Influence of the metal film thickness on the sensitivity of surface plasmon resonance biosensors

The influence of the metal film thickness (i.e., the chromium adhesion promoting film and the gold film) on the sensitivity of surface plasmon resonance (SPR) signals (i.e., resonance angle shift and reflectance change) towards the thickness variation of the nonabsorbing dielectric film is investigated. The sensitivity of reflectance change decreases when a thick chromium film or a thin gold film is employed. Its linear range becomes narrower as the thickness of the metal films increases. The sensitivity and linear range of the resonance angle shift are not affected by the thickness variation of the metal films. The phenomena were theoretically explained based on the attenuated total reflection (ATR) generated evanescent field at the prism/metal interface and the SPR-generated evanescent field at the metal/dielectric interface.     

Transflectance spectra of faceted diamonds acquired by infrared microscopy

A novel transflectance technique using an infrared microscope was employed for spectral acquisition of loose and mounted faceted diamonds. The observed transflectance spectrum shows the same spectral features as those of the well-accepted diffuse reflectance spectrum. Unlike the diffuse reflectance spectrum, the transflectance spectrum was not affected by the diamond arrangements. The technique can be employed for direct spectra acquisition of mounted diamonds without taking the diamonds out of the jewelry bodies. Moreover, an individual diamond on a complex jewelry setting can be selectively measured. Infrared absorption bands unique to the chemical compositions, impurities, and treatment processes of the diamonds are discussed. The observed transflectance spectra can be exploited for diamond classification.     

Crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) studied by 2D IR correlation spectroscopy

Crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) (HHx=12 mol%) was studied by means of two-dimensional infrared (2D IR) correlation spectroscopy. Three types of crystallization; the gradual cooling from the melt, the isothermal crystallization of the supercooled melt, and the isothermal crystallization of the solution-cast film were investigated. The order of crystal growth steps taking place during the three different types of crystallization processes was analyzed in detail. It was revealed by the asynchronous 2D correlation spectra generated from the dynamic IR spectra in the CO stretching band region that the development of the highly ordered crystals occurs prior to that of the less ordered crystals for the gradual cooling crystallization. On the other hand, for the supercooled melt and solution-cast film crystallization, the formation of the less ordered crystals takes place before that of the highly ordered crystals. The transition from the amorphous phase to the less ordered crystals is a simultaneous process for all three types of crystallization.     

Surface melting and crystallization behavior of polyhydroxyalkanoates studied by attenuated total reflection infrared spectroscopy

The surface melting and crystallization behavior of two biodegradable polyesters, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx)) (HHx=12 mol%) and poly(3-hydroxybutyrate) (PHB), were investigated by using attenuated total reflection (ATR) and transmission infrared (IR) spectroscopy coupled with the generalized two-dimensional (2D) correlation analysis. IR bands in the CO stretching vibration region were analyzed to explore the changes in crystallinity at the surface and those in the bulk of the polymer film samples during the melting and crystallization processes. Due to the intrinsic sub-micrometer sampling depth of the ATR technique, spectral information attributed to the chemical moieties situated at the surface region of the film samples can be observed. The present study revealed that the surface melting of P(HB-co-HHx) takes place through an intermediate state. The distribution of crystalline phase detected by the ATR technique and that detected by the transmission technique suggested that the polymer crystals tend to grow at the surface in a manner different from that in the bulk. It is very likely that the population of polymer crystals at the surface is higher than that in the bulk for both P(HB-co-HHx) and PHB. The time-dependent IR spectral variations for P(HB-co-HHx) and those for PHB indicated that P(HB-co-HHx) crystallizes much slower than PHB. This observation suggested that the HHx units incorporated in P(HB-co-HHx) markedly reduce not only the degree of crystallinity but also the crystallization rate of PHB homopolymer.     

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.     

Characterization of supported cylinder-planar germanium waveguide sensors with synchrotron infrared radiation

Cylinder-planar Ge waveguides are being developed as evanescent-wave sensors for chemical microanalysis. The only non-planar surface is a cylinder section having a 300-mm radius of curvature. This confers a symmetric taper, allowing for direct coupling into and out of the waveguide's 1-mm(2) end faces while obtaining multiple reflections at the central <30-microm-thick sensing region. Ray-optic calculations indicate that the propagation angle at the central minimum has a strong nonlinear dependence on both angle and vertical position of the input ray. This results in rather inefficient coupling of input light into the off-axis modes that are most useful for evanescent-wave absorption spectroscopy. Mode-specific performance of the cylinder-planar waveguides has also been investigated experimentally. As compared to a blackbody source, the much greater brightness of synchrotron-generated infrared (IR) radiation allows a similar total energy throughput, but restricted to a smaller fraction of the allowed waveguide modes. However, such angle-selective excitation results in a strong oscillatory interference pattern in the transmission spectra. These spectral oscillations are the principal technical limitation on using synchrotron radiation to measure evanescent-wave absorption spectra with the thin waveguides.     

Novel attenuated total reflection Fourier transform infrared microscopy using a gem quality diamond as an internal reflection element

A novel technique for attenuated total reflection Fourier transform infrared (ATR FT-IR) spectral acquisition by an infrared microscope with a gem-quality faceted diamond as an internal reflection element (IRE) is introduced. Unlike conventional IREs, the novel diamond IRE has a sharp tip configuration instead of a flat tip configuration. Light at normal incidence was coupled into the diamond while the transflected radiation from the diamond was collected through the table facet by the built-in 15x Cassegrainian objective. The number of reflections in the novel diamond IRE equals two. The evanescent field generated under total internal reflection at the pavilion facet was exploited for ATR spectral acquisition of materials attached to the IRE. The observed ATR spectra were compared to those obtained via a traditional zinc selenide IRE.     

Highly sensitive and selective determination of iodide and thiocyanate concentrations using surface-enhanced Raman scattering of starch-reduced gold nanoparticles

In this report, we propose a novel technique for the determination of the concentrations of iodide and thiocyanate by surface-enhanced Raman scattering (SERS) of starch-reduced gold nanoparticles. Starch-reduced gold nanoparticles show an intrinsic Raman peak at 2125 cm(-1) due to the -C≡C- stretching mode of a synthesized byproduct. Because of the high adsorptivity of iodide on a gold surface, the intensity of the SERS peak at 2125 cm(-1) decreases with an increase in the iodide concentration. Thiocyanate also strongly adsorbs on a gold surface, and a new peak appears at around 2100 cm(-1), attributed to the -C≡N stretching vibration in a SERS spectrum of starch-reduced gold nanoparticles. These two peaks were successfully used to determine the iodide and thiocyanate concentrations separately, even in their mixture system. The detection limit of this technique for iodide is 0.01 μM with a measurement range of 0.01-2.0 μM, while the detection limit of this technique for thiocyanate is 0.05 μM with a measurement range of 0.05-50 μM. This technique is highly selective for iodide and thiocyanate ions without interference from other coexisting anions such as other halides, carbonate, and sulfate.     

Surface plasmon resonance spectroscopy based on evanescent field treatment

The reflectance in a surface plasmon resonance (SPR) curve can be expressed in terms of the integration of the product between the evanescent electric field and the imaginary part of the dielectric constant of all absorbing media. The evanescent field in the metal film consists of two fields, one originating at the prism/metal interface and the other at the metal/dielectric interface. Near the resonance angle, the evanescent field strength at the metal/dielectric interface is much greater than that at the prism/metal interface. The evanescent field in dielectric medium has a single origin at the metal/dielectric interface. Due to the optical enhancement at the interface, the amplitude of the evanescent electric field in the dielectric medium is much greater than that in the metal film. This field, however, is not being utilized in conventional SPR where changes in the refractive index of the nonabsorbing dielectric media are of interest. In a system with an absorbing dielectric medium, the absorption of the medium is enhanced by the strong evanescent electric field. The evanescent field distributions in the metal film and in the dielectric medium are significantly altered by the absorbing dielectric, which results in shifting of the resonance angle, increasing of the reflectance, and broadening of the SPR curve. Since the absorption contribution from the absorbing dielectric can be separated from that of the metal film via knowledge of evanescent field distribution, an in-depth analysis of the SPR curve of an absorbing medium and its relationship with the material characteristics are possible.     

Monitoring 2-ethylhexyl-4-methoxycinnamate photoisomerization on skin using attenuated total reflection fourier transform infrared spectroscopy

Photoisomerization and photodimerization of a widely used UVB filter, 2-ethylhexy-4-methoxycinnamate (EHMC) on a ZnSe surface and baby mouse (Mus musculus Linn.) skin were monitored using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR). Differentiation between the E- and the Z-EHMC could be achieved by examining the infrared (IR) peak at 981 cm(-1) (b peak), which corresponds to the CH rocking deformation vibration of Ph-CH=CH- detected only in the E configuration. By plotting the ratios of the peak area of the b peak and an internal standard peak (1060-998 cm(-1)) against mole percentage of Z-isomer in the E-Z mixtures, a linear calibration plot was obtained. Thus, a simple estimation of the mole percentage of each configuration in a sample was obtained. At the same UVB exposure, photostationary equilibrium of the E/Z isomerization on the surface varied with the applied amounts of EHMC. Photoisomerizations on ZnSe and on baby mouse skin were comparable. Less than 10% of E-EHMC changed configuration when the mouse skins applied with 1.0-4.0 mg/cm(2) E-EHMC were exposed to sunlight for 60 min (UVB radiant exposure of approximately 0.30 J/cm(2)). This corresponded to less than 5% loss in UV filtering efficiency. However, at a typical EHMC skin coverage ( approximately 0.2 mg/cm(2)), 0.30 J/cm(2) UVB exposure induced approximately 50% photoisomerization resulting in 25% loss of UV filtering efficiency. No photodimerization was detected even at the extreme EHMC coverage of 4.0 mg/cm(2) after a UVB exposure of 0.90 J/cm(2).