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_____________________________________________________________ Results and Discussion<br />

of influence is attained with a higher applied potential. Conversely, anions in the same layer are<br />

attracted towards the electrode and with this a small fraction of a DNA strand that is in<br />

immediate proximity to the electrode is pulled towards its surface. As a result, the remaining<br />

part of a DNA strand that was outside of the area of influence is brought closer to the electrode<br />

surface. If the same potential is still applied the next part of the DNA strand undergoes the same<br />

process; DNA counterions are repelled together with cations from the solution and the rest of<br />

the DNA strand is brought closer to the surface. This process continues as long as the positive<br />

potential pulse is applied. If the duration of a pulse is long enough, the complete DNA strand<br />

is sequentially confined on the electrode surface. Therefore, regardless of the orientation of the<br />

DNA strand, the anchor group is brought close enough to the electrode surface for the formation<br />

of the Au-S bond.<br />

Figure 3.25. Scheme presenting the zipper-like pulling of a DNA strand towards the<br />

electrode surface during potential-assisted DNA immobilization. Figure adapted from<br />

ref. 5 .<br />

The positive potential pulse is followed by a potential jump to a negative potential with respect<br />

to the pzc (DNA). If an appropriate negative potential is applied, anions in the vicinity of the<br />

electrode are repelled from the surface together with the remaining negatively charged DNA<br />

backbone that was left unscreened. By this, the grafted DNA strand are lifted towards the bulk<br />

of the solution. Thus, additional space is created for new DNA strands to approach to the<br />

3.3 Importance of controlling the surface 60

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