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Photodiode Array Detectors

Photodiode array detectors can be used to measure and detect samples over the entire UV to visible (UV-Vis) spectrum. They are highly beneficial tools in identification and analysis of sample compounds.To detect over an entire spectrum, the detector must proceed in one of two ways. The first is to scan across the entire spectral region, which may be accomplished by a scanning monochromator spectrometer: (Jones,1985)A standard scanning monochromator spectrometer uses a tungsten or deuterium lamp that emits a continuous light source. The light is then directed across a grating or prism which reflects the light through an exit slit to the sample cell. The sample is then detected by a photomultiplier tube. The wavelength of the light can be adjusted by rotating the grating or prism, but only one region can be scanned at a time. Subsequently, data points are obtained at different times, which may hinder efficiency and accuracy (Jones, 1985).The second method involves monitoring the entire UV-Vis region simultaneously. One technique is to use several photomultiplier tubes positioned to detect in the spectral regions of interest. Another is to use the linear photodiode array (LPDA) spectrophotometer which measures in the 190-1100 nm region simultaneously. No monochromatic light is needed and data can be retrieved in milliseconds. The versatility of LPDA rapid detection allows additional applications such as analyzing kinetic or chemical intermediates, or separating and analyzing overlapping chromatographic peaks using spectography (Jones, 1985)Two simultaneous monitoring systems currently used are multiplex and multichannel techniques. In multiplex, encoded information is received at a single detector and transform methods, such as Fourier transform, modify the data into spectral data. Multichannel techniques consist of a radation- sensing element, a charge storage element, and a readout system. They are basically electronic imaging detectors and developments have led to the usage of LPDA's in this technique. The LPDA consists of channels (or array of diodes) which act individually as a light-to-charge converter and storage apparatus. It is more agreeable in UV-Vis spectrometry than other image detectors since it has high quantum efficiency throughout this spectrum (Jones, 1985).It is possible to have a combination multiplex and multichannel system using a common-path interferometer (CPI):(Jones, 1985)Radiation proceeds through a sample into the CPI which constructs an interference pattern (interferogram) that is detected by a LPDA. A computer reconstructs the data from the interferogram using Fourier transform(Currently under construction). In this system there are no slits or moving parts. The usefulness of this type of spectrometer is under investigation although it is commercially available.Another type uses the Tracer Northern optical arrangement, which is a LPDA spectrophotometer that has a reverse-optical arrangement:(Jones, 1985).The source shines a light beam through the sample into the polychromator, which in turn emits the light onto the LPDA situated where the exit slit would be located in a regular spectrophotometer. Each diode on the array corresponds and detects a wavelength or set of wavelengths in the UV-Vis region (X number of diodes separates the spectrum into X number of wavelength sets). It operates in a charge-integrating mode and accomplishes this simulataneously in each wavelength set. The time required to process the data is 4 to 28 µsec for each diode, so rapid data acquisition is no longer a problem for LPDA; instead, complications could occur in mass data storage and rapid display (Jones, 1985).The following is data of the spectrochromatogram of zimeldine and metabolites separated by reversed-phase HPLC:(Jones, 1985).This graph is an example of a three-dimensional isometric chromatogram of absorbance, wavelength, and time. LPDA data is usually received in digitized form, so after display it may be stored, retrieved, and later manipulated using various techniques (Eg., Chemometric data manipulation). 

Jones, D.G. Analytical Chemistry, 1985, Vol. 57, pp. 1057-1073

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