Sample modulation spectroscopy

There are several types of measurements for which standard rapid-scanning interferometers may be inappropriate. These include hyperspectral imaging (Section 14.5), high-speed time-resolved spectrometry (Section 19.2), photoacoustic spectroscopy (Section 20.3), and sample modulation spectroscopy (Chapter 21). For these measurements it is necessary to hold the optical path difference constant while a measurement is made, after which the OPD is rapidly advanced to the next sampling position and then held constant once again for the next measurement. This process is repeated until all the data needed to obtain the interferogram are acquired. Such interferometers are called step-scan interferometers. 

To determine whether PLP was actually associated with the lysine radical, [4 - H]PLP was synthesized and exchanged into the enzyme, and the [4 - H]PLP-enzyme was used to prepare a sample of the putative product radical 3. The EPR spectrum of the sample containing [4 - H]PLP proved to be identical with that of a matched sample containing PLP. The two samples were submitted to electron spin echo envelope modulation spectroscopy (ESEEM). The ESEEM spectra revealed a signal corresponding to the Larmor frequency for deuterium in the sample containing [4 - H]PLP (Fig. 5) and no signal in the PLP sample. This meant that the deuterium in [4 - H]PLP must be... 

Figure 6. Interfacially confined hexadecane measured by SFM shear modulation spectroscopy. The shear response is measured simultaneously with the normal force deflection of the cantilever as function of the cantilever-siicon sample distance. The difference in the bending onset of the two curves defines the interfacially confined boundary layer thickness.

Rapid reversible processes can be studied by FT-IR spectrometry in at least four ways, two using rapid-scan interferometers and two using step-scan interferometers. Three of these approaches, asynchronous sampling and stroboscopic measurements with a rapid-scan interferometer and time-resolved spectroscopy with a step-scan interferometer, were described in Sections 19.2 and 19.3. The fourth approach involves the use of a step-scan interferometer and some type of sample modulation. We have seen one application in the earlier part of this chapter, and two other applications will now be described. The reorientation of liquid crystals induced by rapid switching of the electric field to which they are being subjected has been studied by at least three of these approaches. Results have been summarized in an excellent article by Czamecki [17]. In this section we discuss the application of sample-modulation FT-IR spectrometry to this problem. 

Finally, it should be noted that a more general application of modulation spectroscopy can be used to obtain selective information on an excitable sample. Modulated excitation (ME) spectroscopy can always be applied with samples allowing periodic stimulation via a periodic variation of any external thermodynamic parameter, e.g. temperature, pressure, concentration, electric field, light flux. ME causes a... 

There have been a few other experimental set-ups developed for the IR characterization of surfaces. Photoacoustic (PAS), or, more generally, photothemial IR spectroscopy relies on temperature fluctuations caused by irradiating the sample with a modulated monocliromatic beam the acoustic pressure wave created in the gas layer adjacent to the solid by the adsorption of light is measured as a fiinction of photon wavelength... 

Figure 4.16. To cover all possible transitions in the absorbing nucleus, the energy of the source radiation is modulated by using the Doppler effect, such that the emitted radiation has an energy E v) = Eo(l + vjc). For Fe the required velocities fall in the range (1 to t-1 cm s k In Mossbauer emission spectroscopy, the sample under investigation is the source, and a single line absorber is...

In order to more accurately identify the contaminant, and to determine if the fuel delivery system module filter was the source, both materials were analyzed using 1H NMR spectroscopy Samples were dissolved in a 60 40 mixture of deuterated chloroform/triflouroethanol. It should be noted that the amount of contaminant available for analysis was quite small, so for this sample, the NMR spectral acquisition time was set to 1 h in order to record a spectrum of adequate signal-to-noise ratio. 

A Fourier transform infrared spectroscopy spectrometer consists of an infrared source, an interference modulator (usually a scanning Michelson interferometer), a sample chamber and an infrared detector. Interference signals measured at the detector are usually amplified and then digitized. A digital computer initially records and then processes the interferogram and also allows the spectral data that results to be manipulated. Permanent records of spectral data are created using a plotter or other peripheral device. 

---