Reflection spectroscopy techniques

Aside from the conventional IR spectroscopy of measuring hght transmitted from the sample, the reflection IR spectroscopy was developed using combination of IR spectroscopy with reflection theories. In the reflection spectroscopy techniques, the absorption properties of a sample can be extracted from the reflected Ught. 

Spectra of insoluble solid phenolic prepolymers or crosslinked products can be recorded by diffuse reflectance (DRIFT) and attenual total reflection spectroscopy (ATR). Reflection spectroscopy techniques are qualitative methods for analysis of insoluble materials [228], which work by reflecting the infrared light off the surface of the material to be analyzed. Table 7 gives a summary of wavenumbers of absorbance bands in modified phenolic materials. 

Specular reflection spectroscopy has been actively used in in situ studies of the formation and optical behaviour of monolayer films on surfaces, and for detecting intermediates and products of heterogeneous chemical and electrochemical reactions. The vibrational spectra of the adsorbed species at electrode surfaces are obtained by surface-enhanced Raman scattering and infrared reflectance spectroscopies. Since the mid-1960s, modulated reflection spectroscopy techniques have been employed in elucidating the optical properties and band structure of solids. In the semiconductor electroreflectance, the reflectance change at the semiconductor surface caused by the perturbation of the dielectric properties of... 

The principle of the reflectance spectroscopy technique is to shine a monochromatic light beam, usually polarised in a plane parallel or perpendicular to the plane of incidence, at an electrode surface at a known angle of incidence and to record the intensity of the reflected beam as a function of either wavelength, potential or time. The data obtained are then compared to model calculations made using the same three layer model as is used in ellipsometry, i.e. bulk electrode/interfacial region/bulk solution. These calculations are based on the Fresnel equations [19] and assume that all phases are isotropic. 

These computations were also used to screen the most favorable configuration of a molecule on a given surface. For example, the most stable conformation of a carboxylic acid (oleate) molecule on a fluorite 111 surface was found to be a bidentate conformation (Mielczarski et al. 2002). As shown in Figure 2.7, the theoretically simulated conformation, as indicated through adsorption angles, matched well with that measured experimentally, as obtained through a sophisticated in situ infrared external reflection spectroscopy technique (Mielczarski et al. 1998). 

FIGURE 2.7 Conformation of adsorbed oleate molecule on fluorite 111 surface. The numbers in bracket denote experimental angles obtained through insitu infrared external reflection spectroscopy technique reported by (From Mielczarski, E., Mielczarski, J. A., and Cases, J. M., Langmuir, 14 1739,1998.)... 

The methods of presenting samples such as a tissue or isolated single cell for study in an FT-IR microscope have to date been predominantly confined to transmission and, the so-called, transflection sampling techniques. The latter is actually a reflection-absorption technique vide infra). Of increasing recent interest is use of the so-called ATR sampling technique for the analysis of tissue samples. ATR is an abbreviation for attenuated total reflection and is an internal reflection spectroscopy technique. On the horizon are perhaps nearfield techniques. Each of these will now be considered in turn. 

Figure 4.2 Schematic diagrams of some reflection spectroscopy techniques (a)-(c), internal reflection spectroscopy (a) and (b), single-reflection ATR (c), multiple internal reflection (MIR) (d) transflectance . Notes (i) collimated beam with ATR hemicylinder (ii) the component of specular reflectance (dotted line) will be superimposed on the double-pass transmission spectrum of the film in the transflectance measurement.

While electron or ion beam techniques can only be applied under ultra-high vacuum, optical techniques have no specific requirements concerning sample environment and are generally easier to use. The surface information which can be obtained is, however, quite different and mostly does not contain direct chemical information. While with infra-red attenuated total reflection spectroscopy (IR-ATR) a deep surface area with a typical depth of some micrometers is investigated, other techniques like phase-measurement interference microscopy (PMIM) have, due to interference effects, a much better surface sensitivity. PMIM is a very quick technique for surface roughness and homogeneity inspection with subnanometer resolution. 

Some of the transition metal macrocycles adsorbed on electrode surfaces are of special Interest because of their high catalytic activity for dloxygen reduction. The Interaction of the adsorbed macrocycles with the substrate and their orientation are of Importance In understanding the factors controlling their catalytic activity. In situ spectroscopic techniques which have been used to examine these electrocatalytlc layers Include visible reflectance spectroscopy surface enhanced and resonant Raman and Mossbauer effect spectroscopy. This paper Is focused principally on the cobalt and Iron phthalocyanlnes on silver and carbon electrode substrates. 

Of special Interest as O2 reduction electrocatalysts are the transition metal macrocycles In the form of layers adsorptlvely attached, chemically bonded or simply physically deposited on an electrode substrate Some of these complexes catalyze the 4-electron reduction of O2 to H2O or 0H while others catalyze principally the 2-electron reduction to the peroxide and/or the peroxide elimination reactions. Various situ spectroscopic techniques have been used to examine the state of these transition metal macrocycle layers on carbon, graphite and metal substrates under various electrochemical conditions. These techniques have Included (a) visible reflectance spectroscopy (b) laser Raman spectroscopy, utilizing surface enhanced Raman scattering and resonant Raman and (c) Mossbauer spectroscopy. This paper will focus on principally the cobalt and Iron phthalocyanlnes and porphyrins. 

It is only since 1980 that in situ spectroscopic techniques have been developed to obtain identification of the adsorbed intermediates and hence of reliable reaction mechanisms. These new infrared spectroscopic in situ techniques, such as electrochemically modulated infrared reflectance spectroscopy (EMIRS), which uses a dispersive spectrometer, Fourier transform infrared reflectance spectroscopy, or a subtractively normalized interfacial Fourier transform infrared reflectance spectroscopy (SNIFTIRS), have provided definitive proof for the presence of strongly adsorbed species (mainly adsorbed carbon monoxide) acting as catalytic poisons. " " Even though this chapter is not devoted to the description of in situ infrared techniques, it is useful to briefly note the advantages and limitations of such spectroscopic methods. 

In the early work of Bewick and Robinson (1975), a simple monochromator system was used. This is called a dispersive spectrometer. In the experiment the electrode potential was modulated between two potentials, one where the adsorbed species was present and the other where it was absent. Because of the thin electrolyte layer, the modulation frequency is limited to a few hertz. This technique is referred to as electrochemically modulated infrared reflectance spectroscopy (EMIRS). The main problem with this technique is that data acquisition time is long. So it is possible for changes to occur on the electrode surface. 

In recent years,3 4 however, there has been renewed interest in the study of the electrode/solution interface due in part to the development of new spectroscopic techniques such as surface-enhanced Raman spectroscopy,5-7 electrochemically modulated infrared reflectance spectroscopy and related techniques,8,9 second-harmonic generation,10-12 and others which give information about the identity and orientation of molecular species in the interfacial... 

In materials investigations surface-sensitive techniques are of special interest. The major contribution of infrared spectroscopy to this field is internal reflection spectroscopy (IRS), often called the "attenuated total reflection" (ATR) technique. To describe theory and principle, electromagnetic wave theory must be apphed [33]. 

For many years, meteorites have provided the only means to determine the abundance of 3He in protosolar material. The values obtained by mass spectroscopy techniques in the so-called planetary component of gas-rich meteorites have been critically examined by Geiss (1993) and Galli et al. (1995). The latter recommend the value 3He/4He= (1.5 0.1) x 10-4. The meteoritic value has been confirmed by in situ measurement of the He isotopic ratio in the atmosphere of Jupiter by the Galileo Probe Mass Spectrometer. The isotopic ratio obtained in this way, 3He/4He= (1.66 0.04) x 10 4 (Mahaffy et al. 1998), is slightly larger than, but consistent with, the ratio measured in meteorites, reflecting possible fractionation in the protosolar gas in favor of the the heavier isotope, or differential depletion in Jupiter s atmosphere. 

Until quite recently the very initial stages of metal deposition were difficult to characterize in detail by structure- and morphology-sensitive techniques. As a consequence and for practical purposes - multilayers were more useful for applications than monolayers - the main interest was focussed onto thick deposits. Optical and electron microscopy, ellipsometry and specular or diffuse reflectance spectroscopy were the classic tools, by which the emerging shape of the deposit was monitored [4-7],... 

It was recognized very early that diffuse reflectance spectroscopy could be used to study the interactions of various compounds in a formulation, and the technique has been particularly useful in the characterization of solid state reactions [24]. Lach concluded that diffuse reflectance spectroscopy could also be used to verify the potency of a drug in its formulation. In addition, studies conducted under stress conditions would be useful in the study of drug-excipient interactions, drug degradation pathways, and alterations in bioavailability owing to chemisorption of the drug onto other components in the formulation [24]. 

Although most often connected with investigations of solid dosage forms, diffuse reflectance spectroscopy can also be used to characterize alternative formulations. Through the use of a special sample cell, the technique has been used to study the stability of emulsions [37]. In this work, it was found that information could be obtained that pointed toward subtle changes in the emulsion microenvironment. 

Although UV/VIS diffuse reflectance spectroscopy has not been used extensively in the study of pharmaceutical solids, its applications have been sufficiently numerous that the power of the technique is evident. The full reflectance spectra, or the derived colorimetry parameters, can be very useful in the study of solids that are characterized by color detectable by the human eye. It is evident that questions pertaining to the colorants used for identification purposes in tablet formulations can be fully answered through the use of appropriately designed diffuse reflectance spectral experiments. With the advent of newer, computer-controlled instrumentation, the utility of UV/VIS diffuse reflectance as a characterization tool for solids of pharmaceutical interest should continue to be amply demonstrated. 

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