thin film surfaces under ambient conditions. Patterned deep UV exposure (approximately 60 mJcm(-2), 193 nm) efficiently oxidizes the surface C-Cl bonds of the polymer film, producing an aldehyde species as the major photoproduct. Reductive amination in the presence of ammonium ion and cyanoborohydride reductant selectively converts the aldehyde into an alkylamine, which leads to an amine reactivity template on the film surface. The amines formed are sufficiently reactive to selectively and covalently bind fluorescent dye or electroless Ni metal to the template, which results in negative tone features with micron-scale resolutions (mask limited) in each case. Spectroscopic characterizations of the polymer surface following the photochemical transformation, reductive amination, and grafting steps are presented in support of the process. A key advantage of the method is the use of safe solvents, such as water or simple alcohols, to effect the reductive amination and grafting reactions. This approach mitigates waste disposal and associated environmental concerns, increasing the attractiveness of our method for use with high-throughput track-line processing equipment.