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| - Switchable Surface Properties through the Electrochemical orBiocatalytic Generation of Ag0 Nanoclusters onMonolayer-Functionalized Electrodes
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| - The electroswitchable and the biocatalytic/electrochemical switchable interfacial properties of aAg+−biphenyldithiol (BPDT) monolayer associated with a Au surface are described. Upon the applicationof a potential corresponding to −0.2 V the Ag+−BPDT is reduced to the Ag0−BPDT interface, and silvernanoclusters are generated on the interface. The application of a potential that corresponds to 0.2 Vreoxidizes the monolayer to the Ag+−BPDT monolayer. The reversible electrochemical transformation ofthe Ag+−BPDT monolayer and of the Ag0−BPDT surface was followed by electrochemical means andsurface plasmon resonance spectroscopy (SPR). The SPR experiments enabled us to follow the kineticsof nanoclustering of Ag0 on the surface. The hydrophobic/hydrophilic properties of the surface are controlledby the electrochemically induced transformation of the interface between the Ag+−BPDT and Ag0−BPDTstates. The Ag0−BPDT monolayer reveals enhanced hydrophilicity. The hydrophobic/hydrophilic propertiesof the interface were probed by contact angle measurements and force interactions with a hydrophobically-functionalized AFM tip. The Ag0−BPDT interface was also biocatalytically generated using alkalinephosphatase, AlkPh, and p-aminophenyl phosphate as substrate. The biocatalytically generated p-aminophenol reduces Ag+ ions associated with the surface to Ag0 nanoclusters. This enables the cyclicbiocatalytic/electrochemical control of the surface properties of the modified electrode.
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