Absorption techniques specific characteristics

IR spectroscopy, one of the few surface analytical techniques not requiring a vacuum, provides a large amount of molecular information. The absorption versus frequency characteristics are obtained when a beam of IR radiation is transmitted through a specimen. IR is absorbed when a dipole vibrates naturally at the same frequency as the absorber, and the pattern of vibration is unique for a given molecule. Therefore, the components or groups of atoms that are absorbed into the IR at specific frequencies can be determined, allowing identification of the molecular structure. 

The wavelengths of IR absorption bands are characteristic of specific types of chemical bonds. In the past infrared had little application in protein analysis due to instrumentation and interpretation limitations. The development of Fourier transform infrared spectroscopy (FUR) makes it possible to characterize proteins using IR techniques (Surewicz et al. 1993). Several IR absorption regions are important for protein analysis. The amide I groups in proteins have a vibration absorption frequency of 1630-1670 cm. Secondary structures of proteins such as alpha(a)-helix and beta(P)-sheet have amide absorptions of 1645-1660 cm-1 and 1665-1680 cm, respectively. Random coil has absorptions in the range of 1660-1670 cm These characterization criteria come from studies of model polypeptides with known secondary structures. Thus, FTIR is useful in conformational analysis of peptides and proteins (Arrondo et al. 1993). 

Medical Imaging. An area in which applied mathematics has become fundamentally important is the field of medical imaging, especially as it applies to magnetic resonance imaging (MRI). The MRI technique developed from nuclear magnetic resonance (NMR) analysis commonly used in analytical chemistry to determine molecular structures. In NMR, measurements are obtained of the absorption of specific radio frequencies by molecules held within a magnetic field. The strength of each absorption and specific patterns of absorptions are characteristic of the structure of the particular molecule and so can be used to determine unequivocally the exact molecular structure of a material. 

The PSP toxins represent a real challenge to the analytical chemist interested in developing a method for their detection. There are a great variety of closely related toxin structures (Figure 1) and the need exists to determine the level of each individually. They are totally non-volatile and lack any useful UV absorption. These characteristics coupled with the very low levels found in most samples (sub-ppm) eliminates most traditional chromatographic techniques such as GC and HPLC with UVA S detection. However, by the conversion of the toxins to fluorescent derivatives (J), the problem of detection of the toxins is solved. It has been found that the fluorescent technique is highly sensitive and specific for PSP toxins and many of the current analytical methods for the toxins utilize fluorescent detection. With the toxin detection problem solved, the development of a useful HPLC method was possible and somewhat straightforward. 

In the end, what matters obviously is whether the features of interest distinctly show up in the analytical data, e.g., in a spectrum or a map or image. Thus, even though IR is not ultimately a surface specific technique, when an outermost surface layer reveals characteristic absorption bands that are related to say a property such as adhesion, the technique can be a very valuable one and is extensively applied. 

Within the IR spectroscopy arena, the most frequently used techniques are transmission-absorption, diffuse reflectance, ATR, specular reflectance, and photoacoustic spectroscopy. A typical in situ IR system is shown in Fig. 7. Choosing appropriate probe molecules is important because it will influence the obtained characteristics of the probed solid and the observed structure-activity relationship. Thus, the probe molecules cover a range from the very common to the very rare, in order to elucidate the effect of different surfaces to very specific compounds e.g. heavy water and deuter-ated acetonitrile, CDsCN). The design of the IR cell is extremely important and chosen to suit the purposes of each particular study. For catalytic reactions, the exposure of catalytic metals must be eliminated in cell construction, otherwise the observed effect of the catalyst may not be accurate. 

Spectroscopic Methods. HO and the other peroxy radicals have characteristic absorptions due to various molecular processes. In principle, these spectroscopic features could be used to determine atmospheric concentrations of peroxy radicals. The discussion of spectroscopic techniques in the measurement of peroxy radicals is divided into descriptions of specific spectral regions. General issues related to the use of spectroscopy for quantitative analysis are presented next. 

Analytical techniques are conveniently discussed in terms of the excitation-system-response parlance described earlier. In most cases the system is some molecular entity in a specific chemical environment in some physical container (the cell). The cell is always an important consideration however, its role is normally quite passive (e.g., in absorption spectroscopy, fluorescence, nuclear magnetic resonance, electron spin resonance) because the phenomena of interest are homogeneous throughout the medium. Edge or surface effects are most often negligible. On the other hand, interactions between phases are the central issue in chromatography and electrochemistry. In such heterogeneous techniques, the physical characteristics of the sample container become of critical... 

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