Attenuated total reflection methods

Since solid-state reactions can easily be monitored by continuous measurement of spectra, it is easy to study the mechanism of the reactions. For this purpose, IR spectroscopy is the most useful, because IR spectra can be measured simply as Nujol mulls or directly for any mixture of solid-solid, solid-liquid, or liquid-liquid by using the ATP (attenuated total reflection) method. Some such examples of the mechanistic study are described. 

One can distinguish between methods in which absorption of the evanescent surface wave in different wavelength regions is measured (these are often called attenuated total reflection methods), and methods which use the evanescent wave to excite other, spectroscopic phenomena, like fluorescence and Raman scattering or light scattering. As the methods of conventional fluorescence spectroscopy have been shown to be exceptionally successful in studies of proteins and other biopolymers, their evanescent surface-sensitive counterparts will be reviewed first. 

FTIR-ATR Fourier transform infrared spectroscopy-attenuated total reflection method... 

The photoselection process resulting in the preferential distribution of azo-chromophores in their perpendicular orientation has been mainly performed by irradiation with visible (blue) light. It was confirmed by the attenuated total reflection method that polarized pumping UV light also caused the formation of the Z-isomer, again with perpendicular orientation, in a thin film of poly-(L-glutamate) with azobenzene residues in the side chains.86... 

The most common approach to excitation of surface plasmons is by means of a prism coupler and the attenuated total reflection method (ATR). There are two configurations of the ATR method - Kretschmann geometry [5] and... 

The attenuated total reflection method can be also used to excite coupled surface plasmons on thin metal films. The couphng of a hght into a symmetric or antisymmetric surface plasmon supported by a thin film (Sect. 2.2) can be in principle achieved in a geometry similar to the Otto geometry (Fig. 23) in which the semi-infinite metal is replaced by a thin metal film [20]. 

The potential of surface plasmons for optical sensing was recognized in the early 1980s when surface plasmons, excited in the Kretschmann geometry of the attenuated total reflection method, were used to probe processes at the surfaces of metals [1] and to detect gases [2]. Since then, numerous surface plasmon resonance (SPR) sensors have been reported. 

ATR-FTIR spectroscopy (attenuated total reflectance Fourier transform infrared spectroscopy)—IR spectroscopy uses the absorption of infrared radiation to probe the vibrational frequency of molecular motions. Attenuated total reflectance method uses a crystal of high refractive index to channel the infrared light (using total internal reflectance) into the crystal and causes only a thin layer of a sample in contact with the exterior of the crystal to be sensitively detected. 

Infrared spectroscopy underwent tremendous advances after the second world war and after 1950 with improvements in instrumentation and electronics, which put the technique at the center of chemical research and later in the 80 s in the biosciences in general with new sample handling techniques, the attenuated total reflection method (ATR) and of course the interferometer [13]. The Fourier TransformIR spectrophotometry is now widely used in both research and industry as a routine method and as a reliable technique for quality control. 

Key words surface plasmon polariton, attenuated total reflection method, pbotocurrent, merocyanine LB film, optical absorption. 

Gaboury and Urban [175] have described an attenuated total reflection method for the determination of SiH groups in PDMS. 

Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. Attenuated total redectance (atr) ftir spectroscopy is based on the principle of total internal redection (40). Methods based on internal redection in the uv and visible regions of the spectmm are also common in addition to those in the ir region. The implementation of internal redection in the ir region of the spectmm provides a means of obtaining ir spectra of surfaces or interfaces, thus providing moleculady-specific vibrational information. 

For on-bead analysis vibrational spectroscopy (IR-spectroscopy) can be employed attenuated total reflection is a method allowing fast and nondestructive on-bead analysis of small samples (single bead analysis) without significant sample preparation. Solid phase NMR is the method of choice if complex structural analysis is intended on the support. Spatially resolved analysis on the resin is possible with microscopic techniques. 

A number of techniques have been employed that are capable of giving information about amorphous phases. These include infrared spectroscopy, especially the use of the attenuated total reflection (ATR) or Fourier transform (FT) techniques. They also include electron probe microanalysis, scanning electron microscopy, and nuclear magnetic resonance (NMR) spectroscopy. Nor are wet chemical methods to be neglected for they, too, form part of the armoury of methods that have been used to elucidate the chemistry and microstructure of these materials. 

Fixed pathlength transmission flow-cells for aqueous solution analysis are easily clogged. Attenuated total reflectance (ATR) provides an alternative method for aqueous solution analysis that avoids this problem. Sabo et al. [493] have reported the first application of an ATR flow-cell for both NPLC and RPLC-FUR. In micro-ATR-IR spectroscopy coupled to HPLC, the trapped effluent of the HPLC separation is added dropwise to the ATR crystal, where the chromatographic solvent is evaporated and the sample is enriched relative to the solution [494], Detection limits are not optimal. The ATR flow-cell is clearly inferior to other interfaces. 

The infrared technique has been described in numerous publications and recent reviews were published by Davies and Giangiacomo (2000), Ismail et al. (1997) and Wetzel (1998). Very few applications have been described for analysis of additives in food products. One interesting application is for controlling vitamin concentrations in vitamin premixes used for fortification of food products by attenuated total reflectance (ATR) accessory with Fourier transform infrared (FTIR) (Wojciechowski et al., 1998). Four vitamins were analysed - Bi (thiamin), B2 (riboflavin), B6 (vitamin B6 compounds) and Niacin (nicotinic acid) - in about 10 minutes. The partial least squares technique was used for calibration of the equipment. The precision of measurements was in the range 4-8%, similar to those obtained for the four vitamins by the reference HPLC method. 

The ability to recover monolayers and subject them to meaningful analysis has become practical only in recent years because of the development of new methods of trace analysis. High-performance liquid chromatography and vapor phase chromatography allow separation and identification of such small quantities (54a). Attenuated total reflectance techniques for infrared analysis (56) and field desorption mass spectrometry (68) have been applied to the trans-... 

Solid state spectra can be measured by the Attenuated Total Reflectance or Multiple Internal Reflection methods as well as by simple transmission techniques (222). Brooker (223) has reported the discovery of the translational vibrations of NaN02, NaNOs, and CaCOs (calcite). The orientation of the bonds in (U02)(N0s)2. 6 H2O has been ascertained from the spectra obtained in this manner (223). 

An infrared spectrum is a plot of percent radiation absorbed versus the frequency of the incident radiation given in wavenumbers (cm ) or in wave length ( xm). A variation of this method, diffuse reflectance spectroscopy, is used for samples with poor transmittance, e.g. cubic hematite crystals. Increased resolution and sensitivity as well as more rapid collection of data is provided by Fourier-transform-IR (FTIR), which averages a large number of spectra. Another IR technique makes use of attenuated total reflectance FTIR (ATR-FTIR) often using a cylindrical internal reflectance cell (CIR) (e.g. Tejedor-Tejedor Anderson, 1986). ATR enables wet systems and adsorbing species to be studied in situ. 

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