ABSTRACT
We demonstrate the fabrication of novel functional gel coatings with randomized physical and chemical patterns that enable dual encoding ability to realize unclonable optical tags. This design is based on swelling-mediated massive reconstruction of an ultrathin responsive gelatinous polymer film uniformly adsorbed with plasmonic nanostructures into a randomized network of interacting folds, resulting in bright electromagnetic hotspots within the folds. We reveal a strong correlation between the topology and near-field electromagnetic field enhancement due to the intimate contact between two plasmonic surfaces within the folds, each of them representing a unique combination of local topography and chemical distribution caused by the formation of electromagnetic hotspots. Because of the efficient trapping of the Raman reporters within the uniquely distributed electromagnetic hotspots, the surface enhanced Raman scattering enhancement from the morphed plasmonic gel was found to be nearly 40 times higher compared to that from the pristine plasmonic gel. Harnessing the nondeterministic nature of the folds, the folded plasmonic gel can be employed as a multidimensional (with dual topo-chemical encoding) optical taggant for prospective anticounterfeiting applications. Such novel optical tags based on the spontaneous folding process are virtually impossible to replicate because of the combination of nondeterministic physical patterns and chemical encoding.
ABSTRACT
The bio-enabled synthesis of a novel class of surface enhanced Raman scattering probes is presented for functional imaging with built-in and accessible electromagnetic hotspots formed between densely packed satellites grown on a plasmonic core. The superstructures serve as nanoscale sensors to spatiotemporally map intravesicular pH changes along endocytic pathways inside live cells.
Subject(s)
Gold/chemistry , Metal Nanoparticles/chemistry , Cell Line, Tumor , Cell Tracking , Exocytosis , Humans , Metal Nanoparticles/ultrastructure , Polystyrenes/chemistry , Spectrum Analysis, RamanABSTRACT
The synthesis of plasmonic nanorattles with accessible electromagnetic hotspots that facilitate highly sensitive detection of chemical analytes using surface enhanced Raman scattering (SERS) is demonstrated. Raman spectra obtained from individual nanorattles demonstrate the significantly higher SERS activity compared to solid plasmonic nanostructures.
ABSTRACT
In this work, we demonstrate that plasmonic nanostructures can be employed as nanoscale transducers to monitor the growth and phase transitions in ultrathin polymer films. In particular, gold nanorods with high refractive index sensitivity (~150 nm/refractive index unit (RIU)) were employed to probe the growth and swelling of polyelectrolyte multilayers (PEM). By comparing the wavelength shift and extinction intensity increase of the localized surface plasmon resonance (LSPR) of the gold nanorods coated with PEM in air and water, the swelling of PEM was estimated to be 26% ± 6%. The swelling was quantitatively confirmed with independent thickness measurement of PEM in dry and swollen states using AFM. The deployment of shape-controlled metal nanostructures with high refractive index sensitivity represents a novel and facile approach for monitoring the phase transition in polymers with nanoscale resolution.
