Rapid scanning spectroscopy detectors

Experimental limitations initially limited the types of molecular systems that could be studied by TRIR spectroscopy. The main obstacles were the lack of readily tunable intense IR sources and sensitive fast IR detectors. Early TRIR work focused on gas phase studies because long pathlengths and/or multipass cells could be used without interference from solvent IR bands. Pimentel and co-workers first developed a rapid scan dispersive IR spectrometer (using a carbon arc broadband IR source) with time and spectral resolution on the order of 10 ps and 1 cm , respectively, and reported the gas phase IR spectra of a number of fundamental organic intermediates (e.g., CH3, CD3, and Cp2). Subsequent gas phase approaches with improved time and spectral resolution took advantage of pulsed IR sources. 

Since modern FTIR spectrometers can operate in a rapid scan mode with approximately 50 ms time resolution, TRIR experiments in the millisecond time regime are readily available. Recent advances in ultra-rapid scanning FTIR spectroscopy have improved the obtainable time resolution to 5 ms. Alternatively, experiments can be performed at time resolutions on the order of 1-10 ms with the planar array IR technique, which utilizes a spectrograph for wavelength dispersion and an IR focal plane detector for simultaneous detection of multiple wavelengths. ... 

Fig. 5.6. A block diagram of an optical coherence tomography/Raman spectroscopy system C, circulator RSOD, rapid scanning optical delay BP, 785 bandpass BSO, beam shaping optics DM1, dichroic mirror at 990 nm DM2, dichroic mirror at 800-950 nm LP, long pass at 808 nm GP, galvanometer pair BD, balanced detector BPF, electronic band-pass filter AI-AO DAQ, analog input-output data acquisition (reprinted with permission from [34]. Copyright 2008 Optical Society of America)...

The scope of ultraviolet and visible spectrophotometry can be further extended when combined with a chromatographic separation step such as HPLC. The development of rapid-scanning detectors based on the linear photodiode array permits spectra to be acquired during the elution of peaks. Computer-aided manipulation of these spectra has led to new strategies for the examination of chromatographic peak homogeneity, based on classical techniques in spectroscopy. The use of microcomputers enables the development of archive retrieval methods for spectral characterisation (A. F. Fell etal, J. Chromat., 1984, 316, 423-440). 

The limited availability of affordable commercial RSSF instruments has been an important factor that has prevented the widespread application of RSSF spectroscopy to the study of biological systems. However, in the past year, a significant change in the availability of commercial instrumentation hats come about. There currently are at least five manufacturers of computerized rapid-scanning detector systems. The choices in commercial instrumentation range from a mechanically scanned system with a single photomultiplier detector to photodiode array detector systems. This review includes descriptions of the currently available commercial systems. Because the authors experience in the field of RSSF spectroscopy is limited to the use of diode array detector systems and because most of the commercial instruments have appeared on the market just within the past 12 months, it has not been possible to make detailed performance evaluations and comparisons of the new commercial systems. 

Such FPA detector setups were first used by the group of Lauterbach for the parallel characterization of solid samples and the product gas stream from catalytic reactors [18,19]. These authors also changed the mode of operation from the previously used step-scan mode to the rapid scan mode which made it possible to even record transient processes [20,21]. The group of Lauterbach was also the first to apply FPA IR spectroscopy to a problem from zeolite science, even if it was only in form of a feasibility study. They investigated the adsorption of CO on Cu-ZSM-5 and on Pt/Si02 in order to prove that it would be possible to detect the absorption bands of adsorbed species [19J. Since experiments were carried out at room temperature, bands for CO on the Cu-ZSM-5 would be expected to have very low intensity, and indeed, no spectra for CO on this solid were shown. The band of CO on the noble metal, on the other hand, could clearly be detected without problems, and a signal-to-noise ratio not much different from that obtained for a conventional experiment. 

Both instrument design and capabilities of fluorescence spectroscopy have greatly advanced over the last several decades. Advancements include solid-state excitation sources, integration of fiber optic technology, highly sensitive multichannel detectors, rapid-scan monochromators, sensitive spectral correction techniques, and improved data manipulation software (Christian et al., 1981 Lochmuller and Saavedra, 1986 Cabaniss and Shuman, 1987 Lakowicz, 2006 Hudson et al., 2(X)7). The cumulative effect of these improvements have pushed the limits and expanded the application of fluorescence techniques to numerous scientific research fields. One of the more powerful advancements is the ability to obtain in situ fluorescence measurements of natural waters (Moore, 1994). 

The main factor in beam analysis that affects the reliability of the analytical information is the reproducibility of the surfaces. When using scanning electron microscopy (SEM), the apparati are connected to the computer, which makes it possible to obtain quite a bit of information about the sample, especially by X-ray and AES. However, the apparati cannot assure the same length for beam penetration on the surface, which means that the analytical information can be uncertain. Because the beam analysis is rapid, it requires very fast detectors, e.g., Ge/Li or Si/Li. The LA can be successfully used in surface analysis. An automated system has been constructed, laser-induced breakdown spectrometry (LIBS).213 This is an alternative to other surface techniques — secondary ion mas spectroscopy (SIMS), SEM, X-ray photoelectron spectroscopy (XPS) — and it increases the lateral and depth resolution. 

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