Extraordinary transmission of gold-capped sphere arrays in mid-infrared range.

We report an extraordinary transmission (EOT) of gold-capped silica microsphere monolayers in the mid-infrared range of 5-25 µm. The observed transmittance is significantly greater than that of a flat gold film with the same thickness, although the surface of the microsphere monolayer appeared to be completely covered with gold when observing from above. The calculations based on the finite difference time domain method indicate that light passes through the openings between the gold coating on the substrate and that on the microspheres. The EOT-type studied here occurs over the mid-infrared wavelength range, thus indicating that it is not attributable to the resonance of the surface plasmons. This type of EOT is absent in the visible and near infrared wavelength range, where gold does not function as an ideal metal. In addition, spectral modification originating from localized phonon polariton resonance (LPhPR) in silica microsphere is observed. LPhPR can be interpreted based on the analogy of the localized surface plasmon resonance in metallic nanospheres, in the visible or ultraviolet wavelength range.

Superscattering from cylindrical hyperbolic metamaterials in the visible region.

We report that cylindrical hyperbolic metamaterials (CHMMs) exhibit superscattering (SSc) in the visible region, based on analytical and numerical calculations. It has normalized scattering cross-section (NSCS) twice as large as that from cylinders consisting of homogeneous materials. This large NSCS is due to constructive interference of multipolar resonances. Finite-difference time-domain calculations revealed that the spatial field-distribution at the SSc condition is similar to that of a whispering gallery mode (WGM), suggesting that the WGM-like field distribution is responsible for the large scattering. It is also reported that the SSc can be achieved in CHMM of epsilon near zero materials.

Optical Fiber-Type Sugar Chip Using Localized Surface Plasmon Resonance.

Optical fiber-type Sugar Chips were developed using localized surface plasmon resonance (LSPR) of gold (Au) nanoparticles. The endface of an optical fiber was first aminosilylated and then condensed with α-lipoic acid containing a dithiol group. Second, gold nanoparticles were immobilized onto the endface via an Au-S covalent bond. Finally, sugar moieties were attached to the gold nanoparticle using our original sugar chain-ligand conjugates to obtain fiber-type Sugar Chips, by which the sugar moiety-protein interaction was analyzed. The specificity, sensitivity, and quantitative binding potency against carbohydrate-binding protein were found to be identical to that of a conventional SPR sensor. In this analysis, only a small sample volume (approximately 10 µL) was required compared with 100 µL for the conventional SPR sensor, suggesting that the fiber-type Sugar Chip and LSPR are applicable for nonpure small masses of proteins.

Emission waveguiding in organic thin films supported by metal.

On silver thin film, an organic semiconductor rubrene layer consisting of a planar waveguide exhibits spectrally narrowing photoluminescence (PL) spectra with an increasing emission angle, which are compared with those of rubrene thin films on glass. The PL spectra of rubrene on Ag have a polarization characteristic. In the side direction of the multilayer structure, spectrally very sharp PL was observed. The PL characteristics are discussed from the viewpoint of waveguided modes allowed only for a phase-matching condition. The narrowed PL spectra are attributable to generation of a leaked waveguided mode in the rubrene layer, which is supported by the underlying Ag thin film.

Two-dimensional coherent random laser in photonic crystal fiber with dye-doped nematic liquid crystal.

A random laser of a photonic crystal fiber (PCF) with holes filled with laser dye-doped nematic liquid crystal (NLC) is reported. When the excitation polarization was along the PCF axis, the measured laser threshold was 80 µJ/mm2 per pulse, which is much lower than the previously reported random laser of PCF filled with laser dye-doped organic solvent. This low threshold is due to the high refractive index of the NLC, which produces a greater scattering efficiency. In contrast, when the excitation polarization is perpendicular to the PCF axis, the threshold was much higher or the laser oscillation was absent. This is because of the lower refractive index of the NLC for the perpendicular polarization. The laser oscillation was absent in the isotropic phase because of a low fluorescence efficiency at high temperatures.

Local temperature variation measurement by anti-Stokes luminescence in attenuated total reflection geometry.

Strong temperature dependence of anti-Stokes luminescence intensity from Rhodamine 101 is used to probe local temperature variation at a surface region in the attenuated total reflection geometry (ATR), when heating with laser light. In this method, the measured region can be limited by observing evanescent luminescence. The near-field depth (penetration depth) was changed by the observation angle θout of the evanescent luminescence and the spatial temperature variation was observed.

Direct detection of neuron-specific enolase using a spectrometer-free colorimetric plasmonic biosensor.

Sensitive detection of a tumor marker, neuron-specific enolase (NSE), was performed by a label-free direct immunoassay based on a colorimetric plasmonic biosensor. Reflective plasmonic colors of silver nanodome arrays provided a way for a sensitive refractive index sensor based on spectrometer-free colorimetric detection. The direct detection of NSE was demonstrated by a combination of a sensitive sensor substrate and image processing. The limit of detection (LOD) for NSE was determined to be 270 pM, which is lower than the clinical threshold value of NSE used for medical diagnostics of small-cell lung cancer. Since our substrate-based colorimetric plasmonic biosensor is compatible with smartphone detection, we believe that the presented biosensor will open up a way for biosensor technology for point-of-care testing as well as mobile health applications.

Surface plasmon-enhanced terahertz emission from a hemicyanine self-assembled monolayer.

Emission of terahertz radiation is observed when surface plasmons are excited on a thin film of gold, in the Kretschmann geometry. When a hemicyanine-terminated alkanethiol self-assembled monolayer of thickness 1.2 nm is deposited on the gold film, stronger terahertz emission is observed. Our experimental results confirm that enhanced terahertz emission is possible from planar gold surfaces when surface plasmons are excited.

Terahertz emission from surface-immobilized gold nanospheres.

Electromagnetic wave emission based on optical rectification at terahertz (THz) wavelengths was observed from surface-immobilized gold nanospheres (SIGNs) above a gold surface. Although the excitation wavelength is off-resonant with the localized surface plasmons, the THz emission field was observed to be approximately 4.8 times greater than that from a percolated gold thin film of 10 nm thickness. A theoretical calculation predicts that the light electric field is enhanced in the SIGN system, even at off-resonance wavelengths. The observed THz field amplitude was quadratic with the illumination light field, suggesting that the THz generation is due to a second-order nonlinear optical process.

A new optical label-free biosensing platform based on a metal-insulator-metal structure.

A new label-free biosensing platform is proposed based on a metal-insulator-metal (MIM) structure. This platform allows us to perform biosensing by a simple reflectivity measurement at normal incidence illumination without using any bulky optical setup. Theoretical calculation was made to find optimized MIM structural parameters, and experimental results on the label-free biosensing using the MIM platform are presented. This platform has greater sensitivity and mass resolution with respect to the anomalous reflection method, which is a label-free biosensing platform previously proposed by us. Hence, it is suitable for high throughput analysis of biomolecular detection in a microarray format.

Formation process of self-assembled monolayer on gold nanosphere probed by second harmonic generation.

The formation process of a hemicyanine-terminated alkanethiolate self-assembled monolayer (SAM) on gold nanospheres immobilized on a glass substrate was studied by absorption spectroscopy, optical second harmonic generation, and Monte Carlo simulation. It was found that hemicyanine thiolate SAMs mainly form in the upper hemisphere region of the gold nanospheres in the early stage, followed by the additional SAM formation in the lower region of gold nanospheres. The hemicyanine SAM does not homogeneously form over the nanosphere surface and does not fully cover the nanospheres even after long exposure to the hemicyanine solution. This is because of the narrow space under the nanosphere, where the binding of the alkane disulfide to the gold surface is considered to be a diffusion-controlled reaction. The orientation of the hemicyanine molecules on gold nanospheres is similar to that of hemicyanine on a flat gold substrate. These results are important to understand the surface chemistry at nanostructure surfaces as well as the localized surface plasmon biosensing using metallic nanostructures.

Signal Enhancement Strategies for Refractive Index-Sensitive Nanobiosensor.

BACKGROUND: Direct bio-monitoring essentially involves optical means since photon has insignificant effects over biomolecules. Over the years, laser induced surface Plasmon resonance method with various modifications as well as versatile localized Plasmon excited by incoherent light have facilitated in recording many nanobiological activities. Yet, monitoring interactions of small molecules including drugs requires signal amplification and improvement on signal-to-noise ratio. OBJECTIVES: This paper focused on how the refractive index based nanobio-sensoring gold platform can produce more efficient, adaptable and more practical detection techniques to observe molecular interactions at high degree of sensitivity. It discusses surface chemistry approach, optimisation of the refractive index of gold platform and manipulation of gold geometry augmenting signal quality. METHODS: In a normal-incidence reflectivity, r0 can be calculated using the Fresnel equation. Particularly at λ = 470 nm the ratio of r / r0 showed significant amplitude reduction mainly stemmed from the imaginary part of the Au refractive index. Hence, the fraction of reduction, Δr = 1 - r / r0. Experimentally, in a common reference frame reflectivity of a bare gold surface, R0 is compared with the reflectivity of gold surface in the presence of biolayer, R. The reduction rate (%) of reflectivity, ΔR = 1 - R / R0 is denoted as the AR signal. The method therefore enables quantitative measurement of the surface-bound protein by converting ΔR to the thickness, d, and subsequently the protein mass. We discussed four strategies to improve the AR signal by changing the effective refractive index of the biosensing platform. They are; a) Thickness optimisation of Au thin layer, b) Au / Ag bimetallic layer, c) composing alloy or Au composite, and d) Au thinlayer with nano or micro holes. RESULTS: As the result we successfully 'move' the refractive index, ε of the AR platform (gold only) to ε = -0.948 + 3.455i, a higher sensitivity platform. This was done by composing Au-Ag2O composite with ratio = 1:1. The results were compared to the potential sensitivity improvement of the AR substrate using other that could be done by further tailoring the ε advanced method. CONCLUSION: We suggested four strategies in order to realize this purpose. It is apparent that sensitivity has been improved through Au/Ag bimetallic layer or Au-Ag2O composite thin layer, This study is an important step towards fabrication of sensitive surface for detection of biomolecular interactions.

Simultaneous anomalous reflection and quartz-crystal microbalance measurements of protein bindings on a gold surface.

Protein bindings onto a gold surface were detected simultaneously by QCM (delta F(water)) and anomalous reflection (deltaR) of gold on the same surface in aqueous solutions; the obtained delta F(water)/deltaR values correlated with surface areas and viscosity of proteins.

Anomalous Reflection of Gold: A Novel Platform for Biochips.

The importance of protein detection system for protein functions analyses in recent post-genomic era is rising with the emergence of label-free protein detection methods. We are focusing on a simple and practical label-free optical-detection method called anomalous reflection (AR) of gold. When a molecular layer forms on the gold surface, significant reduction in reflectivity can be observed at wavelengths of 400-500 nm. This allows the detection of molecular interactions by monitoring changes in reflectivity. In this chapter, we describe the AR method with three different application platforms: (1) gold, (2) gold containing alloy/composite (AuAg2O), and (3) metal-insulator-metal (MIM) thin layers. The AuAg2O composite and MIM are implemented as important concepts for signal enhancement process for the AR technique. Moreover, the observed molecular adsorption and activity is aided by a three-dimensional surface geometry, performed using poly(amidoamine) or PAMAM dendrimer modification. The described system is suitable to be used as a platform for high-throughput detection system in a chip format.

Anomalous reflection of gold applicable for a practical protein-detecting chip platform.

A simple, convenient and label-free fiber optic detection system based on the characteristic property, 'anomalous reflection (AR)' of gold was developed and preliminary experiments showed that the AR signals were sensitive enough to monitor protein-peptide interactions on solid surfaces.

Patterning technique for gold nanoparticles on substrates using a focused electron beam.

We propose a novel patterning technique for gold nanoparticles on substrates that combines a chemical reaction with electron beam irradiation. First, gold nanoparticles are placed in a two-dimensional arrangement on the substrate. Then, particular nanoparticles are fixed on the substrate by irradiation with a focused electron beam to produce a desired pattern. Finally, the unfixed nanoparticles are removed. Using this technique, an array of gold nanoparticles, for example, in the form of a line or patterned over an area, are prepared on the substrate. This technique could contribute to the fabrication of plasmonic devices and other applications that require the controlled placement of gold nanoparticles on substrates.

Biometamaterials: Black Ultrathin Gold Film Fabricated on Lotus Leaf.

We report on a black metamaterial of gold fabricated on a lotus leaf that was used as a template. In spite of the extremely thin gold coating (10-nm thick) on the lotus leaf, the surface shows reflectivity below 0.01 over the entire visible spectral range. Finite-difference time-domain (FDTD) calculations suggest that the low reflectivity stems from the secondary structures on the lotus leaf, where randomly oriented nanorods are distributed.

Label and Label-Free Detection Techniques for Protein Microarrays.

Protein microarray technology has gone through numerous innovative developments in recent decades. In this review, we focus on the development of protein detection methods embedded in the technology. Early microarrays utilized useful chromophores and versatile biochemical techniques dominated by high-throughput illumination. Recently, the realization of label-free techniques has been greatly advanced by the combination of knowledge in material sciences, computational design and nanofabrication. These rapidly advancing techniques aim to provide data without the intervention of label molecules. Here, we present a brief overview of this remarkable innovation from the perspectives of label and label-free techniques in transducing nano­biological events.

Sensitive detection of small molecule-protein interactions on a metal-insulator-metal label-free biosensing platform.

The need to develop label-free biosensing devices that enable rapid analyses of interactions between small molecules/peptides and proteins for post-genomic studies has increased significantly. We report a simple metal-insulator-metal (MIM) geometry for fabricating a highly sensitive detection platform for biosensing. MIM substrates consisting of an Au-PMMA-Ag nanolayer were extensively studied using both theoretical and experimental approaches. By monitoring reflectivity changes at the normal incidence angle, we observed molecular interactions as the thickness of the biolayer increased on the substrate surface. These interactions included the adsorption of various proteins (Mw=6-150 kD) and interactions between small molecules (Mw≤2 kD) and the immobilized proteins. The interaction of designed monosaccharide-modified designed peptides with various lectins was also clearly detected. These interactions could not be detected by the conventional Au-only substrate. Thus, the MIM approach affords a powerful label-free biosensing device that will aid our understanding of protein interactions and recognition.