Selective detection

Based on the isolation procedure followed, one can conclude with some degree of certainty whether an isolated compound is an alkaloid or not. Particularly acid/base extraction schemes result in rather specific extraction of alkaloids. Moreover, several reagents that react specifically with alkaloids have been described, e.g., Dragendorffs reagent, potassium iodoplatinate, Mayer s reagent. The first two reagents mentioned are also used as detection 

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The pump-probe concept can be extended, of course, to other methods for detection. Zewail and co-workers [16,18, 19 and 2Q, 93] have used the probe pulse to drive population from a reactive state to a state that emits fluorescence [94, 95, 96, 97 and 98] or photodissociates, the latter situation allowing the use of mass spectrometry as a sensitive and selective detection method [99, 100]. 

Keil and co-workers (Dhamiasena et al [16]) have combined the crossed-beam teclmique with a state-selective detection teclmique to measure the angular distribution of HF products, in specific vibration-rotation states, from the F + Fl2 reaction. Individual states are detected by vibrational excitation with an infrared laser and detection of the deposited energy with a bolometer [30]. 

Recently, the state-selective detection of reaction products tluough infrared absorption on vibrational transitions has been achieved and applied to the study of HF products from the F + H2 reaction by Nesbitt and co-workers (Chapman et al [7]). The relatively low sensitivity for direct absorption has been circumvented by the use of a multi-pass absorption arrangement with a narrow-band tunable infrared laser and dual beam differential detection of the incident and transmission beams on matched detectors. A particular advantage of probing the products tluough absorption is that the absolute concentration of the product molecules in a given vibration-rotation state can be detenuined. 

Trace contaminants such as host cell proteins (HCPs) and DNA are deterrnined by more specialized techniques. Host cell proteins are generally deterrnined using an immunochemical assay, in which an antibody preparation, raised against a mixture of the HCPs, is used to selectively detect the total level of HCPs in the product. DNA can be deterrnined using a labeled mixture, or probe, of complimentary DNA from the host cell. 

As with many of the vitamins, biological assays have an important historical role and are widely used. For example, microbiological assays use l ctobacillusplantarum ATCC No. 8014 (57,59) or l ctobacillus arabinosus (60). These methods are appropriate for both nicotinamide and nicotinic acid. Selective detection of nictonic acid is possible if l euconostoc mesenteroides ATCC No. 9135 is used as the test organism (61). The use of microbiological assays have been reviewed (62). 

Rapid, simple, quaUtative methods suitable for determining the presence of benzene in the workplace or surroundings have been utilized since the 1930s. Many early tests offered methods for detection of aromatics but were not specific for benzene. A straightforward test allowing selective detection of benzene involves nitration of a sample to y -dinitrobenzene and reaction of the resultant ether extract with an ethanoHc solution of sodium hydroxide and methyl ethyl ketone (2-butanone), followed by the addition of acetic acid to eliminate interferences from toluene and xylenes. Benzene imparts a persistent red color to the solution (87). The method is claimed to be sensitive to concentrations as low as 0.27 ppm benzene from 10 mL air samples. 

Plasma atomic emission spectrometry is also employed as a detection method for gc (see Plasma technology). By monitoring selected emission lines a kind of selective detection based on elemental composition can be achieved (see Spectroscopy). 

Conductivity detectors, commonly employed in ion chromatography, can be used to determine ionic materials at levels of parts per million (ppm) or parts per bUHon (ppb) in aqueous mobile phases. The infrared (ir) detector is one that may be used in either nonselective or selective detection. Its most common use has been as a detector in size-exclusion chromatography, although it is not limited to sec. The detector is limited to use in systems in which the mobile phase is transparent to the ir wavelength being monitored. It is possible to obtain complete spectra, much as in some gc-ir experiments, if the flow is not very high or can be stopped momentarily. 

The influence of soil ageing on the recovery of POPs from spiked soil samples was also assessed. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of Endosulfan compounds. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection. 

Many different combinations, separation -i- element-selective detection, have been attempted but HPLC in conjunction with ISP-MS has emerged as one of the best combinations. HPLC is a versatile technique, which due to the vai iety of sepai ation mechanisms developed, can be applied to a great vai iety of medically important analytes. 

Since only relatively few substances are capable of emitting fluorescent radiation, they can be particularly selectively detected. This means that the selectivity of the chromatographic separation, which is always aimed at, is meaningfully extended by the selectivity of detection. Accompanying substances that absorb radiation but do not emit light do not interfere when the analysis is made by the selective determination of fluorescence ... 

Just like the physical and microchemical methods of detection, the indirect, biological-physiological detection procedures are very selective when apphed to thin-layer chromatography. Here it is not chemical functional groups or particular physical properties that are selectively detected but effects on highly sensitive biodetectors . The following detection techniques have been employed ... 

Figure 2.12 Schematic representation of an on-line SPE-GC system consisting of three switching valves (VI-V3), two pumps (a solvent-delivery unit (SDU) pump and a syringe pump) and a GC system equipped with a solvent-vapour exit (SVE), an MS instrument detector, a retention gap, a retaining precolumn and an analytical column. Reprinted from Journal of Chromatography, AIIS, A. J. H. Eouter et al, Analysis of microcontaminants in aqueous samples hy fully automated on-line solid-phase extraction-gas chromatography-mass selective detection , pp. 67-83, copyright 1996, with permission from Elsevier Science.

A. J. H. Louter, C. A. van Beekvelt, P Cid Montanes, J, Slobodnik, J. J. Vreuls and U. A. Th Brinkman, Analysis of microcontaminants in aqueous samples by fully automated on-line solid-phase exti action-gas cliromatography-mass selective detection , 7. Chromatogrl2S 67-83 (1996). 

S. Ulrich and J. Maitens, Solid-phase microextraction with capillai y gas-liquid cliro-matography and niti ogen-phosphoi us selective detection foi the assay of antidepressant drugs in human plasma , J. Chromatogr. B 696 217-234 (1997). 

Flame Photometric Detector3 With the flame photometric detector (FPD), as with the FID, the sample effluent is burned in a hydrogen/air flame. By using optical filters to select wavelengths specific to sulfur and phosphorus and a photomultiplier tube, sulfur or phosphorus compounds can be selectively detected. 

A liquid chromatographic experiment resulted in the same retention time for the electroactive compounds A and B. Which electrochemical detection scheme would offer a selective detection of the two coeluting analytes Explain your selection. (E = +0.43 V Eg = +0.77 V.)... 

Describe the rationale of using electrodes coated with Nation films for selective detection of the cationic neurotransmitter dopamine in the presence of the common interference from anionic ascorbic acid. 

Figure 5.27 Selective detection of lactolated peptides from a tryptic digest of / -lacto-globulins by LC-electrospray-MS-MS, showing (a) the total-ion-cnrrent trace in full-scan mode, and (b) the total-ion-current trace in neutral-loss-scanning mode. Figure from Selective detection of lactolated peptides in hydrolysates by liquid chromatography/ electrospray tandem mass spectrometry , by Molle, D., Morgan, F., BouhaUab, S. and Leonil, J., in Analytical Biochemistry, Volume 259, 152-161, Copyright 1998, Elsevier Science (USA), reproduced with permission from the publisher.

Primary alcohols can be selectively detected using reagent sequences involving an initial oxidation to yield aldehydes that are then reacted in acid medium with electron-rich aromatics or heteroaromatics, according to the above scheme, to yield intensely colored triphenylmethane dyes. 

Analysis of methyl parathion in sediments, soils, foods, and plant and animal tissues poses problems with extraction from the sample matrix, cleanup of samples, and selective detection. Sediments and soils have been analyzed primarily by GC/ECD or GC/FPD. Food, plant, and animal tissues have been analyzed primarily by GC/thermionic detector or GC/FPD, the recommended methods of the Association of Official Analytical Chemists (AOAC). Various extraction and cleanup methods (AOAC 1984 Belisle and Swineford 1988 Capriel et al. 1986 Kadoum 1968) and separation and detection techniques (Alak and Vo-Dinh 1987 Betowski and Jones 1988 Clark et al. 1985 Gillespie and Walters 1986 Koen and Huber 1970 Stan 1989 Stan and Mrowetz 1983 Udaya and Nanda 1981) have been used in an attempt to simplify sample preparation and improve sensitivity, reliability, and selectivity. A detection limit in the low-ppb range and recoveries of 100% were achieved in soil and plant and animal tissue by Kadoum (1968). GC/ECD analysis following extraction, cleanup, and partitioning with a hexane-acetonitrile system was used. 

Stan H-J. 1989. Application of capillary gas chromatography with mass selective detection to pesticide residue analysis. J Chromatogr 467 85-98. 

Leung AM, McDonough DM, West CD. 1998. Determination of endosulfans in soil/sediment samples from Point Mugu, Oxnard, CA, using capillary gas chromatography/mass selective detection (CC/MSD). Environmental Monitoring and Assessment 50(l) 85-94. 

Cool, T.A. et al., Selective detection of isomers with photoionization mass spectrometry for studies of hydrocarbon flame chemistry,. Chem. Phys., 119,8356,2003. 

Adequate techniques to accurately and selectively detect concentration levels are available, but are mostly expensive, slow, and complex. Cheaper sensors are available, but the working principle is usually not very selective. A wealth of different sensing techniques exists where typical sensor principles rely on changes in... 

Pali), P and Stamford, JA (1994) Real-time monitoring of endogenous noradrenaline release in rat brain slices using fast cyclic voltammetry. 3. Selective detection of noradrenaline efflux in the locus coeruleus. Brain Res. 634 275-282. 

P 24] The nitration of naphthalene was carried out with dissolved or in situ generated N2O5 gas [37]. The temperatare was set to -10 to 50 °C and residence times to 15—45 s. The reaction mixtare processed in the micro reactor was quenched with water, extracted and analyzed by HPLC or GC with mass-selective detection. 

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