Specifications detector sensitivity

The analysis of complex matrices, such as natural products, food products, environmental pollutants and fossil fuels, is today a very important area of separation science. The latest developments in chromatographic techniques have yielded highly efficient systems, used with specific detectors to obtain high selectivity and or sensitivity. 

It is usually recognized that general detectors are less sensitive than specific detectors, have a lower dynamic range (see below) and do not give the best results when gradient elution is used. 

Solute property detectors, such as spectroscopic andj electrochemical detectors, respond to a physical or chemical] property characteristic of the solute which, ideally, is] independent of the mobile phase. Althou this criterion is rarely met in practice, the signal discrimination is usually sufficient to permit operation with solvent changes (e.g., flow programming, gradient elution, etc.) and to provide high sensitivity with aj wide linear response range. Table 5.4. Solute-specific detectors complement ulk property detectors as they provide high ... 

Detectors are composed of a sensor and associated electronics. Design and performance of any detector depends heavily on the column and chromatographic system with which it is associated. Because of the complexity of many mixtures analysed and the limitation in regard to resolution, despite the use of high-resolution capillary columns and multicolumn systems, specific detectors are frequently necessary to gain selectivity and simplify the separation system. Many detectors have been developed with sensitivities toward specific elements or certain functional groups in molecules. Those detectors that exhibit the highest sensitivity are often very specific in response, e.g. the electron capture detector in GC or the fluorescence detector in LC. Because... 

Compatibility with a wide variety of sensitive and specific detectors multidetection... 

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. 

When operated as a specific detector the ion-trap detector is more sensitive still but not to the extent that would be expected from the performance of other mass spectrometers operated in this mode in view of the large number of ions monitored in full scan mode there is little more sensitivity to be gained by spending a little extra time scanning a narrow mass range, and the detection limit in this mode is in the region of l-2pg. 

Earlier experiments based on EAG and SSR highlighted the inordinate specificity and sensitivity of the insect olfactory system. While minimal structural modifications to pheromone molecules render them inactive [12], a single molecule of the native ligand is estimated to be sufficient to activate an olfactory neuron in male antennae [14]. The large number of detectors certainly contributes to the sensitivity of the olfactory system, but selectivity is a matter of... 

As a volatile material, bromomethane is readily determined by gas chromatographic analysis. The selectivity and sensitivity of detection are increased by the use of an electron capture detector or a halide-specific detector, both of which are very sensitive for organohalides such as bromomethane. Specificity in detection is achieved with mass spectrometric detectors. 

The pesticides included in this study were fenvalerate, chlordecone (kepone), chlorothalonil, and chlorpyrifos. Fenvalerate is a synthetic pyrethroid insecticide used, for example, for mites on chickens. Its chemical name is cyano(3-phenoxyphenyl)-methyl 4-chloro-alpha-(1-methylethyl)benzeneacetate. Chlordecone is an insecticide, no longer used, and has a chemical name decachloro-octahydro-l,3,4-metheno-2H-cyclobuta(cd)=pentalen-2-one. Chlorothalonil is fungicide used on tomatoes whose chemical name is 2,4,5,6-tetrachloroisophthalonitrile. Chlorpyrifos is an insecticide with a chemical name 0,0-diethyl 0-(3,5,6-trichloro-2-pyridyl)phosphorothioate. Chlorpyrifos is the U. S. Food and Drug Administration chromatographic reference standard since numerous specific detectors (electron capture, flame photometric in both sulfur and phosphorus modes, alkali flame, nitrogen phosphorus, and Hall detectors) are sensitive to it. 

For systems with moderate-to-low probability, CE might not be the chromatographic quantification method of choice, and other alternatives, such as HPLC and GC, should be considered. However, specific procedures (e.g., off-line concentration, stacking techniques, extended light path capillaries) and detectors may be applied to increase solubility and sensitivity of detection, such as derivatization (e.g., carbohydrates, amino acids, amines, etc.) or the use of a specific detector (e.g., contactless conductivity detection, coupling with mass spectrometry, etc.). However, increasing the complexity of the methodology may be counterproductive if it leads to a lower robustness and transferability of the system. 

Certain SEC applications solicit specific experimental conditions. The most common reason is the limited sample solubility. In this case, special solvents or increased temperature are inavoid-able. A possibility to improve sample solubility and quality of eluent offer multicomponent solvents (Sections 16.2.2 and 16.8.2). The selectivity of polymer separation by SEC drops with the deteriorating eluent quality due to decreasing differences in the hydrodynamic volume of macromolecules with different molar masses. The system peaks appear on the chromatograms obtained with mixed eluents due to preferential solvation of sample molecules (Sections 16.3.2 and 16.3.3). The multicomponent eluents may create system peaks also as a result of the (preferential) sorption of their components within column packing [144,145]. The extent of preferential sorption is often sensitive toward pressure variations [69,70,146-149]. Even if the specific detectors are used, which do not see the eluent composition changes, it is necessary to discriminate the bulk sample solvent from the SEC separated macromolecules otherwise the determined molecular characteristics can be affected. This is especially important if the analyzed polymer contains a tail of fractions possessing lower molar masses (Sections 16.4.4 and 16.4.5). 

The most sensitive and specific detector is ED, but the insolubility of the electrolytes in NP eluents preclude its wide application. A FED is generally preferred due to its higher selectivity and specificity than a UV method, but the latter may be preferred in simultaneous analysis of other lipophilic compounds such as TAGs, sterols, and vitamins A, D, and K [448,482,483]. MS and tandem MS have been recently introduced as detector for vitamin E. 

---