Progress in oscillographic chronopotentiometry

The investigation on oscillographic chronopotentiometry after 2000 is reviewed. The development course of oscillographic chronopotentiometry is looked back. Some new instrumentations and new methods about oscillographic chronopotentiometry as well as applications of chemometrics in oscilloanalysis are introduced. The prospects of oscillographic chronopotentiometry development are also discussed in this paper.     

DNA and RNA sensor

The development of DNA sensors attracts recentresearch attention directed at gene analysis, such asdetection of genetic disorders, tissue matching andforensic applications[1,2]. In general, sensors based on the principle differ-ent from that of the tr…     

Progress in oscillographic chronopotentiometry

This review summarizes recent advances in DNA sensor. Major areas of DNA sensor covered in this review include immobilization methods of DNA, general techniques of DNA detection and application of nanoparticles in DNA sensor.     

Local chronopotentiometry of heterogeneous alloys

Abstract-It was shown by the example of zinc-cadmium and lead-antimony alloys that local chrono-potentiometry is promising method for studying anodic and corrosion properties of heterogeneous alloys.     

Application of convolution procedures to chronopotentiometry

Convolution procedures are used to extract the faradaic information from chronopotentiometric data, in conditions where significant distortion by double layer charging occurs. The faradaic component of the imposed current is obtained, after measurement of the double layer capacitance, by differentiation of the initial chronopotentiogram. Convolution of this current with the function (πt)^?1/2 leads to a potential-convoluted current relationship freed from the effect of double layer charging. The kinetic characterization of the system using a combined analysis of this relationship and that relating the faradaic current to the electrode potential is discussed for the various types of reaction mechanism. The efficiency of the proposed procedure is tested on the galvanostatic reduction of fluorenone in DMF.     

Simulation of electroporated cell by chronopotentiometry

Chronopotentiometry on planar lipid bilayer (BLM) is proposed as a method for modeling the electrical phenomena in electroporated cell. Two techniques are discussed: constant-current and linear-current chronopotentiometry. It is proposed that the constant-current chronopotentiometry may provide basis for modeling the electroporated cell shortly after the removal of the electric field, when activity of cellular pumps counteracts ionic fluxes through the electropore and ionic channels. The linear-current method can be considered for modeling the cell in the later stage after electroporation, when energetical resources of the cell are gradually getting exhausted and the activity of pumps decreases. Based on this idea, it may be postulated that the electropore in the cell has fluctuating dynamics whose stochastic characteristics, similarly as biological channels, shows 1/f noise. The model implies that the fluctuations would disappear leaving the electropore with a constant resistance when efficiency of the pumps becomes very small. The results of chronopotentiometry also may suggest that opening time, conductivity and selectivity of the electropore can be controlled by the cell environment or membrane composition.     

Selectivity enhancement of anion-responsive electrodes by pulsed chronopotentiometry

A large and robust selectivity improvement of ion-selective electrodes is presented for the measurement of abundant ions. An improvement in selectivity by more than two orders of magnitude has been attained for the hydrophilic chloride ions measured in a dilute background of the lipophilic ions perchlorate and salicylate in a pulsed chronopotentiometric measurement mode. This is attributed to a robust kinetic discrimination of the dilute lipophilic ions in this measuring mode, which is not possible to achieve in classical potentiometry. Maximum tolerable concentrations of the interfering ions are found to be on the order of 30 μM before causing substantial changes in potential. As an example of practical relevance, the robust detection of chloride in 72 μM salicylate (reflecting 1:10 diluted blood) with a detection limit of 0.5 mM chloride is demonstrated. Corresponding potentiometric sensors did not give a useful chloride response under these conditions.     

Determination of chloride by stripping chronopotentiometry with silver-film electrode

The experimental parameters of cathodic stripping chronopotentiometry of chloride at a silver-film electrode are investigated and optimized. The chloride preconcentration is achieved in the form of silver chloride by a controlled potential oxidation of the working electrode under vigorous stirring. Cathodic stripping of the deposit is obtained by the constant current, under the condition of diffusive mass transfer. Deaeration of the solution is not necessary. A detection limit of 35 μ dm⁻³ (10⁻⁶ mol dm⁻³) is obtained at a deposition time of 180 s, with a reproducibility of 6.7 % (expressed as relative standard deviation, RSD).     

Flow-through stripping chronopotentiometry for the monitoring of mercury in waste waters

A simple method for the determination of total mercury in waste waters is described. It makes use of a flow system incorporating a wall-jet cell equipped with a gold working electrode. The untreated sample is mixed on-line with the acidic carrier electrolyte which contains potassium permanganate and transforms the various species of mercury, especially elementary Hg, to Hg(II). The pre-treated solution enters the cell where mercury is deposited on the gold electrode. In the next step the deposit is stripped at constant current and the time corresponding to the dissolution of the deposit is obtained from the chronopotentiometric signal. The method enables it to determine and monitor Hg in the concentration range of 1 to 1000 μg/L in 5 min intervals. Received: 20 October 1997 / Revised: 23 December 1997 / Accepted: 30 December 1997     

Triangular current-sweep chronopotentiometry at rotating disk and stationary,planar electrodes

A convenient series solution is presented for the evaluation of reactant and product concentrations during triangular current-sweep chronopotentiometry at a rotating disk electrode and at a stationary, planar electrode in the absence of free convection. The advantages of controlled-current processes, relative to controlled-potential processes, for otaining kinetic, thermodynamic, and transport information are elucidated. Theoretical predictions are compared with results obtained for the deposition of cadmium from a dilute, aqueous, cadmium sulfate + potassium sulfate electrolyte. A multidimensional optimization routine, the Levenberg-Marquardt algorithm, is used to evaluate physicochemical parameters.     

Flow-through stripping chronopotentiometry for the monitoring of mercury in waste waters

A simple method for the determination of total mercury in waste waters is described. It makes use of a flow system incorporating a wall-jet cell equipped with a gold working electrode. The untreated sample is mixed on-line with the acidic carrier electrolyte which contains potassium permanganate and transforms the various species of mercury, especially elementary Hg, to Hg(II). The pre-treated solution enters the cell where mercury is deposited on the gold electrode. In the next step the deposit is stripped at constant current and the time corresponding to the dissolution of the deposit is obtained from the chronopotentiometric signal. The method enables it to determine and monitor Hg in the concentration range of 1 to 1000 μg/L in 5 min intervals. Received: 20 October 1997 / Revised: 23 December 1997 / Accepted: 30 December 1997     

Determination of zinc (II) in lubricant oils by stripping chronopotentiometry

A method for the determination of zinc (II) in lubricant oils by stripping chronopotentiometry is described. The only necessary sample pretreatment was the extraction of zinc (II) from the corresponding alkyl derivatives by hot concentrated hydrochloric acid in a suitable extractor. The metal ions were concentrated as the corresponding metals on a glassy carbon working electrode and then stripped by a suitable oxidant. Quantitative analysis was carried out by the method of standard additions; a good linearity was obtained in the range of concentrations examined. Recoveries of 94% were obtained from a lubricant oil spiked at different levels. The detection limit was 0.02 mg g(-1) and the coefficient of variation (mean of nine determinations) was 5.2%. Results obtained on commercial lubricant oils were not significantly different from those obtained by atomic absorption spectrometry.     

Response to high acidity and basicity at a platinum electrode in chronopotentiometry

A simple and rapid method is developed to determine the high acidity and the basicity of solutions by chronopotentiometry with a platinum working electrode. The acidity range from 5.0 mol/l H⁺ to 1.0 mol/l OH⁻ can be measured by the adjustment of deposition potential and time. The response mechanism to acidity and basicity has been explored. The transition potential plateau in chronopotentiograms is caused from the oxidation of hydrogen adsorbed on electrode surface.     

Reductive stripping chronopotentiometry for selenium in biological materials with a flow system

Reductive stripping chronopotentiometry in a flow system is used for determination of selenium in mussels and NBS bovine liver after acid digestion. The automated flow system contains a thin-layer cell with a mercury film electrode. In the deposition step, mercury(II) selenide is formed on the mercury film surface; the stripping step involves reduction to mercury and hydrogen selenide. This reduction is done in a separate solution of almost saturated calcium chloride, which eliminates interferences from oxygen so that solutions need not be deoxygenated. The detection limit is 0.14 μg l^?1 selenium at a deposition time of 120 s.     

Absolute analysis of trace metals through galvanostatic stripping chronopotentiometry with signal accumulation

An electrochemical flow-through cell with a porous working electrode made of vitreous carbon particles and plated with mercury was used for the absolute determination of Pb using galvanostatic stripping chronopotentiometry in a flow system. After completing the potentiostatic electrodeposition of the analyte from the flowing sample solution the flow was stopped and oxygen in the solution inside the pores of the electrode was removed by reducing it. The deposit was then stripped by applying a constant current of 50 to 1000 A and the measured potential vs time (E vs t) data were converted to the dt/dE vs E dependence by a memory mapping technique. Owing to the thin layer properties of the cell, the stripping/deposition steps could be repeated reproducibly enabling the accumulation of the signals while improving the signal to noise ratio. The method was also found to be suitable for the simultaneous determination of Cd, Pb and Cu. The experimental conditions, computerized data handling and signal processing have been investigated. Water, grass and sediment samples were analyzed for traces of Pb.     

Measurement of total calcium by flash chronopotentiometry at polymer membrane ion-selective electrodes

Ionophore-based ion-selective electrodes are widely used for potentiometric electrolyte measurements, in which case they are known to detect the free ion activity. Total ion concentrations cannot be directly assessed by this methodology if the ion is predominantly present in a complexed form. We present here the direct measurement of total calcium using a calcium ion-selective electrode interrogated in a flash chronopotentiometric transduction mode. A high magnitude of cathodic current pulse is applied across a calcium ion-selective membrane containing the ionophore ETH 5234 but void of ion-exchanger to prevent spontaneous extraction. This induces a defined flux of calcium ions from the sample side to the membrane and results in the release of labile bound calcium and a concomitant depletion at the membrane surface at a critical current or time. This is observed as an inflection point on the potential-time curve and the square root of the transition time is linearly related to the total concentration in the sample. It is shown that the responses to solutions of labile calcium complexes of nitrilotriacetic acid (NTA) are in a good agreement with that of the same concentration of calcium chloride in saline solution with this protocol. Initial applications are aimed towards assaying extracellular calcium. Calcium binding to albumin is shown to be inconsequential with sample dilutions typical for clinical assays. Calcium calibration curves in real and artificial dilute serum are finally shown to correspond to that of calcium chloride, suggesting that the methodology is indeed capable of detecting total calcium under these conditions. The present membrane materials allow detection of up to over 0.5 mM total calcium in serum, currently requiring such samples to be diluted about 5-fold. The slopes of the square root of time-concentration dependence for the calibrations of free calcium in a background of NaCl and total serum calcium were found to be 3.857 and 3.717 s^1/2 mM⁻¹, respectively, deviating by just 3.6%. The lower detection limit (3× SD) was calculated as 12 μM.     

Anodic stripping voltammetry and chronopotentiometry of copper at a rotating carbosital disk electrode

The use of a new carbon material — carbosital — for electrodes is reviewed. The behaviour of copper deposited on the carbosital electrode surface in anodic stripping voltammetry and chronopotentiometry is discussed. In anodic stripping voltammetry with a rotating carbosital disk electrode, the peak current and the number of coulombs involved in stripping copper are directly proportional to the square root of the electrode rotation rate during preelectroiysis; the peak current is directly proportional to the potential scan rate during stripping. For anodic stripping voltammetry and anodic stripping chronopotentiometry, linear calibration graphs are obtained in the range 1 X 10^-3–1 x 10^-6 M copper(II). The method is applicable to analysis of high-purity cadmium for copper.     

Trace analysis of aluminum in natural waters with rubeanic acid by adsorption chronopotentiometry

The determination of trace levels of aluminum in natural waters with rubeanic acid (RA) by adsorption chronopotentiometry is developed in this paper. Optimum experimental conditions include an accumulation potential of -0.40 V, accumulation time of 60 s, and a RA concentration of 6x10(-6) M in 0.2 M NaAc-HAc buffer solution (pH 4.6). The response is linear over the 1x10(-8) approximately 4x10(-7) M concentration range. The detection limit is 5.6x10(-9) M and the relative S.D. (at the 3x10(-7) M level) is 2.6%. Possible interferences are evaluated. The method has been applied to the determination of trace levels of Al in various real samples. Direct determination of toxic forms of Al in surface waters by this technique is also explored.