1IntroductionSignal-triggered release of substances fromc hemicals ystems for variousa pplications [1][2][3][4],p articularly drug release [5][6][7][8][9][10][11][12],a nd more specifically DNAr elease [13,14], for biomedical applications has been extensively studied in the last decades.T he controlled DNAr elease is important for many applications,i ncludingg ene-delivery therapy [13,15],b iosensors [16],b iochips [17] and biocomputing [18].V ariousm ethodso ft he signal-controlled DNA release have been reported recently,i ncluding irradiation of DNA-loaded nanoparticles with an alternating electromagnetic field [19],l ight-triggered capture and release of DNA[ 20],t hermal release of DNAf rom nanostructured systems [ 21,22],e tc. Among different methodso ft he DNAc ontrolled release,e lectrochemically stimulated release of DNAp re-loaded on an electrode surface is particularly convenient and interesting due to its simplicity and versatility of the method. Most of the systems developed for the electrochemically stimulated DNAr elease are based on disassembly of polymeric matrices loaded with DNAm olecules.T his was achieved by decomposition of electrostatically bound multi-layered polymeric structures loaded with DNA [23][24][25][26] or by splittingc ovalent bonds between DNAm olecules and am odified electrode surface [27].T he disadvantage of these approaches is irreversible degradation of the assemblies on the electrode surfaces,w hich allowso nly one-time release process.A nother approach, which allows multiple use of the functional interface,c apable of reversible loading-unloading of DNAm oleculeso nt he electrode surface,i sb ased on electrostatic attraction/repulsion processes for the charged DNAm olecules upon variation of the electrode potential and corresponding charge [28][29][30][31][32].T he reversi-ble adsorption and desorption processes of the negatively charged DNAm olecules are controlled by the charge imposed on the electrode surface upon application of variable potentials [33].W hile the experimental realization of the potential-controlled DNAa dsorption/desorption process has been studied recently,t he theoretical background for this phenomenon wase stablished in the research of A. N. Frumkin early in 1920s [34].M odernn anotechnological advances allowed DNAr elease inside living cells fromn ano-size electrode needles inserted into the cells [35].While electrostatically controlled DNAa dsorption on an electrode surface followed by its desorption upon the change of the applied potential is av ery simple and powerful method,a lso allowing multiple reversible deposition and release of DNA, it hasa ni nherent drawback. Indeed, az ero-charge potential depends on the electrode environment and adsorption of other biomolecules, particularly,w hen the electrode operates in biofluidsw ith complex biomolecularc omposition [36].T his can shift the potential regionsw here the electrode is positively charged for the electrostatic DNAd eposition and negatively charged for the DNAr epulsion and release.T her...