Fluorescence instrumentation electronics

Because the fluorescence spectrum is recorded and stored in the computer memory, it subsequently can be conveniently manipulated. Blank or reference spectra can be subtracted spectra can be normalized, smoothed according to some spline function and integrated, and multiplied or divided by different factors for spectral comparison and differences between spectra can be reviewed. Finally, the output of such instruments can be conveniently formatted to whatever representation one requires. 

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For sensors that are truly mass sensitive and for which the mass flow of sample through the sensing element is held constant as a function of pressure (for example, by use of electronic mass-flow controllers), instrument response is proportional to the mixing ratio independent of the pressure. For concentration-sensitive detectors, such as simple spectrophotometric instruments measuring absorbance or fluorescence, instrument response is a function of the absolute concentration, and the response will decrease for a constant mixing ratio as the pressure decreases. For example, the response of a pulsed fluorescence SO instrument sampling air containing a fixed... 

The function of the spectrometer is to accept as much light from the source as possible and to isolate the required spectral lines. This may be impossible where there is a continuous spectrum in the same region as the analytical line for example, the magnesium line of 286.2 nm coincides with a hydroxyl band. In direct reading instruments, electronic devices may be used to supplement the resolution of the spectrometer by modulating the intensity of the analytical signal. In absorption and fluorescence the light source is modulated in emission the spectral line is scanned (816) or the sample flow modulated (M23). 

The above section has outlined the physical parameters that describe the fluorescence process. One can measure the fluorescence spectrum, P(X), the singlet excited state lifetime, xs, and determine the Tliese parameters can be interpreted in terms of the structure, environment and ( mamics of the molecule of interest. In this section, the different optical and electronic components comprising an instrument that can measure Fl( ) and will be described. This instrument is generally known as a steady state fluorescence spectrometer, since it integrates the fluorescence intensity over a given time period. Time-resolved fluorescence instrumentation that is used to measure the excited singlet state decay times is described in Chapter 3. 

A schematic of an X-ray fluorescence instrument is presented in Figure 3. The X-ray tube is used as the source of primary radiation hv. The vacancies in inner shells of atoms of the substance investigated are formed as a result of primary radiation action. These vacancies are filled by other inner or outer electrons. This is accompanied by X-ray fluorescent photons hv2 being emitted. This fluorescence radiation is spread out into the spectrum by means of a crystal analyser (or, for the ultrasoft X-ray region, by means of diffraction gratings) in accordance with Bragg s law... 

Instrumental Methods for Bulk Samples. With bulk fiber samples, or samples of materials containing significant amounts of asbestos fibers, a number of other instmmental analytical methods can be used for the identification of asbestos fibers. In principle, any instmmental method that enables the elemental characterization of minerals can be used to identify a particular type of asbestos fiber. Among such methods, x-ray fluorescence (xrf) and x-ray photo-electron spectroscopy (xps) offer convenient identification methods, usually from the ratio of the various metal cations to the siUcon content. The x-ray diffraction technique (xrd) also offers a powerfiil means of identifying the various types of asbestos fibers, as well as the nature of other minerals associated with the fibers (9). 

Cathodoluminescence (CL), i.e., the emission of light as the result of electron-beam bombardment, was first reported in the middle of the nineteenth century in experiments in evacuated glass tubes. The tubes were found to emit light when an electron beam (cathode ray) struck the glass, and subsequendy this phenomenon led to the discovery of the electron. Currendy, cathodoluminescence is widely used in cathode-ray tube-based (CRT) instruments (e.g., oscilloscopes, television and computer terminals) and in electron microscope fluorescent screens. With the developments of electron microscopy techniques (see the articles on SEM, STEM and TEM) in the last several decades, CL microscopy and spectroscopy have emerged as powerfirl tools for the microcharacterization of the electronic propenies of luminescent materials, attaining spatial resolutions on the order of 1 pm and less. Major applications of CL analysis techniques include ... 

Oscillograph. A cathode-ray oscilloscope in which a photographic or other permanent record is produced by the electron beam of a cathode-ray tube. A cathode-ray oscilloscope is a test instrument that uses a cathode-ray tube to make visible on a fluorescent screen the instantaneous values and waveforms of electrical quantities that are rapidly varying as a function of time... 

The most common final separation techniques used for agrochemicals are GC and LC. A variety of detection methods are used for GC such as electron capture detection (BCD), nitrogen-phosphorus detection (NPD), flame photometric detection (FPD) and mass spectrometry (MS). For LC, typical detection methods are ultraviolet (UV) detection, fluorescence detection or, increasingly, different types of MS. The excellent selectivity and sensitivity of LC/MS/MS instruments results in simplified analytical methodology (e.g., less cleanup, smaller sample weight and smaller aliquots of the extract). As a result, this state-of-the-art technique is becoming the detection method of choice in many residue analytical laboratories. 

Because of the underlying photophysics, fluorescence lifetimes are intrinsically short, usually on the order of a few nanoseconds. Detection systems with a high timing resolution are thus required to resolve and quantify the fluorescence decays. Developments in electronics and detector technology have resulted in sophisticated and easy to use equipment with a high time resolution. Fluorescence lifetime spectroscopy has become a popular tool in the past decades, and reliable commercial instrumentation is readily available. 

Three analytical techniques which differ in how the primary vacancies are created share the use of such X-rays to identify the elements present. In X-ray fluorescence, the solid sample is irradiated by an X-ray beam (called the primary beam), which interacts with the atoms in the solid to create inner shell vacancies, which then de-excite via the emission of secondary or fluorescent X-rays - hence the name of the technique. The second uses a beam of electrons to create the initial vacancies, giving rise to the family of techniques known collectively as electron microscopy. The third and most recently developed instrumentation uses (usually) a proton beam to cause the initial vacancies, and is known as particle- (or proton-) induced X-ray emission (PIXE). 

Exposure of elements to a broad spectrum of X-rays results in the ejection of electrons from their inner shells. Electrons from outer shells falling into these vacancies emit radiation of specific wavelengths (see Figure 14.13). Analysis of this radiation, referred to as X-ray fluorescence (XRF), allows for the identification of the element from which the photon is emitted. Instruments for carrying out this analysis can be either laboratory sized or can be handheld... 

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