Foundations of nucleic acid electrochemistry were laid down in 1960-1980´s using mercury and carbon electrodes.

After the discovery of the DNA electroactivity it was shown that signals of ds and ss DNA and RNA greatly differ.
This made it possible to detect: traces of ssDNA in dsDNA samples, DNA damage, single-strand breaks, chemical modification, depurination, ...

Important findings:
DNA premelting: beginning of the 1960´s
DNA unwinding at the electrode surface: middle of 1970´s
Polymorphy of the DNA double helix: middle of 1970´s

New approaches important for future DNA electrochemical sensors:
First covalently bound electroactive labels: beginning of 1980´s
First DNA-modified electrodes: middle of 1980´s