A computerized electrochemical detection system for application
after HPLC, provided with a cyclic voltammetric oxidative and
reductive module, is described for the on-line qualitative determination
of electroactive antineoplastic agents and metabolites in urine
samples, collected from cancer patients, following intravenous
administration.
The application of two cyclic voltammetric detection modes
provides an insight into both oxidative and reductive electrode
reactions of compounds, passing the detector and the occurrence of
(it)reversible chemical and electrochemical processes at the electrode
surface. In this way, redox properties of drugs and metabolites
characteristic of their molecular structure, can be established, which
may provide information related to their (enzymatic) bioactivation.
In the cyclic voltammetric mode, the system permits automatic
detection of a compound in the cell, recording, storage and plotting
of voltammograms and calculation of the retention times, the
half-wave potentials and the peak potentials of each scan of all
individual compounds. For routine use, storage of 68 voltammograms
on-line is sufficient for the analysis of biological samples in
clinical-pharmacological research. Special attention has been paid
to automatic, multi-reference-point component detection.
Based on their concentrations in urine, the oxidative cyclic
voltammetric mode, using a glassy carbon electrode, permits the
determination of etoposide and teniposide, whereas the reductive
cyclic voltammetric mode, with a static mercury drop electrode,
permits the determination of adriamycin and its metabolite
adriamycinol.