Glassy carbon beads are selectively functionalized on one side with an ultrathin organic layer by bipolar electrochemical reduction of diazonium salts to give Janus‐type beads with a hybrid organic–inorganic composition (see scheme). The presence of the grafted organic layers is revealed either by co‐adsorption of gold nanoparticles or by coupling with a fluorescent molecule.
Vertically aligned carbon nanotubes (VACNTs) were grown on the inner wall of the pores of an anodic aluminum oxide template by using chemical vapor deposition. The versatile bipolar electrochemistry approach was applied to selectively modify the tubes at one end with an organic layer of 4‐aminophenyl moieties. The presence of the template during the bipolar experiments intrinsically protects the outer surface of the tubes from the grafting of the organic layer. The layer is, thus, not only selectively grafted at the cathodic side of the tubes, but also exclusively onto the inner surface of the tubes. For longer deposition times, one end of the tubes was completely capped with a dense organic layer. Thus, bipolar electrochemistry can not only generate CNTs bearing organic functionalities on the tube surface for biosensing or bio‐electrocatalytic applications, but can also create a dense organic layer as a cap at one end of the tubes, opening up applications in the fields of drug storage and delivery.
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