DNA and RNA have
been measured with many techniques but often with
relatively long analysis times. In this study, we utilize fast-scan
cyclic voltammetry (FSCV) for the subsecond codetection of adenine,
guanine, and cytosine, first as free nucleosides, and then within
custom synthesized oligos, plasmid DNA, and RNA from the nematode
Caenorhabditis elegans
. Previous studies have shown
the detection of adenosine and guanosine with FSCV with high spatiotemporal
resolution, while we have extended the assay to include cytidine and
adenine, guanine, and cytosine in RNA and single- and double-stranded
DNA (ssDNA and dSDNA). We find that FSCV testing has a higher sensitivity
and yields higher peak oxidative currents when detecting shorter oligonucleotides
and ssDNA samples at equivalent nucleobase concentrations. This is
consistent with an electrostatic repulsion from negatively charged
oxide groups on the surface of the carbon fiber microelectrode (CFME),
the negative holding potential, and the negatively charged phosphate
backbone. Moreover, as opposed to dsDNA, ssDNA nucleobases are not
hydrogen-bonded to one another and thus are free to adsorb onto the
surface of the carbon electrode. We also demonstrate that the simultaneous
determination of nucleobases is not masked even in biologically complex
serum samples. This is the first report demonstrating that FSCV, when
used with CFMEs, is able to codetect nucleobases when polymerized
into DNA or RNA and could potentially pave the way for future uses
in clinical, diagnostic, or research applications.