Abstract

This paper presents the optimization of instrumental and solution parameters for determination of tamoxifen in urine and plasma and formulation by fast Fourier transform square wave voltammetry (SWV) using a gold microelectrode in flow-injection system. The samples are subjected by the same buffer solution and are injected in the flow-injection apparatus. By applying a novel square wave voltammetry method to perform as a sensitive method the voltamograms are recorded. The method used for determination of tamoxifen by measuring the changes in admittance voltammogram of a gold ultramicroelectrode (in 0.05 mol L −1 H 3PO 4 solution) caused by adsorption of the tamoxifen on the electrode surface. The best sensitivity was achieved using a frequency of 600 Hz and a medium composed of 0.05 mol L −1 phosphate buffers at pH 2.0. The best performance was obtained with the pH value of 2, pulse amplitude 25 mV, frequency 600 Hz, accumulation potential of −100 mV and accumulation time of 0.5 s. Furthermore, signal-to-noise ratio has significantly increased by application of discrete fast Fourier transform (FFT) method, background subtraction and two-dimensional integration of the electrode response over a selected potential range and time window. Calibration plots are given for solutions containing 1.0 × 10 −11 to 3.0 × 10 −6 mol L −1 of tamoxifen. The detection limit is calculated to be 3.0 × 10 −12 mol L −1 (∼2 pg mL −1). The relative standard deviation at concentration 2.0 × 10 −8 M is 6.1% for five reported measurements.

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