Coupled fiber-optic probes

There are many examples of second-order analyzers that are used in analytical chemistry including many hyphenated spectroscopic tools such as FTIR-TGA, IR-microscopy, as well as GC-MS, or even two-dimensional spectroscopic techniques. Another hyphenated technique that is being developed for the study of solid-state transitions in crystalline materials is dynamic vapor sorption coupled with NIR spectroscopy (DVS-NIR).26 DVS is a water sorption balance by which the weight of a sample is carefully monitored during exposure to defined temperature and humidity. It can be used to study the stability of materials, and in this case has been used to induce solid-state transitions in anhydrous theophylline. By interfacing an NIR spectrometer with a fiber-optic probe to the DVS, the transitions of the theophylline can be monitored spectroscopically. The DVS-NIR has proven to be a useful tool in the study of the solid-state transitions of theophylline. It has been used to identify a transition that exists in the conversion of the anhydrous form to the hydrate during the course of water sorption. 

Figure 3.40 shows the layout of a typical Raman analyzer that uses fiber optics for process application. In a Raman process system, light is filtered and delivered to the sample via excitation fiber. Raman-scattered light is collected by collection fibers in the fiber-optic probe, filtered, and sent to the spectrometer via return fiber-optical cables. A charge-coupled device (CCD) camera detects the signal and provides the Raman spectrum. To take advantage of low-noise CCD cameras and to minimize fluorescence interference, NIR diode lasers are used in process instruments. 

A similar design that coupled fiber optic NSOM probes with AFM cantilevers was also reported [28]. In this approach, shown in Fig. 14, a standard fiber optic NSOM probe was carefully inserted through the 7 pm hole that was cut into the end of an AFM probe. Once glued into place, the excess fiber on the backside of the AFM cantilever was removed using FIB milling. This approach... 

All plasma exposures were carried out in an IPC (International Plasma Corporation) 2005 capacitance-coupled barrel reactor at 13.56MHz. The reactor was equipped with an aluminum etch tunnel and a temperature controlled sample stage. Pressure was monitored with an MKS capacitance manometer RF power was monitored with a Bird R.F. power meter and substrate temperature was measured with a Fluoroptic thermometer utilizing a fiber optic probe which was immune to R.F. noise. 

Fortunately, automated fiber-optic probe-based dissolution systems have begun to appear for these solid dosage-form applications. One such system uses dip-type UV transflectance fiber-optic probes, each coupled to a miniature photodiode array (PDA) spectrophotometer to measure drug release in real time. This fiber-optic dissolution system can analyze immediate- and controlled-release formulations. The system is more accurate and precise than conventional dissolution test systems, and it is easier to set up than conventional manual sampling or automated sipper-sampling systems with analysis by spectrophotometry or HPLC. 

PE O Rourke, RR Livingston. Fiber optic probe having fibers with endfaces formed for improved coupling efficiency and methods using the same. U.S. Patent 5,402,508 (March 28, 1995). 

Figure 18 Comparison of Raman spectra collected of sheep aorta in vivo and in vitro (a) spectrum of aorta collected in vivo arrows indicate most prominent signal contributions of blood (b) in vitro spectrum of aorta (luminal side) (c) in vitro spectrum of freshly drawn heparinized blood. Experimental conditions laser power =100 mW laser wavelength = 830 nm signal collection time = 30 sec Visionex Enviva fiber-optic probe coupled to a customized Renishaw system 100 Raman spectrometer.

Figure 1 (A) Afibre optic spectroscopy system with separate illumination and collection path is based on an excitation source, which is a laser or a white light source (reflectometry) or a monochromator filtered arc lamp (fluorescence). Optics couple the excitation light into the flexible probe. A probe collects the emitted light. Coupling optics adapt the numerical aperture of the probe to the spectrograph or filter system. An optical detector (charge coupled device (CCD), photodiode array, photomultiplier tube) is read out and digitized. (B) A fibre optic spectroscopy system with a probe that incorporates one optical fibre needs a dichroic beam splitter and well aligned optics to separate excitation and fluorescence light. Reproduced with permission of Optical Society of America Inc. from Greek LS, Schulze HG, Blades MW, Haynes CA, Klein K-F and Turner RFB (1998) Fiber-optic probes with improved excitation and collection efficiency for deep-UV Raman and resonance Raman spectroscopy. Applied Optics Z7 ).

Raman spectra were acquired on a Kaiser Optical Systems Holoprobe Raman Spectrometer, equipped with a remote fiber optic probe. Data for offline calibration were acquired from fiber bundles that were mounted in a sample holder and oriented vertically, with respect to the probe mounted on an x-y stage. At least five Raman spectra were acquired and averaged for each fiber sample used in the calibration. Typical data acquisition parameters were 20 second acquisition, two accumulations, dark subtraction and cosmic ray filter turned ON and white light correction turned OFF. Full power of a 400 mW, 785 nm NIR laser (Invictus, Kaiser Optical Systems, Ann Arbor MI) was injected into a 15 m, 50 m core multimode excitation fiber. A 15 m, 100 m multimode collection fiber was used to couple the... 

A particularly difficult problem in microwave processing is the correct measurement of the reaction temperature during the irradiation phase. Classical temperature sensors (thermometers, thermocouples) will fail since they will couple with the electromagnetic field. Temperature measurement can be achieved either by means of an immersed temperature probe (fiber-optic or gas-balloon thermometer) or on the outer surface of the reaction vessels by means of a remote IR sensor. Due to the volumetric character of microwave heating, the surface temperature of the reaction vessel will not always reflect the actual temperature inside the vessel [7]. 

The subsequent development of laser diode sources at low cost, and improved electronic detection, coupled with new probe fabrication techniques have now opened up this field to higher-temperature measurement. This has resulted in an alexandrite fluorescence lifetime based fiber optic thermometer system,(38) with a visible laser diode as the excitation source which has achieved a measurement repeatability of l°C over the region from room temperature to 700°C, using the lifetime measurement technique. 

Fiber-optic-coupled spectrophotometers (single beam and double beam) are the best choice for on-line analyses. The advent of nonsolarizing optical fiber has made possible on-line analyses in which the spectrophotometer may be located remotely from the process and light is carried to/from the process by the optical fiber. A rugged probe or flow cell provides the sample interface. 

Design and selection of the sample interface is vital to provide the best-quahty data for an analysis. The sample interface may be located in the sample cavity of a spectrophotometer, as in the cases of laboratory cuvettes, vials, and flow cells. The sample interface may also be fiber-coupled and located closer to the process. Fiber-optic sample interfaces include flow cells, insertion probes, and reflectance probes. 

Bauer et al. describe the use of a noncontact probe coupled by fiber optics to an FT-Raman system to measure the percentage of dry extractibles and styrene monomer in a styrene/butadiene latex emulsion polymerization reaction using PLS models [201]. Elizalde et al. have examined the use of Raman spectroscopy to monitor the emulsion polymerization of n-butyl acrylate with methyl methacrylate under starved, or low monomer [202], and with high soUds-content [203] conditions. In both cases, models could be built to predict multiple properties, including solids content, residual monomer, and cumulative copolymer composition. Another study compared reaction calorimetry and Raman spectroscopy for monitoring n-butyl acrylate/methyl methacrylate and for vinyl acetate/butyl acrylate, under conditions of normal and instantaneous conversion [204], Both techniques performed well for normal conversion conditions and for overall conversion estimate, but Raman spectroscopy was better at estimating free monomer concentration and instantaneous conversion rate. However, the authors also point out that in certain situations, alternative techniques such as calorimetry can be cheaper, faster, and often easier to maintain accurate models for than Raman spectroscopy, hi a subsequent article, Elizalde et al. found that updating calibration models after... 

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