Evanescent wave absorbance

Biirck J., Mayer J., Zimmermann B., Aache H.-J., Integrated optical sensor for chemical analysis based on near-inlfared evanescent wave absorbance measurements, SPIE, 1995 2508 243-252. 

Optical detection for the system described here is based on evanescent wave absorbance spectroscopy (EWAS). This method takes advantage of the reflections of light... 

Figure . Top Standard absorption measurement Bottom evanescent wave absorbance spectroscopy.

Current research is now directed towards realizing a miniaturized sensor by using integrated optics technology and planar waveguide structures. The construction of planar evanescent wave absorbance sensors offers some advantages compared to the existing fiber-optic sensor ... 

Figure 5.5 (a) Schematic of the experimental setup of evanescent wave absorbance-based detection using polymer waveguides, (b) Closer look into the U-bent polymer waveguide coupled with the light source and detector. 

ATR is one of the most useful and versatile sampling modes in IR spectroscopy. When radiation is internally reflected at the interface between a high-refractive index ATR crystal (usually Ge, ZnSe, Si, or diamond) and the sample, an evanescent wave penetrates inside the sample to a depth that depends on the wavelength, the refractive indices, and the incidence angle. Because the penetration depth is typically less than 2 pm, ATR provides surface specific information, which can be seen as an advantage or not if surface orientation differs from that of the bulk. It also allows one to study thick samples without preparation and can be used to characterize highly absorbing bands that are saturated in transmission measurements. 

Simply visualised, the infrared beam penetrates (of the order 0.3-3 pm, dependent on its wavelength) just beyond the ATR crystal-specimen boundary before it is reflected back and makes its way through the crystal to the detector. On this short path (of the evanescent wave) into the sample surface layer, light is absorbed, and the reflected beam carries characteristic spectral information of the sample. The decaying amplitude of the evanescent wave and the depth of penetration dp at which it has decreased to a proportion of 1 /e is defined by the Harrick equation (Equation (2)), where X is the wavelength of the incoming... 

Fig. 10. A SPR Detection realized in a BIAcore system. A fan of polarized light passes a prism and is focused at the interface to an aqueous phase under conditions of total reflection. An evanescent wave enters the solvent phase. If the prism is coated with a thin gold layer at the interface the free electrons in the metal absorb energy from the evanescent wave for a distinct angle, depending on the refractive index of the solvent near the interface. B The gold layer can be modified with, e.g., a carboxydextrane matrix, where catcher molecules can be immobilized by standard chemistry. If a ligand is applied with the aqueous phase it may interact with the catcher and accumulate in the matrix, causing a shift in the resonance angle. If no specific binding occurs the refractive index in proximity of the sensor is less affected...

Fig. 4 Waveguide evanescent wave (EW) principle. Light is propagated through the waveguide (n ) and an electromagnetic field (called EW) is generated in the external medium (n2). The EW interacts with immobilized molecules that absorb energy, leading to attenuation in the reflected light of the waveguide...

A fiber-optic device has been described that can monitor chlorinated hydrocarbons in water (Gobel et al. 1994). The sensor is based on the diffusion of chlorinated hydrocarbons into a polymeric layer surrounding a silver halide optical fiber through which is passed broad-band mid-infrared radiation. The chlorinated compounds concentrated in the polymer absorb some of the radiation that escapes the liber (evanescent wave) this technique is a variant of attenuated total reflection (ATR) spectroscopy. A LOD for chloroform was stated to be 5 mg/L (5 ppm). This sensor does not have a high degree of selectivity for chloroform over other chlorinated aliphatic hydrocarbons, but appears to be useful for continuous monitoring purposes. 

Attenuated total reflectance infrared (ATR-IR) is used to study films, coatings, threads, powders, interfaces, and solutions. (It also serves as the basis for much of the communication systems based on fiber optics.) ATR occurs when radiation enters from a more-dense material (i.e., a material with a higher refractive index) into a material that is less dense (i.e., with a lower refractive index). The fraction of the incident radiation reflected increases when the angle of incidence increases. The incident radiation is reflected at the interface when the angle of incidence is greater than the critical angle. The radiation penetrates a short depth into the interface before complete reflection occurs. This penetration is called the evanescent wave. Its intensity is reduced by the sample which absorbs. 

Attenuated Total Reflection (ATR).4c A sample brought in contact with the totally reflecting surface of a high-refractive-index material (the ATR crystal), will, on IR irradiation, give an evanescent wave in the less dense medium that extends beyond the reflecting interface. This wave will be attenuated in regions of the IR spectrum where the sample absorbs energy. Observation of such waves constitute ATR measurements. Only the small amounts of beads necessary to cover the area of the ATR crystal are required. 

OF optical fibers, IOS integrated optical sensors, A absorbance, R reflectance, F fluorescence, ev evanescent wave, ISP isopropyl alcohol, DOS bis(2-ethylhexyl)sebacate, o - NPOE ortho-nitrophenyl octyl ether, TOP tris(2-ethylhexyl)phosphate... 

Luminescent evanescent wave-based sensors use optical fibers and planar waveguides [105,106] as fight-guiding structures, and they are more complex than the absorbance ones. However, such optodes have been satisfactorily applied to measure fluorescence of indicators or labels for the measurement of gas molecules, proteins or labeled antigen-antibody interactions as well as directly in solution [24,107] when immobilized in matrices [23,109]. 

Quantitative determinations of the thicknesses of a multiple - layered sample (for example, two polymer layers in intimate contact) by ATR spectroscopy has been shown to be possible. The attenuation effect on the evanescent wave by the layer in contact with the IRE surface must be taken into account (112). Extension of this idea of a step-type concentration profile for an adsorbed surfactant layer on an IRE surface was made (113). and equations relating the Gibbs surface excess to the absorbance in the infrared spectrum of a sufficiently thin adsorbed surfactant layer were developed. The addition of a thin layer of a viscous hydrocarbon liquid to the IRE surface was investigated as a model of a liquid-liquid interface (114) for studies of metal extraction ( Ni+2, Cu+2) by a hydrophobic chelating agent. The extraction of the metals from an aqueous buffer into the hydrocarbon layer was monitored kinetically by the appearance of bands unique to the complex formed. 

As previously mentioned, the evanescent wave could interact with the optically rare medium not only by being absorbed but also by being scattered either elastically (Rayleigh Scattering) or inelastically (Raman Scattering). Because it is not within the scope of this paper to review the complete history and theory of Raman scattering, further information is indicated in Ref. 

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