The assembling of thiacalix[4]arene-based dendrimers in cone, partial cone, and 1,3-alternate configuration on the surface of a glassy carbon electrode coated with carbon black or multiwalled carbon nanotubes has been characterized using cyclic voltammetry, electrochemical impedance spectroscopy, and scanning electron microscopy. Native and damaged DNA were electrostatically accumulated on the modifier layer. The influence of the charge of the redox indicator and of the macrocycle/DNA ratio was quantified and the roles of the electrostatic interactions and of the diffusional transfer of the redox indicator to the electrode interface indicator access were established. The developed DNA sensors were tested on discrimination of native, thermally denatured, and chemically damaged DNA and on the determination of doxorubicin as the model intercalator. The limit of detection of doxorubicin established for the biosensor based on multi-walled carbon nanotubes was equal to 1.0 pM with recovery from spiked human serum of 105-120%. After further optimization of the assembling directed towards the stabilization of the signal, the developed DNA sensors can find application in the preliminary screening of antitumor drugs and thermal damage of DNA. They can also be applied for testing potential drug/DNA nanocontainers as future delivery systems.
Keywords: DNA sensing; cyclic voltammetry; doxorubicin; electrochemical impedance spectroscopy; supramolecular dendrimers; thiacalix[4]arene.