Approaches are needed for the tailored assembly of plasmonic building blocks on the surface of substrates to synergistically enhance their properties. Here we demonstrate selective immobilization and assembly of gold nanorods (NRs) on substrates modified and patterned with end-grafted poly(ethylene glycol) (PEG) layers. The ligand exchange from the initial cetyltrimethylammonium bromide to sodium citrate was necessary for the immobilization of gold NRs onto PEG grafted substrates. Linear nanopatterns of PEG were fabricated using electrospun nanofibers as masks in oxygen plasma etching. The selective immobilization of citrate-stabilized gold NRs with a length of ∼50 nm and a width of 20 nm on the nanopatterned PEG layers led to linear and registered arrays of rods. The number of gold NRs per line depended on the width of the patterns and approached 1 when the width of the patterns was comparable to the length of the rods. The confinement of the binding regions led to a ∼3 fold increase in the number of gold NRs immobilized per unit area. The selective and dense immobilization of gold NRs on the nanoscale patterns of PEG resulted in spatially defined and strong surface-enhanced Raman scattering activity enabling detection of molecules at concentrations as low as 1 nM.
Perovskite nanocrystals (PNCs) are emerging luminescent materials for a wide range of technological applications. The broad adaptation of PNCs will be greatly improved by addressing their intrinsically low stability and developing processes for their assembly into 2D and 3D structures using facile approaches. Inspired by the mechanism of natural protection of leaves, this paper proposes natural carnauba wax (CW) as an encapsulation material for PNCs. The synthesis of PNCs is performed in the presence of CW, which is derived from the leaves of Copernicia prunifera palm. CW acts as a solvent and replaces the commonly used octadecene in the preparation of PNCs. The facile synthesis in CW results in PNCs with greatly improved thermal, water, and air stability. Furthermore, the thermal and mechanical properties make PNC-Wax a highly suitable solid ink for versatile processing of these materials into 2D and 3D architectures. PNC-Wax can be printed via a pen-on-paper approach by heating at modest temperatures. The rapid plasticization of PNC-Wax by mechanical agitation enables hand-shaping of the material in a manner similar to playdoughs, which would possibly enable the versatile use of this material for various applications.
We report completely sustainable processes and materials for inexpensive and scalable fabrication of plasmonically active solid substrates, which are critical for emerging applications in sensing, catalysis, and metasurfaces. Our approach involves grafting of poly(ethylene glycol) (PEG) onto silicon oxide terminated solid substrates using all-water based processing leading to an ultrathin (12 nm) and smooth (roughness of ∼1 nm) functional layer. The resulting surfaces facilitate robust and effective immobilization of gold nanoparticles (NPs) with a density that is superior to the organic solvent based processing. This new process achieves size dependent assembly of the citrate-stabilized gold NPs resulting in high plasmonic activity in surface-enhanced Raman scattering (SERS). The use of leaf extracts derived from Quercus pubescens as a reducing and stabilizing agent allowed for green synthesis of gold NPs with an average diameter of 25.6 ± 11.1 nm. The assembly of the green synthesized gold NPs on all-water processed PEG grafted layers enabled a fully sustainable route for fabrication of plasmonically active solid substrates. The resulting substrates exhibited high SERS response over the entire (∼1 cm 2 ) substrate surface with an analytical enhancement factor of 9.48 × 10 4 for the probe molecule rhodamine 6G under 532 nm laser excitation. A microfluidic device was also constructed on the fabricated platform for SERS mediated simultaneous detection of two nonsteroidal anti-inflammatory drugs, dexketoprofen and ibuprofen, which are widely used in human medicine and present as contaminants in wastewater. The biocompatibility of PEG together with all-water based processing overcome the need for waste management and ventilation of the working place enabling cost and energy efficient, environmentally benign fabrication of plasmonic devices.
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