Quantum Dot-Induced Blue Shift of Surface Plasmon Spectroscopy.

We experimentally demonstrate the spectral blue shift of surface plasmon resonance through the resonant coupling between quantum dots (QDs) and surface plasmons, surprisingly in contrast to the conventionally observed red shift of plasmon spectroscopy. Multimode optical fibers are used for extended resonant coupling of surface plasmons with excited states of QDs adsorbed to the plasmonic metal surface. The long-lived nature of excited QDs permits QD-induced negative change in the local refractive index near the plasmonic metal surface to cause such a blue shift. The analysis utilizes the physical causality-driven optical dispersion relation, the Kramers-Kronig (KK) relation, attempting to understand the abnormal behavior of the QDs-induced index dispersion extracted from blue shift measurement. Properties of QDs' gain spectrally resonating with plasmons can account for such blue shift, though their absorbance properties never allow the negative index change for the blue shift observed according to the KK relation. We also discuss the limited applicability of the KK relation and possible QDs gain saturation for the experiment-theory disagreement. This work may contribute to the understanding of the photophysical properties critical for plasmonic applications, such as plasmonic local index engineering required in analyte labeling QDs coupled with plasmons for biomedical imaging or assay.

Coupling of silver nanoparticle-conjugated fluorescent dyes into optical fiber modes for enhanced signal-to-noise ratio.

We present the optical coupling of the silver nanoparticles (AgNPs)-conjugated dye molecule into fiber optical modes for detecting fluorescence with the enhanced signal-to-noise (S/N) ratio. This near field coupling of the excited state of organic dye (FAM) molecules into the fiber multimodes occurs by immobilizing them on the exposed surface of fiber core, permitting the coupled light to be guided along the fiber for detection. This fiber based scheme is the first attempt to single out the fluorescence using fiber modes not for carrying excitation light but only for collecting emission light via the dye-fiber coupling. The emission-selective coupling into fiber modes turns out to be effective in reducing the unwanted background noise arising from both the false detection of excitation light and bulk autofluorescence. This scheme differs from the previously reported fluorescence sensors based on waveguides where guided modes at λex excite dye molecules via their evanescent fields. In addition, the local fields enhanced by AgNPs in close proximity to FAM molecules on the fiber core surface increase the rates of dye excitation and radiative decay/AgNP supported surface plasmon coupled emission. While focusing on demonstrating the proof-of-concept of the scheme presented, we obtain the maximum of 4.2-fold enhancement of the signal-to-noise (S/N) ratio in detecting fluorescence as compared to a conventional fluorescence detection scheme. The results presented in the fiber-based scheme may find an application where high S/N ratio fluorescence based biochemical assay is required in a small-sized device with remote sensing capability.

Liquid Cladding Mediated Optical Fiber Sensors for Copper Ion Detection.

We present a label-free optical fiber based sensor device to detect copper ions (Cu2+) in water. A multimode optical fiber, with its polymer cladding removed along a 1-cm length, is used for the optical sensor head, where the injected Cu2+ in the liquid phase acts as a liquid cladding for the optical mode. The various Cu2+ concentrations modulate the numerical aperture (NA) of the liquid cladding waveguide part. The degree of NA mismatch between the liquid cladding and solid cladding guided parts gives rise to an optical power transmittance change, forming the sensing principle. The presented liquid cladding fiber sensor exhibits a minimum resolvable refractive index of 2.48 × 10-6. For Cu2+ detection, we functionalize the sensor head surface (fiber core) using chitosan conjugated ethylenediaminetetraacetic acid (EDTA) which captures Cu2+ effectively due to the enhanced chelating effects. We obtain a limit of detection of Cu2+ of 1.62 nM (104 ppt), which is significantly lower than the tolerable level in drinking water (~30 µM), and achieve a dynamic range of 1 mM. The simple structure of the sensor head and the sensing system ensures the potential capability of being miniaturized. This may allow for in-situ, highly-sensitive, heavy metal sensors in a compact format.