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Results and Discussion<br />

3.2 Importance of knowing the surface<br />

In order to tailor optimal DNA-modified surfaces for the envisaged sensing platforms it is of<br />

utmost importance to understand processes occurring at the electrode surface during the DNA<br />

assay build-up. Only in this way, the properties of the surface can be controlled in a reproducible<br />

manner. Electrochemical impedance spectroscopy is an excellent technique for this due to<br />

which it gained a wide popularity in the field of bioelectroanalysis 70,71 . It is a non-destructive<br />

technique allowing one to monitor surface modification without altering the system’s response.<br />

Moreover, due to its sensitivity it is a great tool for following very subtle changes in the surface<br />

architecture. EIS is a very informative technique that allows in depth investigation of processes<br />

occurring at the electrified interface by sequentially following each step of the build-up of DNA<br />

assays 5,72 .<br />

Furthermore, to understand the behavior of DNA strands in front of an electrode surface we<br />

need to investigate not only physico-chemical properties of the DNA itself but it is essential to<br />

also observe the electrode and the surrounding solution as important components of the system.<br />

Since the DNA is essentially a negatively charged polyelectrolyte (depending on the ionic<br />

strength of the surrounding solution), the charge of the surface has a significant impact on the<br />

behavior of DNA at the interface. Therefore, it is of great importance to know how the surface<br />

is polarized (positive or negative) upon application of different potentials. Consequently, the<br />

potential of zero charge (pzc) of the bare polycrystalline electrode was determined.<br />

Additionally, the influence of the surface modification with DNA on the pzc was also<br />

investigated.<br />

3.2 Importance of knowing the surface 34

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