Potential step methods detection

Pulse amperometric detection (PAD) has been used for the detection on a PDMS chip. This method is useful for analysis of underivatized compounds, such as carbohydrates, amino acids, and sulfur-containing antibiotics, which easily caused electrode fouling. In PAD, a high positive potential (1.4-1.8 V) is first applied in order to clean the electrode (e.g., Au) surface. This is followed by a negative potential step (-0.5 V) to reactivate the electrode surface. A third moderate potential (+0.5 to +0.7 V) is applied for detection of the target analyte [752]. 

From the experimental standpoint, the use of a.c. techniques offers many advantages. Sensitivity is much higher than in d.c. measurements, since phase-sensitive detection can be used and very small probe signals can be employed ( 5mV). The technique is therefore a truly equilibrium one, unlike cyclic voltammetry. An alternative approach to the commonly used sinusoidal signal superimposed on the selected d.c. potential is to use a potential step and to employ Laplace transform methods. Instrumentally, this is rather more demanding and the advantages are not clear [51]. Fourier transform methods have also been considered and their use will have advantages in terms of the time-scale for an experiment, especially at very low frequencies. 

This group of methods relies on potentiometric measurement at the detection side to determine the hydrogen concentration. Three basic variations of this approach have been described the step, pulse, and sinusoidal methods [97j. In the step method, the hydrogen concentration is initially homogeneous throughout the membrane. The concentration is then increased at the input side and kept constant under potentiostatic control. The change in concentration at the detection side is followed by monitoring the potential. The... 

The pulse method involves subjecting the membrane to a short cathodic current pulse. The concentration gradient created at the input side during this pulse decreases as hydrogen diffuses to the other side. As with the step method, the change in concentration at the detection side is monitored through the potential. 

As seen in previous sections, the response to a potential step is a pulse of current, which decreases with time as the electroactive species near the electrode surface is consumed and consists of a faradaic, /f, and a capacitive contribution, Iq. The advantage of most pulse techniques results from the measurement of the current flow near the end of the pulse when the faradaic current has decayed, often to a diffusion-limited value but when the capacitive current is insignificant. Pulse widths, tp, are adjusted to satisfy this condition and the additional condition that time has not been allowed for natural convection effects to influence the response. There is a greatly improved signal-to-noise ratio (sensitivity) compared to steady state techniques and in many cases, greater selectivity. Detection limits are of the order of 10 M. Furthermore, for analytical purposes, most current-voltage profiles from the pulse techniques are faster to interpret than those of dc voltammograms, because they are peak-shaped rather than the typical step curve of conventional voltammet-ric methods. 

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