IR absorbance spectroscopy

Vibrational spectroscopy, too, has been used to study supercritical fluid systems. Buback reviewed (59) this area however, much of his discussions are on fluid systems that are well removed from ambient conditions or difficult to handle easily (e.g., H20, HC1). In an early report, Hyatt (21) used IR absorbance spectroscopy to determine the influence of several solvent systems, including COz, on the vibrational frequencies ( ) of solute molecules. Specifically, he studied the vc=o of acetone and cyclohexanone and vs.H of pyrrole. The goal of this work was to determine the suitability of supercritical fluids as reaction solvent. Hyatt concluded that the ketones experienced an environment similar to nonpolar hydrocarbons in COz and that there were no differences between liquid and supercritical CO2. In contrast, the pyrrole studies indicated that the solvent strength of CO2 was between ether and ethyl acetate. This apparent anomalous result was a manifestation of the, albeit weak, degree of pyrrole hydrogen bonding to CO2. 

A fundamental property of chemical bonds is that they exhibit vibrations at distinct frequencies. The vibrational frequency of a given chemical bond is intrinsic to the chemical bond of interest [6]. The characteristic frequencies of a given molecule are called a vibrational spectrum. There are many methods for the investigation of vibrational spectra. The most basic measurement technique for molecular vibrations is IR absorbance spectroscopy. In practice IR absorbance spectra are measured by FT methods, which are described later in this chapter. The vibrations measured by an FT-IR are often enough to uniquely chemically identify small amounts of... 

The effect of antioxidants such as hindered phenohcs, secondary amine, and thioester on the radiation cross-linking efficiency of LDPE has been reported [260]. Amount of cross-linking at a given dose decreases with aU the antioxidants, the thioester being the most effective. IR absorption spectroscopy has been used to demonstrate dose-rate dependence of trani -vinylene unsaturation in irradiated Marlex 50 PE [261]. When the irradiated polymer is stored in vacuum a decrease is observed in trani-vinylene absorbance over a period of several weeks. After high dose-rate irradiation the decay is preceded by an initial increase. These phenomena have been ascribed to the reaction of trapped radicals. 

The adsorption of transition metal complexes by minerals is often followed by reactions which change the coordination environment around the metal ion. Thus in the adsorption of hexaamminechromium(III) and tris(ethylenediamine) chromium(III) by chlorite, illite and kaolinite, XPS showed that hydrolysis reactions occurred, leading to the formation of aqua complexes (67). In a similar manner, dehydration of hexaaraminecobalt(III) and chloropentaamminecobalt(III) adsorbed on montmorillonite led to the formation of cobalt(II) hydroxide and ammonium ions (68), the reaction being conveniently followed by the IR absorbance of the ammonium ions. Demetallation of complexes can also occur, as in the case of dehydration of tin tetra(4-pyridyl) porphyrin adsorbed on Na hectorite (69). The reaction, which was observed using UV-visible and luminescence spectroscopy, was reversible indicating that the Sn(IV) cation and porphyrin anion remained close to one another after destruction of the complex. 

Figure 5.11 Diffuse Reflectance Absorbance Spectroscopy Taking In Chemometiics (DRASTIC), a FT-IR-based method for rapid screening for metabohtes. Different concentrations of ampicillin (ranging from 0 to 5 mg/mL) were mixed with a constant amount E. coli cells, dried and analyzed by FT-IR (Winson et at, 1997).

More information about the sequential pathway versus one in which the 0—0 and C C bond homolyses occur conceitedly was obtained by means of picosecond IR absorption spectroscopy. While IR spectroscopy, in principle, can provide more structural information, hmitations stemming from the weakness of some IR intensities can be detrimental to the detection of a reactive intermediate. In this case, the CO2 photoproduct was monitored (near 2335 cm ) instead of radical intermediates 2 or 3. It was argued that neither 1, 2, nor 3 absorbed in this region. Excitation of 1 in CCLi was achieved with a 308-nm, 1-ps pulse. The 1.3-ps probe pulse may be tuned to cover a range from 2000 to 4300 cm with the spectrometer that was used, but in these specific experiments the interrogation window was from... 

Absorbance subtraction can be considered as a spectroscopic separation technique for some problems in polymers. An interesting application in FT-IR difference spectroscopy is the spectral separation of a composite spectrum of a heterophase system. One such example is a semicrystalline polymer which may be viewed as a composite system containing an amorphous and crystalline phase53). In general, the infrared spectrum of each of these phases will be different because in the crystalline phase one particular rotational conformation will predominate whereas in the disordered amorphous regions a different rotamer will dominate. Since the infrared spectrum is sensitive to conformations of the backbone, the spectral contributions will be different if they can be isolated. The total absorbance A, at a frequency v of a semicrystalline polymer may be decomposed into the following contributions... 

Infrared spectroscopy can provide a great deal of information on molecular identity and orientation at the electrode surface [51-53]. Molecular vibrational modes can also be sensitive to the presence of ionic species and variations in electrode potential [51,52]. In situ reflectance measurements in the infrared spectrum engender the same considerations of polarization and incident angles as in UV/visible reflectance. However, since water and other solvents employed in electrochemistry are strong IR absorbers, there is the additional problem of reduced throughput. This problem is alleviated with thin-layer spectroelectro-chemical cells [53]. 

Immunity to interfering species is perhaps the most important consideration in any gas detection method. Because gases absorb IR light over a narrow spectral range and only at characteristic wavelengths, instruments based on IR absorption spectroscopy offer greater selectivity than most other techniques. 

An interesting technique recently published uses FTIR spectroscopy to detect anions [149]. Thin films of tetraalkylated ferrocenium salts were evaporated onto ATR crystals. Exposure to anion-containing solutions caused incorporation of the anions, and they could then be detected via their IR absorbances. Limits of detection for 10-min analyses varied from 10 6 to 10 s M for a variety of anions however, this technique cannot be used to detect anions that do not have IR absorbances, such as halides. 

With infrared reflection absorption spectroscopy (IRRAS), it is possible to obtain information about the orientation of enzyme molecules adsorbed on flat metal surfaces (3,4). Electric dipole-transition moments oriented perpendicular to a flat metal surface show enhanced IR absorbance. IR bands due to vibrations of groups with transition moments oriented parallel to the surface are not observed. The IR-beam component which is polarized perpendicular to the plane of incidence (parallel to the surface) contains no information and can be eliminated by using a polarizer. 

Time-resolved spectroscopy is performed using a pump-probe method in which a short-pulsed laser is used to initiate a T-jump and a mid-IR probe laser is used to monitor the transient IR absorbance in the sample. A schematic of the entire instrument is shown in Fig. 17.4. For clarity, only key components are shown. In the description that follows, only those components will be described. A continuous-wave (CW) lead-salt (PbSe) diode laser (output power <1 mW) tuned to a specific vibrational mode of the RNA molecule probes the transient absorbance of the sample. The linewidth of the probe laser is quite narrow (<0.5 cm-1) and sets the spectral resolution of the time-resolved experiments. The divergent output of the diode laser is collected and collimated by a gold coated off-axis... 

Kell DB, Winson MK, Goodacre R, Woodward AM, Alsberg BK, Jones A, Timmins EM, Rowland JJ (1998) DRASTIC (Diffuse Reflectance Absorbance Spectroscopy Taking In Chemometrics). A novel, rapid, hyperspectral, FT-IR-based approach to screening for biocatalytic activity and metabolite overproduction. In Kieslich K (ed) New Frontiers in Screening for Microbial Biocatalysts. Elsevier Science B. V., The Netherlands, p 61... 

Very thin films (monolayer or multilayer) can be studied by IR spectroscopy, provided that the IR beam crosses a reasonably large fraction of the monolayer this can be done by (i) grazing-angle techniques (whereby the IR beam angles of incidence and reflection are of the order of 1° to 3°) or (ii) multiple internal reflections of the IRbeam inside the monolayer (infrared reflectance and absorbance spectroscopy (IRRAS). Fig. 11.19 shows the chemical structure of an analyte (Fullerene-fcz s-[ethylthio-tetrakis(3,4-dibutyT2-thiophene-5-ethenyl)-5-bromo-3,4-dibutyl-2-thiophene] malonate),... 

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