Techniques differential pulse polarography

The use of polarographic assays for the determination of drugs in blood is the most demanding on the detection limitations of the technique. Differential pulse polarography, stripping voltammetry, and LCEC are the only electrochemical methods currently available for routine determination of drugs below 1.0 ng/mL of blood. 

Kalvoda has reviewed different electrochemical methods suppression of polarographic maxima, eletrocapillary measurements, Kalousek commutator technique, differential pulse polarography and tensammetric methods for the determination of oily substances in various types of waters. These compounds are neither reducible nor oxidizable but are surface active. The study of oil fractions has shown that the Kalousek technique responds only to higher levels of dissolved petroleum fractions (0.02 to 100 mg/1) found only in pollution sources such as harbors and refinery effluents.Recent results indicate that the water pollution with petroleum can be determined by differential pulse tensammetry. Good calibration graphs were obtained with Diesel oil at a concentration from 30-50 /xg to 0.5 mg/1 and with Saratov petroleum from 0.1-0.2 to 3.3 mg/1. ... 

In just the same way as differential pulse polarography represents a vast improvement over conventional polarography (see Section 16.10), the application of a pulsed procedure leads to the greatly improved technique of differential pulsed anodic (cathodic) stripping volammetry. A particular feature of this... 

In conclusion, synthetic dyes can be determined in solid foods and in nonalcoholic beverages and from their concentrated formulas by spectrometric methods or by several separation techniques such as TEC, HPLC, HPLC coupled with diode array or UV-Vis spectrometry, MECK, MEECK, voltammetry, and CE. ° Many analytical approaches have been used for simultaneous determinations of synthetic food additives thin layer chromatography, " " derivative spectrophotometry, adsorptive voltammetry, differential pulse polarography, and flow-through sensors for the specific determination of Sunset Yellow and its Sudan 1 subsidiary in food, " but they are generally suitable only for analyzing few-component mixtures. 

The ability of differential pulse polarography to resolve multicomponent systems and evaluate concentrations with excellent sensitivity has made this technique an attractive candidate for simultaneous measurement of CO, O, and some inhalation anesthetics Though very preliminary, the results appear promising and will likely lead to more intensive investigation of the approach. 

The Model 384B (see Fig. 5.10) offers nine voltammetric techniques square-wave voltammetry, differential-pulse polarography (DPP), normal-pulse polar-ography (NPP), sampled DC polarography, square-wave stripping voltammetry, differential pulse stripping, DC stripping, linear sweep voltammetry (LSV) and cyclic staircase voltammetry. 

Lopez-Fonseca et al. [11] discussed the theory of reverse pulse polarography and the technique was applied in the determination of penicillamine electrochemically coated on a dropping-mercury electrode. Using long drop times and short pulses, the drug can be determined at levels as low as 50 nM in the presence of Cu(II), and the technique compares well with normal-pulse and differential-pulse polarography. 

Mercury was determined after suitable digestion by the cold vapour atomic absorption method [40]. Lead was determined after digestion by a stable isotope dilution technique [41-43]. Copper, lead, cadmium, nickel, and cobalt were determined by differential pulse polarography following concentration by Chelex 100 ion-exchange resin [44,45], and also by the Freon TF extraction technique [46]. Manganese was determined by flameless atomic absorption spectrometry (FAA). 

The following analytical techniques seem to be adequate for the concentrations under consideration copper and nickel by Freon extraction and FAA cold vapour atomic absorption spectrometry, cobalt by Chelex extraction and differential pulse polarography, mercury by cold vapour atomic absorption absorptiometry, lead by isotope dilution plus clean room manipulation and mass spectrometry. These techniques may be used to detect changes in the above elements for storage tests Cu at 8 nmol/kg, Ni at 5 nmol/kg, Co at 0.5 nmol/kg, Hg at 0.1 nmol/kg, and Pb at 0.7 nmol/kg. 

The cavity of diphenylglycoluril derivative 3 is well suited to partially encapsulate a [4Fe-4S] cluster. Compound 29 which contains four arms terminating with thiol groups was synthesized and treated with (n-Bu)4N 2 Fe4S4Cl4) in dimethylformamide to give cluster complex 30 [31]. The product was characterized by a number of techniques, including cyclic voltammetry and differential pulse polarography. The current response of 30 was very small, but improved upon addition of a modulator, e.g. Ba or Na" ions. This behavior is similar to that observed for certain redox active enzymes [32]. As in the natural systems, a maximum response is observed when the Ba concentration is... 

Many of the experimental parameters for normal-pulse polarography are the same as with differential-pulse polarography. Differential-pulse polarography is a technique that uses a series of discrete potential steps rather than a linear potential ramp to optimize specific applications (130). Unlike normal-pulse polarography, each potential step has the same amplitude, whereas the return potential after each pulse is slightly negative of the potential prior to the step. In this manner, the total waveform applied to the dropping mercury electrode is very much like a combination of a linear ramp with a superimposed square wave. 

The mathematics outlined in this section are fairly well applicable to a technique named differential pulse polarography [21, 48, 50]. The potential is programmed as a sequence of normal potential steps each with a small amplitude potential pulse superimposed [see Fig. 14(a)]. The problem of separating the small amplitude current is met by sampling the current at two different moments in one period (i) just before the application of the small amplitude pulse, i.e. at t t0 and (ii) at a moment tm — t0 + tp within the duration of the pulse. The difference of the two samples is recorded as a function of E. It is not difficult to... 

Steady-state and pseudo-steady state techniques (d.c. polarography, pulse and differential pulse polarography, a.c. polarography) are especially suitable for analytical purposes, i.e. the determination of the composition of a sample and of concentrations of single species in such a sample. It is less commonly recognized that these techniques are also indispensable for the determination of less interesting properties of the components... 

Generally, sensitivity in the analytical sense is greater if the technique employed is faster, i.e. the electrolysis time is shorter, or the frequency of a periodic electrolysis is higher. Resolution of half-wave potentials, and thus accuracy of standard potentials and stability constants, is better if a derivative technique such as differential pulse polarography, a.c. polar-ography, and, preferably, the second derivative technique second-harmonic a.c. polarography, is employed. 

Cyclic voltammetric methods, or other related techniques such as differential pulse polarography and AC voltammetry,3 provided a convenient method for the estimation of equilibrium constants for disproportionation or its converse, comproportionation. In this respect, the experimentally measured quantity of interest in a cyclic voltammetric experiment is E>A, the potential mid-way between the cathodic and anodic peak potentials. For a one-electron process, E,A is related to the thermodynamic standard potential Ea by equation (4).13 In practice, ,/2 = E° is usually a good approximation. 

Determination of free MDA by HPLC Below a pH of 4.65, free MDA exists in an undissociated cyclic form ( 245 = 30000). Although it can be determined by UV-absorptiometry (Kwon and Watts, 1963 Kukuda et al., 1981) and differential pulse polarography, HPLC techniques are far superior, because they are sensitive and specific. 

Polarography (discovered by Jaroslav Heyrovsky in 1922) is a technique in which the potential between a dropping mercury electrode and a reference electrode is slowly increased at a rate of about 50 200 mV min while the resultant current (carried through an auxihary electrode) is monitored the reduction of metal ions at the mercury cathode gives a diffusion current proportional to the concentration of the metal ions. The method is especially valuable for the determination of transition metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Mo, W, V, and Pt, and less than 1 cm of analyte solution may be used. The detection hmit is usually about 5 X 10 M, but with certain modifications in the basic technique, such as pulse polarography, differential pulse polarography, and square-wave voltammetry, lower limits down to 10 M can be achieved. 

Phenylarsine oxide is used as a titrant for the direct and indirect determination of residual chlorine and ozone in water and wastewater. Preliminary investigations on the direct measurement of PAO by differential pulse polarography (DPP) indicate that this technique is a promising method for lowering the detection limits in the indirect measurement of these oxidants. The control of pH is a necessary consideration in free and combined chlorine analysis with as well as the stability and measurement of... 

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