Voltammetric studies of the interaction of lumazine with cyclodextrins and DNA.

The interaction of lumazine, an antibacterial drug, with alpha-, beta-cyclodextrins and DNA in aqueous solution was studied by differential pulse stripping voltammetry and cyclic voltammetry as well as UV-vis spectroscopy. The electrochemical and absorption spectral data indicated a 1:1 complex formation of lumazine with alpha-, beta-cyclodextrins and DNA. The nature of the process, taking place at the hanging mercury drop electrode, was clarified. It was found that the complexation of lumazine molecules enhances the stacking interactions which might facilitate the formation of a perpendicularly stacked layer of lumazine-alpha-cyclodextrin complex on the electrode surface. Based on the variations in the current or absorbance, the formation constants and consequently, the Gibbs energy of these complexes were determined. The small size cavity of alpha-cyclodextrin was found to have a greater affinity for lumazine than the beta-cyclodextrin. Moreover, the interactions of lumazine-alpha-cyclodextrin or lumazine-beta-cyclodextrin inclusion complex with DNA have been investigated by means of voltammetry. The results suggest that lumazine displayed high affinity for DNA and the inclusion complex decomposed when it binds to DNA.

Cathodic adsorptive stripping voltammetric determination of nalidixic acid in pharmaceuticals, human urine and serum.

The quinolone antibacterial agent nalidixic acid (NAL) was studied by cyclic voltammetry (CV) and cathodic adsorptive stripping voltammetry (CASV). A sensitive method is described for the determination of NAL in its pure form, dosage forms and biological fluids. Controlled adsorptive accumulation of NAL on a hanging mercury drop electrode provides the basis for the direct stripping measurement of that compound in the nanomolar concentration level. Different variables were studied and optimized. The proposed method depends upon the voltammetric activity of NAL in Britton-Robinson buffer, whereby a well-defined cathodic peak is produced at pH 5.0 in presence of NO(3)(-). The calibration graph to determine NAL was linear in the range 7.4x10(-8)-2.5x10(-5) M by CASV. CAS voltammetry has been proved to be advantageous over a liquid chromatographic (LC) technique, allowing to detection limit signal to noise ratio, (s/n=3) of 0.766 ng ml(-1) (3.3x10(-9) M) NAL to be reached. The relative standard deviation (n=5) was 5.2% at concentration level of 1.0x10(-7) M NAL. The degree of interference from coexisting metal ions on the CASV signal for NAL was evaluated. The method was applied to two different commercial pharmaceutical products (Negram tablets and suspension) with very good recoveries. It was also shown that the method was successfully applied to the determination of NAL in human urine and blood serum. Mean recoveries were 98.8+/-0.3 and 98.9+/-0.41%, respectively.