Synthesis, electrochemical and spectral properties of some omega-N-quinonyl amino acids.

Four series of omega-N-quinonyl amino acids were synthesized by Michael-like additions. The quinones include 2-phenylthio-1,4-benzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone and 2,3-dichloro-1,4-naphthoquinone. These modified amino acids can be used for post chain assembly modifications of biologically active peptides, which target the quinonic drug to a cancer damaged area. The electron-transfer capabilities of the modified amino acids were probed by cyclic voltammetry measurements. The results described in this paper show that the novel N-quinonyl amino acids are effective in producing semiquinone radicals similarly to the unconjugated quinones themselves. A direct relation was found between the first reduction potentials of the quinones and their reactivity towards the omega-amino acids. The successful generation of stable semiquinone radicals by the novel quinone derivatives is a prerequisite for the manifestation of site-directed antitumor activity of corresponding quinone-peptide conjugates.

Viscosity and binder composition effects on tyrosinase-based carbon paste electrode for detection of phenol and catechol.

The systematic study of the effect of binder viscosity on the sensitivity of a tyrosinase-based carbon paste electrode (CPE) biosensor for phenol and catechol is reported. Silicon oil binders with similar (polydimethylsiloxane) chemical composition were used to represent a wide range of viscosities (10-60 000 mPa s(-1) at 25 degrees C) while minimizing polarity effects. The highest response for both phenol and catechol was achieved using a silicon oil binder of intermediate viscosity (100 mPa s(-1)). The binder viscosity showed no appreciable effect on the direct oxidation of phenol and catechol using a plain CPE, suggesting the involvement of diffusion kinetics in the binder matrix for the enzyme-based CPE. The effect of the relative binder concentration in the carbon paste was measured over the range of 30-70%. Optimal results were obtained using 40% silicon oil. For comparison of the viscosity effects observed with the carbon paste electrode (CPE) containing silicon oil, other low and high viscosity mineral oils and paraffin waxes were also examined.