Identification spectroscopic techniques

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. 

Before the advent of modern hyphenated techniques (GC/HS, GC/FTIR), numerous qualitative physical and chemical tests were devised for the identification of peaks in a gas chromatograa [705]. For the most part these tests were simple to perform, inexpensive, required minimum instrument modification and, in a few instances, provided a simple and easy solution to an otherwise complex problem. They still have some value today as spectroscopic techniques do not solve.all problems. 

A chroaatogreuB provides information regarding the complexity (numlser of components), quantity (peak height or area) and identity (retention par uleter) of the components in a mixture. Of these parameters the certainty of identification based solely on retention is considered very suspect, even for simple mixtures. When the identity can be firmly established the quantitative information from the chromatogram is very good. The reverse situation applies to spectroscopic techniques which provide a rich source of qualitative information from which substance Identity may be inferred with a reasonable degree of certainty. Spectroscopic Instruments have, however, two practical limitations it is often difficult to extract quantitative... 

Current trends in GC relate to miniaturisation, fast-GC, improved selectivity (mainly for short columns), stability of column stationary phases (reduction of bleeding) and increasing use of MS detection [117]. Finally, GC can be readily hyphenated with spectroscopic techniques without using involved interfaces and thus can easily provide unambiguous solute identification. 

TLC plates are of particular interest as substrates for spectroscopy (i) as a storage device for offline spectroscopic analysis (ii) for efficient in situ detection and identification and (iii) for exploitation of spectroscopic techniques that cannot be used in HPLC. Thin-layer chromatography combined with HR MAS (NMR) can be used for compound identification without the need for elution from the stationary phase [413]. Recently also TLC-XRF was found suitable for in situ TLC imaging of elements [414]. The combination... 

The identification of xanthophylls in vivo is a complex task and should be approached gradually with the increasing complexity of the sample. In the case of the antenna xanthophylls, the simplest sample is the isolated LHCII complex. Even here four xanthophylls are present, each having at least three major absorption transitions, 0-0, 0-1, and 0-2 (Figure 7.4). Heterogeneity in the xanthophyll environment and overlap with the chlorophyll absorption add additional complexity to the identification task. No single spectroscopic method seems suitable to resolve the overlapping spectra. However, the combination of two spectroscopic techniques, low-temperature absorption and resonance Raman spectroscopy, has proved to be fruitful (Ruban et al., 2001 Robert et al., 2004). 

Closs and Trifunac, 1970 Baldwin and Andrist, 1971 Lepley and Closs, 1972 Bethell and McDonald, 1977). The formation of free radicals from aromatic carbenes is often easily detected by the fast laser spectroscopic techniques discussed earlier. The radicals generally have characteristic absorption spectra and reactivity patterns that make their identification certain. The direct insertion reaction of singlet carbenes is not expected to generate free radicals. 

However, spectroscopic techniques, although nondestructive, do not provide the spatial information that can be critical in solving performance issues, or in developing true product and process understanding. Only techniques that combine both spatial and chemical identification information provide a complete set of tools to determine both product and process understanding. 

Molecular spectroscopic techniques have been widely used in pharmaceutical analysis for both qualitative (identification of chemical species) and quantitative purposes (determination of concentration of species in pharmaceutical preparations). In many cases, they constitute effective alternatives to chromatographic techniques as they provide results of comparable quality in a more simple and expeditious manner. The differential sensitivity and selectivity of spectroscopic techniques have so far dictated their specihc uses. While UV-vis spectroscopy has typically been used for quantitative analysis by virtue of its high sensitivity, infrared (IR) spectrometry has been employed mainly for the identihcation of chemical compounds on account of its high selectivity. The development and consolidation of spectroscopic techniques have been strongly influenced by additional factors such as the ease of sample preparation and the reproducibility of measurements, which have often dictated their use in quality control analyses of both raw materials and finished products. 

Identifying pharmaceuticals, whether APIs or excipients used to manufacture products, and the end products themselves is among the routine tests needed to control pharmaceutical manufacturing processes. Pharmacopoeias have compiled a wide range of analytical methods for the identification of pharmaceutical APIs and usually several tests for a product are recommended. The process can be labor-intensive and time-consuming with these conventional methods. This has raised the need for alternative, faster methods also ensuring reliable identification. Of the seven spectroscopic techniques reviewed in this book, IR and Raman spectroscopy are suitable for the unequivocal identification of pharmaceuticals as their spectra are compound-specific no two compounds other than pairs of enantiomers or oligomers possess the same IR... 

Interpretation of the spectroscopic data from the individual spectroscopic techniques is generally done as the data are amassed. When all of the data are available, it is useful for the participating scientists to integrate their respective data, which is discussed in more detail below. The overall elapsed time for the isolation and identification of a new impurity or degradation product is quite variable. The difficulty of the actual isolation and the structural complexity of the molecule both impinge on the process. On the basis of the author s experience. 

The preparative isolation of impurities may become necessary when an unambiguous identification cannot be achieved using hyphenated chromatographic-spectroscopic techniques, as discussed in Chapter 6 and in an excellent review [1]. The purpose of the isolation is to provide material... 

Chromatographic and spectroscopic techniques for detection and identification of organic conqwunds. 

Typically, sample detection in electromigration techniques is performed by on-column detection, employing a small part of the capillary as the detection cell where a property of either the analyte, such as UV absorbance, or the solution, such as refractive index or conductivity, is monitored. This section briefly describes the major detection modalities employed in capillary electromigration techniques, which are accomplished using UV-visible absorbance, fluorescence spectroscopy, and electrochemical systems. The hyphenation of capillary electromigration techniques with spectroscopic techniques employed for identification and structural elucidation of the separated compounds is also described. 

The hyphenation of capillary electromigration techniques to spectroscopic techniques which, besides the identification, allow the elucidation of the chemical structure of the separated analytes, such as mass spectrometry (MS) and nuclear magnetic resonance spectroscopy (NMR) has been widely pursued in recent years. Such approaches, combining the separation efficiency of capillary electromigration techniques and the information-rich detection capability of either MS or NMR, are emerging as essential diagnostic tools for the analysis of both low molecular weight and macromolecular compounds. 

Scully, M. O., Kattawar, G. W., Lucht, R. P., Opatmy, T., PUloff, H., Rebane, A., Sokolov, A. V., and Zubairy, M. S. 2002. FAST CARS Engineering a laser spectroscopic technique for rapid identification of bacterial spores. Proc. Natl. Acad. Sci. USA 99(17) 10994-11001. 

Before a species is analyzed with respect to its flavonoid content, knowledge about earlier reports on the chemistry and flavonoid distribution within the genus and related species may be of value. The most exhaustive source for such information is Chemical Abstracts, and excellent reviews on structures and distribution of flavanoids have been compiled regularly.Several reviews have recently addressed the general field of flavonoid analysis.Among the earlier reviews in the field, we will particularly recommend consulting Techniques of Flavonoid Identification by Markham and Plant Phenolics by Harborne. References to review articles on specific spectroscopic techniques applied on flavonoids will be cited under the various spectroscopic methods covered in this chapter. Spectroscopic information of importance is also presented in several other chapters in this book. 

In this review, we shall mainly consider the electrochemical behavior of sulfur and polysulfide ions (i.e. the reduced forms of sulfur) in solution. Recent works (see Sect. 8.3.1) gave a better understanding of the elementary steps leading from sulfur Sg to polysulfide ions S (or S ) in non-aqueous solvents. This has been achieved by using spectroscopic techniques for the identification of chemical species, the direct coupling of spectroscopic and electrochemical techniques, and by using digital simulation calculations for the validation of the proposed models. 

Pitts, J. N., Jr., H. W. Biermann, E. C. Tuazon, M. Green, W. D. Long, and A. M. Winer, Time-Resolved Identification and Measurement of Indoor Air Pollutants by Spectroscopic Techniques Nitrous Acid, Methanol, Formaldehyde, and Formic Acid, J. Air Pollut. Control Assoc., 39, 1344-1347 (1989). 

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