Electro-Click Modification of Conducting Polymer Surface Using Cu(I) Species Generated on a Bipolar Electrode in a Gradient Manner

Abstract

The electro-click reaction of azide-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT-N 3 ) and a terminal alkyne was investigated using electrogenerated Cu(I) species on a bipolar electrode in a gradient manner. The introduction of a perfluoroalkyl group derived from the alkyne moiety onto the PEDOT surface only at the cathodic part of the bipolar electrode was successfully characterized by X-ray analyses and the surface properties of the modified film were studied. The spectroscopic analysis of the rhodamine-functionalized PEDOT prepared similarly in a gradient manner was also performed with a UV−vis spectrophotometer.

Fabrication of gradient polymer surfaces using bipolar electrochemistry

“…The fluorine-content profile revealed that the electrogenerated Cu(I)-mediated click reaction reflected the potential profile on the BPE (Figure 5b). 27 Then, the surface property of the gradually perfluoroalkylated PEDOT was investigated by measuring the static contact angle of a water droplet on the film. As expected, the contact angle at the fluorinated surface was significantly larger than that at the pristine surface (Figure 5c).…”

Electrochemical nanoarchitectonics and layer-by-layer assembly: From basics to future

“…Its application to electroclick was reported recently by Shida et al [382]. A PEDOT-N 3 coated bipolar electrode could be functionalized only on its cathodic part and in a gradient manner with various alkyne-bearing molecules (Fig.…”

“…Cu(I) ions are indeed unstable in the presence of dissolved oxygen, which restricts their diffusion and permits the coupling reactions to occur only close to the electrode. Consequently, micro-electrodes [330], local probe microscopies [380,381], bipolar electrodes [382] and gradient devices [383,384] have been used to locally induce electroclick as described in Fig. 17.…”

“…Local generation and propagation of Cu(I) catalytic ions can be triggered by (a) microelectrodes [330], (b) local probes [380,381], (c) electrogenerated gradients [383,384], and (d) bipolar electrochemistry [382]. [381,387,388] Azido-silane monolayer Electro-generated gradients 50 Biomaterials, cellular migration control [383,384,389] PEDOT-N 3 Bipolar electro-chemistry Unknown Energetic devices, Biomaterials [382] resolution. For instance, by using 25 and 12.5 m diameter UMEs at a distance of 10 m from the surface, Quinton et al could improve the resolution to 75 m [387].…”

Reactive monolayers for surface gradients and biomolecular patterned surfaces

“…By means of stenciled 135 or bipolar 136 "e-click", surface gradients of covalently bound alkyne-bearing molecules were created on azide-functionalized conductive polymers.…”