Hexagonal 2D arrays of Au nanorods support discrete plasmon resonance modes at visible and near-infrared wavelengths when coupled with light at normal incidence (k(z)). Reflectance spectra of nanorod arrays mounted on a thin Au baseplate reveal multiple resonant attenuations whose spectral positions vary with nanorod height and the dielectric medium. Simulations using 3D finite-element method calculations reveal harmonic sets of longitudinal standing waves in cavities between nanorods, reminiscent of acoustic waves generated by musical instruments. The nodes and antinodes of these quarter-wave plasmon modes are bounded, respectively, at the base and tips of the array. The number of harmonic resonances and their frequencies can be adjusted as a function of nanorod height, diameter-spacing ratio, and the refractive index of the host medium. Dispersion relations based on these standing-wave modes show strong retardation effects, attributed to the coupling of nanorods via transverse modes. Removal of the metal baseplate is predicted to result in resonant transmission through the Au nanorod arrays, at frequencies defined by half-wave modes within the open-ended cavities.
Pathogenic bacteria obtain the iron necessary for survival by releasing an iron chelator, termed a siderophore, and retrieving the iron-siderophore complex via a cell surface siderophore receptor. We have exploited the high affinity of Yersinia enterocolitica for its siderophore, deferoxamine, to develop a rapid method for capture and identification of Yersinia. In this methodology, a deferoxamine-bovine serum albumin conjugate is printed onto a gold-plated chip in a parallel line pattern. After flowing a suspension of Yersinia across the siderophore-derivatized chip, any Yersinia that binds to the chip is detected by dark-field microscopy analysis of the scattered light, followed by Fourier transform analysis of the scattering pattern. Since peak intensities are found to correlate with pathogen concentration, pathogen titers as low as 10(3) cfu/ml can be readily detected. Moreover, immobilized deferoxamine can distinguish Y. enterocolitica, which binds ferrioxamine (deferoxamine-Fe), from Staphylococcus aureus, Mycobacterium smegmatis and Pseudomonas aeruginosa, which don't. Because human pathogens cannot easily mutate their iron retrieval systems without loss of viability, we suggest that few if any mutant Yersinia will emerge that can avoid detection. Together with previous results demonstrating selective capture of Pseudomonas aeruginosa by its immobilized siderophore (pyoverdin), these data suggest that pathogen-specific siderophores may constitute effective and immutable capture ligands for rapid detection and identification of their cognate pathogens.
The rapid capture and label-free detection of Staphylococcus aureus , an opportunistic bacterium that can infect upon contact, can be performed using periodic microarrays of ligand-protein conjugates created by noncontact (inkjet) printing, darkfield imaging conditions, and a FFT-based readout method. Ink solutes were prepared using bovine serum albumin (BSA) conjugated to a glycan with high affinity for bacterial adhesins and printed as dot-matrix arrays with periodicities of 80-120 μm using a thermal injection method. Upon exposing the glycan-BSA microarrays to live strains of S. aureus , patterns emerge that can be detected under optical darkfield conditions. These patterns can be decoded by fast Fourier transform (FFT) analysis to generate fault-tolerant readout signals that correspond to the capture of S. aureus, with a limit of detection between 10(2) and 10(3) cfu/mL. Inkjet printing provides independent control over array periodicity, enabling FFT signals to be assigned to specific frequencies in reciprocal k-space.
Bi-exponential decay of dye fluorescence near the surface of plasmonic metamaterials and core-shell nanoparticles is shown to be an intrinsic property of the coupled system. Indeed, the Dicke, cooperative states involve two groups of transitions: super-radiant, from the most excited to the ground states and sub-radiant, which cannot reach the ground state. The relaxation in the sub-radiant system occurs mainly due to the interaction with the plasmon modes. Our theory shows that the relaxation leads to the population of the sub-radiant states by dephasing the super-radiant Dicke states giving rise to the bi-exponential decay in agreement with the experiments. We use a set of metamaterial samples consisting of gratings of paired silver nanostrips coated with Rh800 dye molecules, having resonances in the same spectral range. The bi-exponential decay is demonstrated for Au\SiO2\ATTO655 core-shell nanoparticles as well, which persists even when averaging over a broad range of the coupling parameter.
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