• electrochemistry;
  • microarrays;
  • redox-active monolayers;
  • scanning electrochemical probe;
  • surface chemistry


A reagentless strategy for template-free patterning of uniformly inert surfaces is suggested. A layer of p-hydroquinone (HQ) protected by the tert-butyldimethylsilyl (TBDMS) group is electrografted onto glassy carbon electrodes. Chemoselective activation is performed through electrochemically controlled cleavage of the TBDMS group, which yields the redox-active surface-confined quinone moieties. The latter are shown to undergo electrochemically induced Michael addition, which serves for subsequent functionalization of the electrode surface. Patterning of the TBDMS–quinone-modified surface is accomplished by using selective localized cleavage of the protecting group. State-of-the-art direct-mode scanning electrochemical microscopy (SECM) patterning fails to yield the anticipated interfacial reaction; however, the electrochemical scanning droplet cell (SDC) is capable of conducting the localized chemoselective reaction. In a small area, dictated by the dimensions of the droplet, electrochemically induced cleavage of the protecting group can be performed locally to give rise to arrays of active quinone spots. Upon deprotection, the redox signals, attributed to the hydroquinone/benzoquinone couple, provide the first direct evidence for chemoselective electrochemical patterning of sensitive functionalities. Subsequent SECM studies of the resulting modified areas demonstrate spatial control of the proposed patterning technique.