Raman technique

Introducing a new multivariate method based on targeted orthogonal partial least squares (T-OPLS) analysis, Abbas et al. could display even small changes of carotenoid distribution within algae cells of Dunailella (Chlamydomonadales) andPhaeodactylum (diatoms) [162]. 

This method offers the evaluation of spectra showing strong background noise and only low spectral variation and the prediction of the relative carotenoid concentration by using only a single reference spectrum. In addition, this reference compound does not need to be structurally identical to the target compound, as demonstrated for the predicted versus measured target spectrum for carotenoids [162]. 

In a later work combining the T-OPLS approach with SERS, the successful detection of l,l,3,3-tetrabromo-2-2-heptanone (THB), an antibacterial substance of the red alga Bonnemaisonia hamifera, at the concentration levels around some tens of femtograms per square micrometers is presented [163]. 

By the use of gold colloids (60 nm particle size) covered with a monolayer of 4 mercaptobenzonitrile serving as an internal standard for normalization of variations in the SERS effect, Abbas and coworkers could accurately calculate the distribution of THB over cell surfaces and close vicinity [163]. 

Oh and coworkers [165] successfully designed a special Raman approach based on statistic filters and PLS in data processing for a real-time assessment of glucose content on microalgae. 

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Laser Raman diagnostic teclmiques offer remote, nonintnisive, nonperturbing measurements with high spatial and temporal resolution [158], This is particularly advantageous in the area of combustion chemistry. Physical probes for temperature and concentration measurements can be debatable in many combustion systems, such as furnaces, internal combustors etc., since they may disturb the medium or, even worse, not withstand the hostile enviromnents [159]. Laser Raman techniques are employed since two of the dominant molecules associated with air-fed combustion are O2 and N2. Flomonuclear diatomic molecules unable to have a nuclear coordinate-dependent dipole moment caimot be diagnosed by infrared spectroscopy. Other combustion species include CFl, CO2, FI2O and FI2 [160]. These molecules are probed by Raman spectroscopy to detenuine the temperature profile and species concentration m various combustion processes. 

It is important to realize that electronic spectroscopy provides the fifth method, for heteronuclear diatomic molecules, of obtaining the intemuclear distance in the ground electronic state. The other four arise through the techniques of rotational spectroscopy (microwave, millimetre wave or far-infrared, and Raman) and vibration-rotation spectroscopy (infrared and Raman). In homonuclear diatomics, only the Raman techniques may be used. However, if the molecule is short-lived, as is the case, for example, with CuH and C2, electronic spectroscopy, because of its high sensitivity, is often the only means of determining the ground state intemuclear distance. 

Raman technique is usually more than an order of magnitude less than that of FTIR. 

The vibrational spectrum of cis- and fr s-[Pt(II) (NH3)2C12] in the crystalline phase has also been measured with laser-Raman techniques by Dr. Hoeschele of the Biophysics Department, Michigan State University. This technique shows great promise. 

Nevertheless, there has been a renewed interest in Raman techniques in the past two decades due to the discovery of the surface-enhanced Raman scattering (SERS) effect, which results from the adsorption of molecules on specially textured metallic surfaces. This large enhancement was first... 

Bussotti L., Castellucci E., Matteini M., The Micro-Raman Technique in the Studies for the Conservation of Art Works Identification of Lakes in Paints, Science and Technology for Cultural Heritage 1996 5 (1) 13. 

Most chemists tend to think of infrared (IR) spectroscopy as the only form of vibrational analysis for a molecular entity. In this framework, IR is typically used as an identification assay for various intermediates and final bulk drug products, and also as a quantitative technique for solution-phase studies. Full vibrational analysis of a molecule must also include Raman spectroscopy. Although IR and Raman spectroscopy are complementary techniques, widespread use of the Raman technique in pharmaceutical investigations has been limited. Before the advent of Fourier transform techniques and lasers, experimental difficulties limited the use of Raman spectroscopy. Over the last 20 years a renaissance of the Raman technique has been seen, however, due mainly to instrumentation development. 

The number of fundamental vibrational modes of a molecule is equal to the number of degrees of vibrational freedom. For a nonlinear molecule of N atoms, 3N - 6 degrees of vibrational freedom exist. Hence, 3N - 6 fundamental vibrational modes. Six degrees of freedom are subtracted from a nonlinear molecule since (1) three coordinates are required to locate the molecule in space, and (2) an additional three coordinates are required to describe the orientation of the molecule based upon the three coordinates defining the position of the molecule in space. For a linear molecule, 3N - 5 fundamental vibrational modes are possible since only two degrees of rotational freedom exist. Thus, in a total vibrational analysis of a molecule by complementary IR and Raman techniques, 31V - 6 or 3N - 5 vibrational frequencies should be observed. It must be kept in mind that the fundamental modes of vibration of a molecule are described as transitions from one vibration state (energy level) to another (n = 1 in Eq. (2), Fig. 2). Sometimes, additional vibrational frequencies are detected in an IR and/or Raman spectrum. These additional absorption bands are due to forbidden transitions that occur and are described in the section on near-IR theory. Additionally, not all vibrational bands may be observed since some fundamental vibrations may be too weak to observe or give rise to overtone and/or combination bands (discussed later in the chapter). 

Much of the microscopic information that has been obtained about defect complexes that include hydrogen has come from IR absorption and Raman techniques. For example, simply assigning a vibrational feature for a hydrogen-shallow impurity complex shows directly that the passivation of the impurity is due to complex formation and not compensation alone, either by a level associated with a possibly isolated H atom or by lattice damage introduced by the hydrogenation process. The vibrational band provides a fingerprint for an H-related complex, which allows its chemical reactions or thermal stability to be studied. Further, the vibrational characteristics provide a benchmark for theory many groups now routinely calculate vibrational frequencies for the structures they have determined. 

The FT-IR technique using reflection-absorption ( RA ) and transmission spectra to quantitatively evaluate the molecular orientation in LB films is outlined. Its application to some LB films are demonstrated. In particular, the temperature dependence of the structure and molecular orientation in alternate LB films consisting of a phenylpyrazine-containing long-chain fatty acid and deuterated stearic acid (and of their barium salts) are described in relation to its pyroelectricity. Pyroelectricity of noncentrosymmetric LB films of phenylpyrazine derivatives itself is represented, too. Raman techniques applicable to structure evaluation of pyroelectric LB films are also described. 

The Raman technique allows us to determine the intensity of Raman bands, and thereby to quantify the concentration of the chemical components in a complicated mixture (a Beer s law calibration graph of intensity against concentration is advisable see Section 9.1). 

A full range of spectral data was routinely reported for each of the new compounds isolated. Nuclear magnetic resonance (NMR) spectroscopy and X-ray crystallography have essentially only been used as methods of structure determination/ confirmation and the results are unexceptional. The use of mass spectrometry in these series of compounds has been mainly confined to molecular ion determination. Ultraviolet (UV), infrared (IR), and Raman techniques have been used for confirmation of structures, but no special report has been published. The major data in this field are well documented in CHEC-II(1996) and will not be reproduced in this chapter. Over the last decade, all these methods played a major role in establishing the structure, but did not provide new interesting structural information on these bicyclic systems. In consequence, these methods are not considered worthy of mention in detail here. 

The nature of coordination of anions such as nitrate, perchlorate, and thiocyanate has been studied by both infrared and Raman techniques. In the case of anions, such as nitrate and perchlorate, the vibrational spectra indicate whether they are ionic or coordinated and if coordinated, whether they are unidentate, bidentate or bridging. In the case of thiocyanate, the vibrational spectra are useful in deciding the site of coordination. The change in the site symmetry of the anion upon coordination leads to changes in vibrational spectra of anions like perchlorate, nitrate, perrhenate and hexa-fluorophosphate. These changes in the vibrational spectra have been used to indicate the nature of coordination. 

M. Kim, H. Chung, Y. Woo and M.S. Kemper, A new non-invasive, quantitative Raman technique for the determination of an active ingredient in pharmaceutical liquids by direct measurement through a plastic bottle. Anal. Chim. Acta, 587, 200-207 (2007). 

As the laser beam can be focused to a small diameter, the Raman technique can be used to analyze materials as small as one micron in diameter. This technique has been often used with high performance fibers for composite applications in recent years. This technique is proven to be a powerful tool to probe the deformation behavior of high molecular polymer fibers (e.g. aramid and polyphenylene benzobisthiazole (PBT) fibers) at the molecular level (Robinson et al., 1986 Day et al., 1987). This work stems from the principle established earlier by Tuinstra and Koenig (1970) that the peak frequencies of the Raman-active bands of certain fibers are sensitive to the level of applied stress or strain. The rate of frequency shift is found to be proportional to the fiber modulus, which is a direct reflection of the high degree of stress experienced by the longitudinally oriented polymer chains in the stiff fibers. 

They are derived from x-ray and neutron diffraction of crystals, and from electron diffraction and spectroscopic measurements with microwave, infrared and Raman techniques on the gaseous phase. For optimization of PEFs on small molecules, gas-phase structures are used. They are rather numerous, and they are all calculated... 

It is uncertain to what extent thermal equilibria are achieved in different parts of the flames. — A number of procedures are (in principle) available to determine flame temperatures The immediate measurement, for example by thermocouples, the thermochemical calculation, line reversal methods for electronic excitation temperatures, determination of vibrational or rotational temperatures. In addition more recent methods like advanced Raman techniques may be applied. 

Most divalent cation molybdates and tungstates crystallize in the scheelite lattice with the space group C n, Z=A. These compounds have been studied using the usual IR and Raman techniques 94—96). Single crystal studies 96—98) and samples with pure isotopes of Mo and Ca 99—101) have been reported. Additionally, recent information shows that vt hes above v% 84). It should be pointed out here that one cannot speak about purely internal vibrations since couphng with lattice vibrations is not neghgible, as seen in Ref. 101). 

In the case of the sulphur triimide S(NBu-f)3, the dispersive Raman technique applying a double monochromator and a CCD camera was employed to obtain the information from polarized measurements (solution studies) and also to obtain high-resolution spectra by low-temperature measurements. In the case of the main group metal complex, only FT-Raman studies with long-wavenumber excitation were successful, since visible-light excitation caused strong fluorescence. The FT-Raman spectra of the tetraimidosulphate residue were similar to those obtained from excitation with visible laser lines. 

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