Gold island films on indium tin oxide for localized surface plasmon sensing

Mechanically, chemically and optically stable gold island films were prepared on indium tin oxide (ITO) substrates by direct thermal evaporation of thin gold films (2-6?nm) without the need for pre-?or post-coating. The effect of mild thermal annealing (150?°C, 12?h) or short high temperature annealing (500?°C, 1?min) on the morphology of the gold nanostructures was investigated. ITO covered with 2?nm gold nanoislands and annealed at 500?°C for 1?min was investigated for its ability to detect the adsorption of biotinylated bovine serum albumin using local surface plasmon resonance (LSPR), and its subsequent molecular recognition of avidin.     

Electrochemical thinning of thicker gold film with qualified thickness for surface plasmon resonance sensing

To meet the requirement of surface plasmon resonance (SPR) sensing, controlling the thickness of the gold film is very important. Here, we report an efficient and simple approach to prepare a SPR-active substrate when the thickness of the gold film is larger than the optimizing 50 nm and smaller than 100 nm. This method is based on anodic electrodissolution of gold in electrolyte containing chloride ions. Using this method, the thickness of gold films can be easily changed at a nanometer scale by controlling the number of potential scans and the concentrations of chloride ions in the electrolyte. At the same time, the influence of gold film thickness on the SPR signal is recorded by SPR in real time. To assess the change of the surface roughness and morphology of gold film through anodic electrodissolution, atomic force microscopy was used. The surface roughness of the same Au film before and after anodic electrodissolution is 1.179 and 2.767 nm, respectively. The change of the surface roughness of Au film brings out a slight angle shift of SPR. This indicates that surface electrodissolution of the gold does not affect the character of the original bulk film and this film can be used for SPR experiments. To confirm our expectation, a simple adsorption experiment of cytochrome c (Cyt c) on the gold film treated with anodic electrodissolution modified by 11-mercaptoundecanic acid was carried out. The angle shift of SPR confirmed the adsorption of Cyt c, and the cyclic voltammetry of Cyt c provided a complementary confirmation for the adsorption of Cyt c. These results show that this approach provides a good way to change the thicker gold film to an optimized thickness of SPR sensing. The great advantage brought by this approach is in that it can convert the waste gold films with greater thicknesses fabricated by the vacuum deposition method or other methods into useful materials as active SPR substrates.     

Optimization of localized surface plasmon resonance transducers for studying carbohydrate-protein interactions

Noble metal nanostructures supporting localized surface plasmons (SPs) have been widely applied to chemical and biological sensing. Changes in the refractive index near the nanostructures affect the SP extinction band, making localized surface plasmon resonance (LSPR) spectroscopy a convenient tool for studying biological interactions. Carbohydrate-protein interactions are of major importance in living organisms; their study is crucial for understanding of basic biological processes and for the construction of biosensors for diagnostics and drug development. Here LSPR transducers based on gold island films prepared by evaporation on glass and annealing were optimized for monitoring the specific interaction between Concanavalin A (Con A) and D-(+)-mannose. The sugar was modified with a PEG-thiol linker and immobilized on the Au islands. Sensing assays were performed under stationary and flow conditions, the latter providing kinetic parameters for protein binding and dissociation. Ellipsometry and Fourier transform-infrared (FT-IR) data, as well as scanning electron microscopy (SEM) imaging of fixated and stained samples, furnished independent evidence for the protein-sugar recognition. Enhanced response and visual detection of protein binding was demonstrated using Au nanoparticles stabilized with the linker-modified mannose molecules. Mannose-coated transducers display an excellent selectivity toward Con A in the presence of a large excess of bovine serum albumin (BSA).     

Bimetallic multifunctional core@shell plasmonic nanoparticles for localized surface plasmon resonance based sensing and electrocatalysis

Smart bimetallic core@shell nanoparticles were fabricated based on gold nanoparticles (AuNPs) decorated with pH-sensitive polymer shell. Concretely, AuNPs having poly(4-vinylpyridine) (P4VP) on the surface were first fabricated through surface-initiated atom transfer radical polymerization (SI-ATRP). Then, they were mixed with selected metal precursor solutions followed by reduction using reducing agent. The metal NPs thus introduced were uniformly distributed in P4VP polymer shells. In order to explore the diversity and viable function of the resultant nanostructures, we controlled the size of AuNP, pH, selectivity of metal precursors, etc. We investigated the structural alteration during the sequential synthetic process. The bimetallic nanostructures of AuNP@P4VP nanocomposites containing another type of metal NP at the P4VP periphery exhibit a controlled sensing property in terms of the change in the refractive index of surrounding media and a typical electrocatalytic activity for methanol oxidation reaction.     

Distance-dependent plasmon resonant coupling between a gold nanoparticle and gold film

We present an experimental analysis of the plasmonic scattering properties of gold nanoparticles controllably placed nanometers away from a gold metal film. We show that the spectral response of this system results from the interplay between the localized plasmon resonance of the nanoparticle and the surface plasmon polaritons of the gold film, as previously predicted by theoretical studies. In addition, we report that the metal film induces a polarization to the single nanoparticle light scattering, resulting in a doughnut-shaped point spread function when imaged in the far-field. Both the spectral response and the polarization effects are highly sensitive to the nanoparticle-film separation distance. Such a system shows promise in potential biometrology and diagnostic devices.     

Simultaneous excitation of propagating and localized surface plasmon resonance in nanoporous gold membranes

Materials multifunctionality for optical sensing of adsorbates has obvious advantages-in addition to the potential for greater sensitivity, the different length scales associated with a variety of optical phenomena allow a greater variety of adsorption characteristics to be examined. Here, we show that ultrathin (approximately 100 nm) nanoporous gold membranes possess features of both planar metal films that exhibit propagating SPR excitations and nanofeatured metals that exhibit localized SPR excitations. This is the first report of such multifunctionality in an optically active metal. We give illustrative examples of using this material to probe biorecognition reactions and to probe the structure evolution of a layer-by-layer deposition of charged dendrimers. Our results are consistent with the very different lengths of the tail of the evanescent field decays associated with each of these plasmon excitation modes.     

In situ sensing of single binding events by localized surface plasmon resonance

Single binding events of nanoparticle-labeled DNA strands were detected as stepwise peak shifts in localized surface plasmon resonance by single particle measurement. We confirmed the number of binding events by observing label particles by scanning electron microscopy. Our simulation based on a multiple multipole program showed that the peak shift is dependent on interparticle gap size and binding position. The experimental peak shift distribution was also reproduced by simulation.     

Palm-sized biodetection system based on localized surface plasmon resonance

We present a complete palm-sized, battery-operated biodetection system based on highly sensitive localized surface plasmon resonance (LSPR). We have replaced the spectrum analyzer by four pulse-powered light-emitting diodes (LED), each with different emission spectra. The reflected light beams from all LEDs were detected by a single photodiode. Its composite output current was demultiplexed by a four-channel lock-in amplifier. Device performance was demonstrated using an LSPR chip covered with a mixture of ethanol/water and 2-propanol/water at different concentrations. The miniaturized system does not require any external power supply or personal computer and it is therefore suitable for point-of-care and field applications.     

Plasmon line shaping using nanocrosses for high sensitivity localized surface plasmon resonance sensing

The detection of small changes in the wavelength position of localized surface plasmon resonances in metal nanostructures has been used successfully in applications such as label-free detection of biomarkers. Practical implementations, however, often suffer from the large spectral width of the plasmon resonances induced by large radiative damping in the metal nanocavities. By means of a tailored design and using a reproducible nanofabrication process, high quality planar gold plasmonic nanocavities are fabricated with strongly reduced radiative damping. Moreover, additional substrate etching results in a large enhancement of the sensing volume and a subsequent increase of the sensitivity. Coherent coupling of bright and dark plasmon modes in a nanocross and nanobar is used to generate high quality factor subradiant Fano resonances. Experimental sensitivities for these modes exceeding 1000 nm/RIU with a Figure of Merit reaching 5 are demonstrated in microfluidic ensemble spectroscopy.     

Signal sensing and magnetic film memory array design

A signal-to-noise analysis is presented to show its influence on the design of magnetic film memory arrays. The device geometry and array dimensions are varied independently to find the design limits within which reliable signal detection can be performed, that is, the range within which adequate signal-to-noise ratio is obtained at the sense amplifier. The result is a plot of the required number of READ pulses for any combination of line width and line length in the range of interest. Line widths between 1/2- and 4-Mil and array sizes up to 4096 × 4096 bits were investigated. Multipulse readout is required for line widths less than 1.5-mils. A 256 × 256 array of 1/2-mil lines on 1-mil centers requires 12 signal pulses of 3-ns duration each, whereas a 1024 × 1024 array of 1-mil lines on 2-mil centers requires 7 signal pulses. It should be noted that in addition to adequate signal-to-noise ratio, a minimum of signal is needed (not obtainable through multiple READs) commensurate with the gain of the sense amplifier. These considerations are all combined in a set of design curves which can be used to make design tradeoffs between device size, array size, and cycle time.     

Microsurface plasmon resonance biosensing based on gold-nanoparticle film

We use a gold-nanoparticle coated film to achieve highly spatially resolved biosensing that is based on localized surface-plasmon resonance. Unlike the planar gold film employed for conventional surface-plasmon resonance sensing, the gold-nanoparticle film relies exclusively on shifting of the peak extinction wavelength for detection of biointeraction and does not depend critically on the angle of incidence. These characteristics permit integration of surface-plasmon resonance with large-numerical-aperture optics to achieve biosensing with high sensitivity and spatial resolution as high as 25 microm.     

Reversible tuning of plasmon coupling in gold nanoparticle chains using ultrathin responsive polymer film

We demonstrate large and reversible tuning of plasmonic properties of gold nanoparticles mediated by the reversible breaking and making of linear and branched chains of gold nanoparticles adsorbed on an ultrathin (1 nm) responsive polymer film. Atomic force microscopy revealed that at pH below the isoelectric point of the polybase (extended state of the polymer chains), gold nanoparticles adsorbed on the polymer layer existed primarily as individual nanoparticles. On the other hand, at higher pH, the polymer chains transition from coil to globule (collapsed) state, resulting in the formation of linear and branched chains with strong interparticle plasmon coupling. Reversible aggregation of the nanoparticles resulted in large and reversible change in the optical properties of the metal nanostructure assemblies. In particular, we observed a large redistribution of the intensity between the individual and coupled plasmon bands and a large shift (nearly 95 nm) in the coupled plasmon band with change in pH. Large tunability of plasmonic properties of the metal nanostructure chains reported here is believed to be caused by the chain aggregates of nanoparticles and un-cross-linked state of the adsorbed polymer enabling large changes in polymer chain conformation.     

Sensing characteristics of NIR localized surface plasmon resonances in gold nanorings for application as ultrasensitive biosensors

The optical responses of 75-150 nm diameter gold nanorings to changes in local refractive index have been quantified by near-infrared extinction spectroscopy and compared to DDA calculations and an analytical approach. The "bulk" refractive index sensitivities of gold nanorings are substantially (>5 times) larger than those of nanodisks with similar diameters. Nanorings retain a significantly larger sensitivity than nanodisks at the same spectral position, demonstrating a clear shape dependence that may correlate to a systematic difference in the influence of the dielectric substrate. The nanoring bulk refractive index sensitivity scales linearly with plasmon peak position. The spectral sensitivity to thin films of alkanethiols gave a shift of approximately 5.2 nm/CH2 unit while bulk sensitivities as high as 880 nm/RIU were observed, the highest such reported sensitivities. Both bulk and thin dielectric film sensitivities correlated well with theory. Real-time label-free monitoring of protein binding via molecular recognition was demonstrated.     

Improved vapor selectivity and stability of localized surface plasmon resonance with a surfactant-coated Au nanoparticles film

Here, we report the use of tetraoctylammonium bromide (TOABr)-coated Au nanoparticles (NPs) for the optical sensing of volatile organic compounds (VOCs). We find that the film responded selectively to the presence of polar and nonpolar vapors by changes in the maximum wavelength (λ(max)) toward higher and lower wavelengths, respectively, as determined by UV-visible spectroscopy. We also observed that the organic coating reorganizes when vapors partition into the film indicated by FT-IR and the film contracts in the presence of water indicated by scanning electron microscopy (SEM). In the present sensor, the metallic Au core serves as the plasmonic signal while the organic coating acts as the receptor material providing vapor selectivity and sensor stability. Correlating changes in (λ(max)) with changes in the refractive index (RI) and nanoparticle-to-nanoparticle separation in the film is important both fundamentally and for improving selectivity in localized surface plasmon resonance (LSPR) sensors.     

Atomically localized plasmon enhancement in monolayer graphene

Plasmons in graphene can be tuned by using electrostatic gating or chemical doping, and the ability to confine plasmons in very small regions could have applications in optoelectronics, plasmonics and transformation optics. However, little is known about how atomic-scale defects influence the plasmonic properties of graphene. Moreover, the smallest localized plasmon resonance observed in any material to date has been limited to around 10 nm. Here, we show that surface plasmon resonances in graphene can be enhanced locally at the atomic scale. Using electron energy-loss spectrum imaging in an aberration-corrected scanning transmission electron microscope, we find that a single point defect can act as an atomic antenna in the petahertz (10(15) Hz) frequency range, leading to surface plasmon resonances at the subnanometre scale.     

Use of gold island films in design of reflectors with high luminosity

We describe the optical properties of gold island films embedded between SiO2 and/or TiO2 layers. Plasmonic properties of gold films have been characterized using spectrometry and variable angle spectroscopic ellipsometry for various combinations of the embedding media. The obtained refractive indices of embedded gold island films have been used in the design of several types of multilayer reflectors.     

Synthesis of Ag-Au bimetallic film at liquid-liquid interface and its application in vapor sensing

We demonstrate a novel process for preparing densely packed film of silver nanoparticles at the liquid-liquid interface followed by a transmetallation reaction with gold ion to yield a film of bimetallic nanoparticles. Films of assembled silver as well as Ag-Au bimetallic were characterized by UV-vis-spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis. I-V measurement shows linear behavior for both the films with ca. five orders of magnitude drop in resistance for the Ag-Au bimetallic film. Temperature dependent I-V measurement revealed a semiconductor to metal transition after transmetallation reaction. The films where checked for their potential application in chemical vapor sensing to ammonia vapors.     

Label-free DNA biosensor based on localized surface plasmon resonance coupled with interferometry

In this report, we developed a new optical biosensor in connection with a gold-deposited porous anodic alumina (PAA) layer chip. In our sensor, we observed that the gold deposition onto the chip surface formed a "caplike" layer on the top of the oxide nanostructures in an orderly fashion, so we called this new surface formation a "gold-capped oxide nanostructure". As a result of its interferometric and localized surface plasmon resonance properties, the relative reflected intensity (RRI) at surface of the chip resulted in an optical pattern that was highly sensitive to the changes in the effective thickness of the biomolecular layer. We demonstrated the method on the detection of picomolar quantities of untagged oligonucleotides and the hybridization with synthetic and PCR-amplified DNA samples. The detection limit of our PAA layer chip was determined as 10 pM synthetic target DNA. The capability of observing both RRI increment and wavelength shift upon biomolecular interactions promises to make our chip widely applicable in various analytical tests.     

Improving the instrumental resolution of sensors based on localized surface plasmon resonance

The colorimetric variations induced upon changes in interfacial refractive index of nanoscale noble metal structures exhibiting localized surface plasmon resonance (LSPR) provides a convenient means of label-free, affinity-based detection of biomolecular recognition reactions. However, despite being similar in nature to conventional SPR, LSPR has so far suffered from significantly lower data quality in terms of its signal-to-noise ratio (S/N) in typical biomolecular recognition analysis. In this work, generic data analysis algorithms and a simple experimental setup that provide a S/N upon protein binding that is comparable to that of state-of-the art SPR systems are presented. Specifically, it is demonstrated how temporal variations (rate approximately 0.5 Hz) in parameters proportional to the resonance peak position can be recorded simultaneously, yielding a peak position precision of <5 x 10(-4) nm and an extinction noise level of <5 x 10(-6) absorbance units (Abs). This, in turn, is shown to provide a S/N of approximately 2000 (equivalent to a detection limit of <0.1 ng/cm(2)) for typical protein binding reactions. Furthermore, the importance of utilizing changes in both peak position and magnitude is highlighted by comparing different LSPR active noble metal architectures that respond differently to bulk and interfacial refractive index changes.     

A localized surface plasmon resonance based immunosensor for the detection of casein in milk

In this research, a localized surface plasmon resonance (LSPR) immunosensor based on gold-capped nanoparticle substrate for detecting casein, one of the most potent allergens in milk, was developed. The fabrication of the gold-capped nanoparticle substrate involved a surface-modified silica nanoparticle layer (core) on the slide glass substrate between bottom and top gold layers (shell). The absorbance peak of the gold-capped nanoparticle substrate was observed at ∼520 nm. In addition, the atomic force microscopy (AFM) images demonstrated that the nanoparticles formed a monolayer on the slide glass. After immobilizing anti-casein antibody on the surface, our device, casein immunosensor, could be applied easily for the detection of casein in the raw milk sample without a difficult pretreatment. Under the optimum conditions, the detection limit of the casein immunosensor was determined as 10 ng/mL. Our device brings several advantages to the existing LSPR-based biosensors with its easy fabrication, simple handling, low-cost, and high sensitivity.