P. Singhal et Wg. Kuhr, ULTRASENSITIVE VOLTAMMETRIC DETECTION OF UNDERIVATIZED OLIGONUCLEOTIDES AND DNA, Analytical chemistry, 69(23), 1997, pp. 4828-4832
Electrochemical detection of nucleotides, ssDNA, and dsDNA was accompl
ished by using sinusoidal voltammetric detection at copper microelectr
odes, Generally, detection of these molecules utilizes the electroacti
ve nature of adenine and guanine residues at most electrode surfaces.
The detection approach used in this study is based on the electrocatal
ytic oxidation of sugars and amines at copper surfaces, All nucleotide
s and DNA molecules comprise a ribose sugar backbone and primary amine
s present on the different nucleobases. Consequently, the detection ap
proach is universal to all types of nucleotides, As the number of suga
r moieties increases with the length of an oligonucleotide, the detect
ion sensitivity is enhanced for bigger oligonucleotides, Irreversible
adsorption of these oligonucleotides and other biomacromolecules like
dsDNA on the electrode surface was avoided with sinusoidal voltammetry
since it is a scanning electrochemical technique, The sensitivity of
the detection strategy is, however, still preserved due to the effecti
ve decoupling of the faradaic signal from the capacitive background cu
rrents in the frequency domain. The ssDNA and dsDNA were detected in t
he picomolar concentration range. The electrochemical signal due to ds
DNA is actually higher than that due to ssDNA due to the larger number
of easily accessible sugars on the outer perimeter of a dsDNA double
helix compared to those on a ssDNA of the same size, This is in contra
st to the existing electrochemical detections techniques based on the
electroactivity of the nucleobase.