Electroswitchable wetting of electrode surfaces modified with redox-active monolayers and thin films
is described. Electrocatalytic and bioelectrocatalytic processes that are activated by the redox-active interfaces
associated with electrodes control the hydrophobic/hydrophilic properties of the surfaces, thus allowing
the probing of the chemical transformations by static contact angle measurements. A Prussian Blue film
associated with an ITO electrode undergoes redox transformations between the hydrophilic reduced state,
PB4-, the hydrophobic semioxidized state, PB0, and the hydrophilic fully oxidized state, PB3+. Contact
angle measurements follow the reversible switching of the film between the three states. The oxidized
state, PB3+, electrocatalyzes the oxidation of NADH, and thus, the ratio of PB3+/PB0 on the film interface
upon the electrochemical oxidation of NADH is controlled by the cofactor concentration. This enables
following the electrocatalyzed oxidation of NADH by static contact angle measurements. Similarly, the
hydrophobic/hydrophilic properties of a naphthoquinone-functionalized polyethylenimine film are reversibly
electroswitched by the reduction and oxidation of the film. In the reduced state of the film the
naphthohydroquinone units catalyze the reduction of O2, thus leading to a hydrophobic film that originates
from the high naphthoquinone/naphthohydroquinone ratio associated with the film. The hydrophobic/hydrophilic properties of an Au electrode modified with a ferrocene monolayer are electroswitched between
a hydrophilic state in the presence of the ferrocenylium (Fc+) oxidized monolayer and a hydrophobic state
in the presence of the ferrocene (Fc) monolayer configuration. The ferrocenylium monolayer activates the
bioelectrocatalyzed oxidation of glucose in the presence of glucose oxidase. The bioelectrocatalyzed oxidation
of glucose leads to the control of the Fc+/Fc ratio associated with the monolayer by the glucose concentration
in the system. This enables following the bioelectrocatalytic oxidation of glucose by static contact angle
measurements.
DNA mag Corrol, Peroxynitrit nicht: Wasserlösliches Mangancorrol ist ein viel besserer Katalysator für die Zersetzung von Peroxynitrit (HOONO) als das analoge Porphyrin. Auch die Wechselwirkungen der beiden Komplexe mit DNA unterscheiden sich deutlich. Positiv geladene Corrole könnten sich somit als sehr nützlich für Therapieansätze erweisen, die auf spezifische Wechselwirkungen mit DNA bauen.
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