Infrared fingerprinting methods

With recent developments in analytical instrumentation these criteria are being increasingly fulfilled by physicochemical spectroscopic approaches, often referred to as whole-organism fingerprinting methods.910 Such methods involve the concurrent measurement of large numbers of spectral characters that together reflect the overall cell composition. Examples of the most popular methods used in the 20th century include pyrolysis mass spectrometry (PyMS),11,12 Fourier transform-infrared spectrometry (FT-IR), and UV resonance Raman spectroscopy.16,17 The PyMS technique... 

The simplest approach to this problem is to search a database for an identical , i.e., similar within certain tolerances, spectrum. This was developed for Infrared spectra (a technique ideally suited to such a fingerprinting method). The method was enhanced to include a more sophisticated statistical approach when applied to NMR spectra.In NMR spectra, variation in peak position due to concentration and temperature effects is larger than the peak width, and a more sophisticated approach is mandatory. In either case, the method is clearly one which yields limited or even confusing information for novel compounds. 

Despite the refinements yet to be made with the use of infrared fingerprinting of oils, there is no doubt that it is one of the better methods. 

Internal reflection spectroscopy of solids Mid-infrared internal reflection accessories were developed initially largely for studying the surface layer characteristics of a continuous flat solid sample, e.g., a polymer film although they may also be used as convenient methods of sample identification, when a surface layer spectrum may be taken as indicative of a sample s bulk characteristics. The sample surface is brought and held under low pressure into optical contact with the clean surface of an internal reflection element. Other common traditional uses have included the direct examination of fibers, foams, and malleable (soft) powders. It has, however, become common practice nowadays, with the sensitivity now available with FT-IR spectroscopy, to use single (or low-number) internal reflection accessories to conveniently and easily record a mid-infrared fingerprint... 

To detect adulteration of wine. Bums et al. (2002) found that the ratios of acetylated to p-coumaroylated conjugates of nine characteristic anthocyanins served as useful parameters to determine grape cultivars for a type of wine. Our laboratory utilized mid-infrared spectroscopy combined with multivariate analysis to provide spectral signature profiles that allowed the chemically based classification of antho-cyanin-containing fruits juices and produced distinctive and reproducible chemical fingerprints, making it possible to discriminate different juices. " This new application of ATR-FTIR to detect adulteration in anthocyanin-containing juices and foods may be an effective and efficient method for manufacturers to assure product quality and authenticity. 

High performance spectroscopic methods, like FT-IR and NIR spectrometry and Raman spectroscopy are widely applied to identify non-destructively the specific fingerprint of an extract or check the stability of pure molecules or mixtures by the recognition of different functional groups. Generally, the infrared techniques are more frequently applied in food colorant analysis, as recently reviewed. Mass spectrometry is used as well, either coupled to HPLC for the detection of separated molecules or for the identification of a fingerprint based on fragmentation patterns. ... 

Silylenes are short-lived intermediates, and their detection requires fast methods such as ultraviolet (UV)24 or laser-induced fluorescence spectroscopy.25 The characteristic absorption maxima in the UV-visible spectra of these species, which are assigned to n - p transitions of electrons at the silicon atom, were used as a fingerprint to prove the occurrence of silylenes in matrices or solution. In addition, these transient species, which under normal conditions are too short lived to be observed by a slow detection method such as infrared (IR) spectroscopy, can be isolated in inert hydrocarbon or noble gas matrices, thus allowing the accurate measurement of their IR spectra. 

Jeltes and Van Tonkelaar [20] investigated problems of oil pollution, the nature of the contaminants and the chemical methods used for their detection. In particular, the use of gas chromatography to obtain fingerprint chromatograms of oil pollutants in water, and of infrared spectrophotometry to determine the oil contents of soils and sediments, is discussed. 

The role of infrared spectroscopic characterization of catalysts should become increasingly important in catalyst development, but present problems, both experimental and theoretical must be recognized and overcome before reliable information can be routinely obtained using infrared methods. Techniques and understanding will improve as more information becomes available, but detailed interpretation of spectra will continue to present problems for some time. Partial interpretation and "fingerprinting can still be... 

Infrared spectroscopy can be applied to V. the characterization of polymeric materials at various levels of sophistication. As most commonly used, it is a rapid and easy method for the qualitative identification of major components through the use of group frequencies and distinctive patterns in the fingerprint region of the spectrum. Let s look at a couple of examples. 

More frequently than chemical techniques, the spectroscopic methods of analysis are used for the determination of polymer chemical composition. Among these techniques the use of infrared (IR) absorption spectra as fingerprints for polymer identification is probably the most common. The IR absorption is produced tjy the transition of the molecules from one vibrational quantum state into another, and most polymers generate characteristic spectra. Large databases containing polymer spectra (typically obtained using Fourier transform infra-red spectroscopy or FTIR) are available, and modern instruments have efficient search routines for polymer identification based on matching an unknown spectrum with those from the library. For specific polymers, the IR spectra can reveal even some subtle composition characteristics such as interactions between polymer molecules in polymeric blends. 

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