Application of two-dimensional spectral surface plasmon resonance to imaging of pressure distribution in elastohydrodynamic lubricant films

What we believe to be a novel two-dimensional spectral surface plasmon resonance imaging technique determining pressure distribution in elastohydrodynamic lubricant films is presented. This technique makes use of the spectral characteristics associated with the surface plasmon resonance (SPR) effect, and it provides more spectral information in refractive index mapping than conventional contrast SPR imaging. Two-dimensional imaging is demonstrated and applied to a highly pressurized liquid lubricant trapped inside an elastohydrodynamic lubrication (EHL) dimple. The hydrostatic pressure inside the EHL dimple causes a localized change of the refractive index of the lubrication oil. This also results in a shift in the spectral SPR absorption dip. By monitoring the color changes within the SPR image and calibrating with lubricants of known refractive index profiles, we can obtain a direct measurement of the refractive index distribution within the EHL dimple. PB 2400 lubricant dimples were studied in our experiments. The proposed SPR imaging approach is irrespective of the absolute lubricant film thickness h, therefore overcoming the major limitations of a conventional optical interference technique. With further development of the two-dimensional refractive index mapping technique, widespread applications in various fields are possible, including high-throughput sensors and the detection of bioaffinity interactions.     

Silicon-based surface plasmon resonance sensing with two surface plasmon polariton modes

Surface plasmon resonance (SPR) sensing on a silicon-based platform is considered. We have studied properties of SPR in a combined silicon-dielectric layer-gold film-sample medium structure and established conditions of the simultaneous excitation of two plasmon polariton modes that provide narrow and well-separated minima of the reflected intensity. It has been shown that the external mode over the gold-sample medium interface demonstrates a highly sensitive response to a change in the refractive index of the sample medium, whereas the internal mode over the dielectric-gold interface is almost insensitive to medium parameters. We propose that the internal mode can be used as an effective reference zero point for miniature and portable SPR-based systems designed for field and multichannel sensing.     

Inverse surface plasmon resonance based effective hydrogen sensing using nanoscale palladium films

We demonstrate a nanoscale palladium (Pd) based inverse surface plasmon resonance (ISPR) setup for sensing highly inflammable hydrogen (H₂) gas. The ISPR setup was employed in Kretschmann configuration to assess the sensitivity of the Pd-films when subjected to H₂ gas exposure. With an adequate broadening of the SPR peak maxima, the SPR angle was found to shift from a value of 46.57° to 50.97°, when the concentration of H₂ was varied between 0% and 0.9%. The shifting can be attributed to the transient development of isolated PdH_x (x < 1) clusters within Pd lattices, resulting in an appreciable change of refractive index locally. The dynamical behaviour of switching on/off states exhibited by a ∼20 nm Pd-film and exposed to 0.1% H₂ gas was monitored over several cycles repetitively. The ISPR based H₂ sensor, as demonstrated in ambient environment, would find scope to detect low level H₂ in industrial and other hazardous areas.     

表面等离子共振氢气传感研究进展

基于表面等离子共振原理的光学氢气传感已经成为氢气传感技术研究的热点.表面等离子共振传感器具有安全可靠、灵敏度高、实时性好、便于分布式多点检测等优点,在氢气泄漏检测方向具有广阔的应用前景.本综述介绍了表面等离子共振氢气传感器的三种主要结构类型:棱镜耦合结构,光栅耦合结构和光纤耦合结构的检测原理、典型结构及其研究进展;重点论述了表面等离子共振氢气传感技术中氢敏感膜系的研究现状和技术难题;分析了目前表面等离子共振氢气传感实际应用所面临的瓶颈,并对未来的研究方向进行了展望.结合实际,提出了开发基于光纤微结构和纳米材料的新型氢气传感器件,并且将传感原理延伸至局域表面等离子体共振,表面等离子体共振成像等新兴技术.     

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).     

Localized surface plasmon resonance sensing properties of photocatalytically prepared Au/TiO2 films

Photocatalytic deposition of Au nanoparticles from a mixed aqueous solution of HAuCl₄ and ethylene glycol onto TiO₂ films (Au/TiO₂ films) was carried out by using ultraviolet light irradiation at room temperature. In the optical absorption spectra of the Au/TiO₂ film, the localized surface plasmon resonance (LSPR) peak of Au nanoparticles was observed at 534.5 nm. When the film was immersed in various kinds of solutions, such as alcohols, NaCl and d-glucose aqueous solutions, a linear relation was clearly observed between the LSPR peak wavelength and the refractive index of the solutions, in the range of 1.0003–1.4181.     

Ultrafast pump-probe surface plasmon resonance spectroscopy of thin gold films

A time-resolved reflection pump-probe method was combined with a surface plasmon resonance technique in Kretschmann geometry for the investigation of ultrafast light-induced processes in thin films. Transient changes in the gold layer's reflectivity were observed when the layer was excited by 3 ps duration pulses with photon energy exceeding the interband transition and by probing with photon energy close to the interband transition. Comparison of the experimental and modeling results has shown that the imaginary part of the dielectric function of gold increases linearly during excitation, whereas the real part remains unchanged. The decay of the light-induced changes has two components. The first component is faster than the pulse duration, and the second is much longer than 1.5 ns; they are related to cooling of the electron plasma and lattice, respectively.     

Characterization of high refractive index semiconductor films by surface plasmon resonance

Si-based surface plasmon resonance (SPR) in the Kretschmann-Raether geometry is considered as a platform for the optical measurement of high refractive index films. The implementation of the SPR effect becomes possible due to the relatively high index of refraction of Si compared to most materials. As examples we study the SPR responses for some important semiconductor-based films, including laser-ablated porous silicon and thin germanium films. Using SPR data, we determine the refractive indices of these films for different parameters (thickness and porosity) and ambiences. We also discuss novel SPR biosensor architectures with the use of these solid films.     

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.     

Advances in surface plasmon resonance sensing with nanoparticles and thin films: nanomaterials, surface chemistry, and hybrid plasmonic techniques

Nanomaterials developed for localized surface plasmon resonance (LSPR) are increasingly integrated to classical prism-based SPR sensors, providing enhanced sensitivity and lower detection limits. The unique properties of these novel nanomaterials in addition to novel surface chemistry to minimize nonspecific adsorption and surface plasmon-coupled techniques with other spectroscopic or mass spectrometry techniques are highlighted in this article.     

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.     

Differential-phase surface plasmon resonance biosensor

In this paper, a novel differential-phase-sensitive surface plasmon resonance biosensor (DP-SPRB) is proposed and developed, in which a two-frequency laser is integrated with a differential amplifier in order to analytically convert the phase modulation into amplitude modulation. With the use of the conventional envelope detection technique, the differential phase is precisely decoded in real time in terms of the demodulated amplitude. In order to verify high detection sensitivity of the DP-SPRB, a sucrose-water solution and glycerin-water solution at low concentrations were both tested, and the experimental results confirm that the detection sensitivity on wt % concentration of the sucrose solution is 0.00001%. Moreover, the real-time monitoring mouse IgG/antimouse IgG interaction shows the minimum concentration of mouse IgG to be at 10 fg/mL. To our knowledge, this is the highest sensitivity ever measured by a surface plasmon resonance biosensor. However, because of the limited dynamic range of DP-SPRB, it can only apply to biomolecule interactions at extremely low concentration.     

Wavelength-scanning surface plasmon resonance imaging

A new surface plasmon resonance (SPR) imaging technique was proposed. After measurements were conducted at varying wavelengths, the wavelength affording the minimum brightness (SPR wavelength) was determined at each pixel of the image. A two-dimensional map of the SPR wavelength could be converted to a thickness profile by use of a nonlinear calibration curve, which was obtained by Fresnel calculation. An array of protein thin layers on a gold film was evaluated in air to present the layers' surface structure in nanometer scale.     

利用表面等离子激元共振生物传感器研究聚合酶与敏感表面上自组装的DNA的相互作用

利用SPR生物传感器研究了人的型DNA聚合酶与DNA模板一引物二聚体以及单链DNA的相互作用情况.同时,观察了两种抑制剂(神经酸和亚油酸)对这些相互作用的影响.结果表明,神经酸和亚油酸可以使β聚合酶与DNA二聚体的亲和力分别下降20倍和5倍,神经酸的抑制作用更加明显.利用这些方法,有助于清楚了解抑制剂对β聚合酶与DNA相互作用的影响和抗癌及抗病毒药物的研制.     

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.     

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.     

Theoretical limit of localized surface plasmon resonance sensitivity to local refractive index change and its comparison to conventional surface plasmon resonance sensor

In this paper, the theoretical sensitivity limit of the localized surface plasmon resonance (LSPR) to the surrounding dielectric environment is discussed. The presented theoretical analysis of the LSPR phenomenon is based on perturbation theory. Derived results can be further simplified assuming quasistatic limit. The developed theory shows that LSPR has a detection capability limit independent of the particle shape or arrangement. For a given structure, sensitivity is directly proportional to the resonance wavelength and depends on the fraction of the electromagnetic energy confined within the sensing volume. This fraction is always less than unity; therefore, one should not expect to find an optimized nanofeature geometry with a dramatic increase in sensitivity at a given wavelength. All theoretical results are supported by finite-difference time-domain calculations for gold nanoparticles of different geometries (rings, split rings, paired rings, and ring sandwiches). Numerical sensitivity calculations based on the shift of the extinction peak are in good agreement with values estimated by perturbation theory. Numerical analysis shows that, for thin (≤10 nm) analyte layers, sensitivity of the LSPR is comparable with a traditional surface plasmon resonance sensor and LSPR has the potential to be significantly less sensitive to temperature fluctuations.     

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.     

Evanescent field in surface plasmon resonance and surface plasmon field-enhanced fluorescence spectroscopies

The highly sensitive nature of surface plasmon resonance (SPR) spectroscopy and surface plasmon field-enhanced fluorescence spectroscopy (SPFS) are governed by the strong surface plasmon resonance-generated evanescent field at the metal/dielectric interface. The greatest evanescent field amplitude at the interface and the maximum attenuation of the reflectance are observed when a nonabsorbing dielectric is employed. An absorbing dielectric decreases the evanescent field enhancement at the interface. The SPR curve of an absorbing dielectric is characterized by a greater reflectance minimum and a broader curve, as compared to those of the nonabsorbing dielectric with the same refractive index. For a weakly absorbing dielectric, such as nanometer-thick surface-confined fluorophores, the absorption is too small to induce a significant change in the SPR curve. However, the presence of a minute amount of the fluorophore can be detected by the highly sensitive SPFS. The angle with the maximum fluorescence intensity of an SPFS curve is always smaller than the resonance angle of the corresponding SPR curve. This discrepancy is due to the differences of evanescent field distributions and their decay characteristics within the metal film and the dielectric medium. The fluorescence intensity in an SPFS curve can be expressed in terms of the evanescent field amplitude. Excellent correlations between the experimentally measured fluorescence intensities and the evanescent field amplitudes are observed.     

An absorption-based surface plasmon resonance sensor applied to sodium ion sensing based on an ion-selective optode membrane

A surface plasmon resonance (SPR) sodium ion sensor using an ion optode membrane film was experimentally and theoretically described based on an absorption-based SPR principle proposed in our previous article (Kurihara, K; Suzuki, K. AnaL Chem. 2002, 74, 696-701). The sodium ion concentrations from 10(-6) to 10(-1) have been successfully determined not only by the resonance angle diagnosis of the SPR curve but also by the minimum reflectance one. The ion optode film was plasticized poly(vinyl chloride) including a neutral sodium ionophore, a pH-sensitive cationic dye, and an anionic additive. Its optical absorption intensity changed with the sodium ion concentrations. The SPR ion sensor physically measured the complex refractive index caused by the absorption in the ion optode film. We have exhaustively investigated the experimental response behavior of the SPR curve relative to the sodium ion concentrations by comparison with numerically simulated SPR curves using a three-layer Fresnel equation including experimental values for the sodium ion optode membrane film. As predicted by the absorption-based SPR principle, the SPR curve behavior of the SPR ion sensors depended on two factors: one was the relation between the excitation frequency of the light source and the absorption maximum frequency in the ion optode film while the other was the gold metallic thickness in the Kretchmann configuration. The concept and practical theory of an absorption-based SPR sensor not only have been proved by the experimental results of the SPR sodium ion sensor but also have successfully allowed flexible ion sensing in an SPR sensor, which would be very difficult without the absorption mechanism in the ion optode film.