Highly sensitive label-free techniques of DNA determination are particularly interesting in relation to the presentdevelopment of the DNA sensors. We show that subnanomolar concentrations (related to monomer content)of unlabeled DNA can be determined using copper solidamalgam electrodes or hanging mercury drop electrodesin the presence of copper. DNA is first treated with acid(e.g., 0.5 M perchloric acid), and the acid-released purinebases are directly determined by the cathodic strippingvoltammetry. Volumes of 5-3
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L of acid-treated DNA caneasily be analyzed, thus making possible the determination of picogram and subpicogram amounts of DNAcorresponding to attomole and subattomole quantities of1000-base pair DNA. Application of this determinationin DNA hybridization detection is demonstrated usingsurface H for the hybridization (superparamagnetic beadswith covalently attached DNA probe) and the mercuryelectrodes only for the determination of DNA selectivelycaptured at surface H.