Detectors specific detectivity

Aqueous distillates are extracted, usually with dichloro-methane (DCM), concentrated to small volumes, generally in a Kuderna-Danish evaporator, and examined by gas chromatography (GC) using a specific detection system. Additional chromatographic cleanup may be required, depending on the complexity of the sample and specificity of the chromatographic detector. 

Drushel [58] and others [31,59] have described the needs of the chromatographer in the area of detectors. Specific texts concern detection in quantitative GC [54], diode-array detection in HPLC [48], selective detectors [39] and element-specific chromatographic detection by AES [60], electrochemical detectors [61] and laser detectors [62]. 

The most important area for packed column use involves modified mobile phases (MPs). Consequently, pSFC needs detection systems in which the MP modifier and possible additive(s) do not interfere, and in which detection of low or non-UV-absorbing molecules is possible in combination with pressure/modifier gradients. The disadvantage of adding even small amounts of modifier is that FID can no longer be used as a detector. In the presence of polar modifiers in pSFC the detection systems are restricted basically to spectroscopic detection, namely UVD, LSD, MSD (using PB and TSP interfaces as in LC). ELSD can substitute FID and covers the quasi-universal detection mode, while NPD and ECD cover the specific detection mode in pSFC on a routine basis. As ELSD detects non-UV absorbing molecules dual detection with UV is an attractive option. 

Mass spectrometry can be specific in certain cases, and would even allow on-line QA in the isotope dilution mode. MS of molecular ions is seldom used in speciation analysis. API-MS allows compound-specific information to be obtained. APCI-MS offers the unique possibility of having an element- and compound-specific detector. A drawback is the limited sensitivity of APCI-MS in the element-specific detection mode. This can be overcome by use of on-line sample enrichment, e.g. SPE-HPLC-MS. The capabilities of ESI-MS for metal speciation have been critically assessed [546], Use of ESI-MS in metal speciation is growing. Houk [547] has emphasised that neither ICP-MS (elemental information) nor ESI-MS (molecular information) alone are adequate for identification of unknown elemental species at trace levels in complex mixtures. Consequently, a plea was made for simultaneous use of these two types of ion source on the same liquid chromatographic effluent. 

Each of the five types of detectors listed has advantages and limitations, making each more or less suitable for an application or a specific risk. There is not a uniform performance standard for flame detectors such as their is with smoke detectors. Flame detection for a particular model has to be analyzed by evaluation of its technical specification to expected fire development. 

Element-specific detection combined with capillary GC has become a key technique in the chemical communication studies of our laboratory. An effective detector of this type is based on the microwave plasma emission (Wylie and Quimby 1989), with a tunable selectivity for several elements and a prominent sensitivity for sulfur-containing compounds, which is significantly greater than... 

The signals from masses 292 and 326 characteristic of tetra- and pentachlorobiphenyl are shown in Fig. 1.6 (b,c). The specific detection mode of the ion-trap detector can be used to improve detection limits. This detector can monitor specific masses that are characteristic of compounds of interest. The detector records the signal for only those masses and ignores all others. Interference from other compounds is virtually eliminated with the Finnigan MAT 700 detector—up to 16 different groups of masses can be monitored or a mass range of up to 40 masses can be handled. With this flexibility it is possible to monitor only the masses of interest and to improve detection limits. 

Bishop, P. The ion trap detector, universal and specific detection in one detector. Finnigan MAT IDT 28. 

Neumayr [3] has discussed methods for sampling soil atmospheres and gives a detailed account of gas chromatographic methods employing electron capture and flame ionization detectors for detecting and estimating specific components of the soil atmosphere. 

Many separation and detection methods applied in combination with liquid chromatography (LC) that are described in the literature for the determination of surfactants are not specific to the detection of these compounds at trace levels. Even ultraviolet (UV) spectra obtained from diode array detectors often give only limited information. Furthermore, non-reproducible retention behaviour as well as coelution interference effects are frequently observed during the separation of surfactant-containing extracts. This is recognised, however, only in those cases where specific detection methods such as mass spectrometry (MS) are applied. 

For reference methods, HPLC with various detectors has become the standard reference technique for analysis of food additives, but new developments in this area are mainly linked to detector technology. Diode array detectors have not totally met the expectations of food analysts in terms of their specificity and LC-MS is likely to fill the gap. Specific detection with biosensor chips may also have a future for certain analyses. The use of combined LC-MS/DAD systems is... 

Figure 3.13 The spectral dependence of the specific detectivity for several photoconduction detectors. The values corresponding to a typical thermopile and to a typical piroelectric detector are also shown.

Figure 3.15 shows the spectral dependence of the specific detectivity, D, reported for germanium and indium arsenide photodiodes, respectively. The main properties of these detectors are also summarized in Table 3.1 for comparison. 

In order to eliminate some of these variables in comparing detector performance characteristics, it is usual to use a parameter described as specific detectivity (D ) and defined as ... 

The infrared radiation caused by the heat of reaction of an enantioselective enzyme-catalyzed transformation can be detected by modern photovoltaic infrared (IT)-thermographic cameras equipped with focal-plane array detectors. Specifically, in the lipase-catalyzed enantioselective acylation of racemic 1-phenylethanol (20), the (K)- and (S)-substrates were allowed to react separately in the wells of microtiter plates, the (7 )-alcohol showing hot spots in the IR-thermographic images (113,114). Thus, enantioselective enzymes can be identified in kinetic resolution. However, quantification has not been achieved thus far by this method, which means that only those mutants can be identified which have E values larger than 100 (113-115). 

Every analyst who has access to CE equipment and ESI-MS may take this new alternative into consideration when appropriate. When is it appropriate If an analytical problem can be solved using affinity capillary electrophoresis and a more universal and specific detection or structural information is required than is accessible with the help of conventional UV diode array detectors, consider ACE/MS. 

Satisfactory results for a method can only be obtained with well-performing equipment. Therefore, before an instrument is used to validate a method, its performance should be verified using universal standards (47). Special attention should be paid to the equipment specifications that are critical for the performance of the method. For example, if detection limit is critical for a specific method, the detector specifications for baseline noise and the response to the specified compounds should be checked. Furthermore, any reagent or reference standard used to determine critical validation parameters should be double-checked for accurate composition and purity. 

The choice of the detector becomes crucial when the concentration of analyte species in the sample is very low and low limits of detection are required. For element-specific detection, the major atomic spectrometric techniques, flame AAS, OES, AFS and ICP-MS, are specially suited as chromatographic... 

Transient signals are typically obtained in atomic spectrometry when samples are introduced by flow injection techniques or when the spectrometer is used as an element-specific detector in hyphenated techniques. Inductively coupled plasma mass spectrometry has nowadays become the detection technique of choice for multielement-specific detection in speciation as it allows multielemental... 

Polychromatic detection. The most sophisticated detectors (e.g. DAD diode-array detectors) either allow the wavelength to be changed during the course of the analysis or simultaneously record the absorbance at several wavelengths. These detectors can be used not only to record the chromatogram but also to provide spectral information that can be used to identify the compounds. This is called specific detection (cf. 11.14). 

EM Fujinari, JD Manes. Nitrogen-specific detection of peptides in liquid chromatography with chemiluminescent nitrogen detector. J Chromatogr A 676 113-120, 1994. 

Since cyclamate has poor UV absorbing characteristics, HPLC methods for the analysis of this sweetener require specific detection systems, such as indirect photometry or conductivity. Herrmann et al. (24) used indirect photometry for the detection of cyclamate at 267 nm against a UV-absorbing mobile-phase component, p-toluenesulphonate. Biemer (17) and Wu et al. (47) used a conductivity detector for the determination of cyclamate. According to Biemer (17) the use of this detector offers distinct advantages, since compounds coeluting with cyclamate may not exhibit an electrochemical response and, hence, not appear in the chromatogram. 

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