Displacement effects, detector

Detector displacement effects are about the only way a detector can produce spurious peaks. If the materials of construction of the sensor cell, or any part of the sensor that comes in contact with the mobile phase, can adsorb materials contained in the mobile phase, then these can be a source of spurious peaks. If solutes are eluted from a sample that are adsorbed more strongly on the sensor parts than the solvent components, then the mobile phase components will be displaced into the mobile phase and appear as a... 

The dispersive (+ n, - m ) mode has already been seen clearly with the duMond diagrams, Figure 2.10. Here, the curves are no longer identical and the crystals must be displaced from the parallel position in order to get simultaneous diffraction. As the crystals are displaced, so the band of intersection moves up and down the curve. When the curves become very different, the K 1 and K 2 intensities are traced out separately. Then the peaks are resolved in the rocking curve, and if no better beam conditioner is available it is important in such cases to remove the K 2 component with a slit placed after the beam conditioner. A slit placed in front of the detector, with the detector driven at twice the angular speed of the specimen, also works very well. This is in effect a low resolution triple-axis measurement. 

The alcohol will come off in the void volume of the column since it has no attraction to the column. The amines will be retained, because at the pH of the acetate solution they are protonated and have a positive charge. As more mobile phase passes the through the column, its sodium ions begin to compete for the sulfonate sites with the bound amines. Through a mass effect, the amines are displaced down the column until, finally, they elute into the detector. The amine that has the strongest charge and binds the tightest is eluted last. 

Reversed-phase high-performance liquid chromatography (RP-HPLC) is the usual method of choice for the separation of anthocyanins combined with an ultraviolet-visible (UV-Vis) or diode-array detector (DAD)(Hebrero et al., 1988 Hong et ah, 1990). With reversed-phase columns the elution pattern of anthocyanins is mainly dependent on the partition coefficients between the mobile phase and the Cjg stationary phase, and on the polarity of the analytes. The mobile phase consists normally of an aqueous solvent (water/carboxylic acid) and an organic solvent (methanol or acetonitrile/carboxylic acid). Typically the amount of carboxylic acid has been up to 10%, but with the addition of a mass spectrometer as a detector, the amount of acid has been decreased to as low as 1 % with a shift from trifluoroacetic acid to formic acid to prevent quenching of the ionization process that may occur with trifluoroacetic acid. The acidic media allows for the complete displacement of the equilibrium to the fiavylium cation, resulting in better resolution and a characteristic absorbance between 515 and 540 nm. HPLC separation methods, combined with electrochemical or DAD, are effective tools for anthocyanin analysis. The weakness of these detection methods is a lack of structural information and some nonspecificity leading to misattribution of peaks, particularly with electrochemical... 

The two other decay processes in Table 5.4 are less common in nature. In K-capture, any orbiting electron (usually in an inner shell) combines with a proton in the nucleus to form a neutron. This relatively rare nuclear transformation process (e + p+ —> n°) is just the opposite of that for P decay, meaning that the formed nucleus also has the same mass but is displaced one element to the left on the periodic table. Conversion of to °Ar by K-capture is an example of the chemical conversion that can attend radioactive decay, in this case leading to transformation of a non-volatile alkali metal into the inert gas Ar, the third most abundant gas in the atmosphere. Although no nuclear particle is emitted by K-capture, the attending cascade of electrons into lower orbitals leads to X-ray emission of characteristic energy that can be measured by the appropriate detectors. The last decay process (also rare) involves emission of a positron (p+), a positively charged electron. The nuclear process (p+ n° + p+) has the same net effect as K-capture and is also characterized by X-ray emission. 

Multi-site detection involves the displacement of the detection unit from one manifold site to one or more other sites (see 7.6.2). As different solutions are inherent to the different sites involved, occurrence of the Schlieren effect is unavoidable. This approach is particularly attractive for improving sample throughput, implementing sequential determinations, re-conditioning the detector and/or exploiting differential kinetics. The potential applications of this approach have been reviewed elsewhere [111]. 

The displacement of the heavy ligand by the lighter molecule HCN yields an increase in the sensitivity, a concept identified as "mass amplification", and was not applied to piezoelectric detectors before. As mass is lost from the coated crystal when exposed to HCN, the frequency increases whereas a decrease in frequency is expected if moisture is absorbed by the coating. The effect of humidity was studied over the range of 40-92% RH, and it was shown that humidity plays a part in the reacation. Since the reaction is irreversible and the nickel complex is prone to hydrolysis, the coated crystal could be used once only. Substitution of other ligands in nickel complexes, including dibenzoylmethane, dipivaloyl-methane, formate and acetate, did not improve the selectivity towards HCN. 

As mentioned above, output stability is important. All sources exhibit some degree of output fluctuation, and so many instruments include a means by which these fluctuations can be monitored. The most common approach is to use a beam-splitter or displacer to generate a reference beam that can be monitored by an auxiliary detector. The reference channel can serve to minimize the effects of instability on detection limits, although various factors (including shot noise) place resflictions on this ability. 

Interferences from plastic containers are often plasticizers that leach into the sample. If they produce strong responses in the electron capture detector, then even small quantities can have a deleterious effect on an assay. Phosphate-based plasticizers have caused problems with nitrogen-phosphorous detection. Furthermore, it has been shown that tris (2-butoxyethyl)phosphate, a plasticizer once used in Vacutainer stoppers, can displace basic drugs... 

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