Controlling the supramolecular assembly of redox-active dendrimers at molecular printboards by scanning electrochemical microscopy

Langmuir. 2006 Nov 7;22(23):9770-5. doi: 10.1021/la0615894.

Abstract

Redox-active ferrocenyl (Fc)-functionalized poly(propylenimine) (PPI) dendrimers solubilized in aqueous media by complexation of the Fc end groups with beta-cyclodextrin (betaCD) were immobilized at monolayers of betaCD on glass ("molecular printboards") via multiple host-guest interactions. The directed immobilization of the third-generation dendrimer-betaCD assembly G3-PPI-(Fc)16-(betaCD)16 at the printboard was achieved by supramolecular microcontact printing. The redox activity of the patterned dendrimers was mapped by scanning electrochemical microscopy (SECM) in the positive feedback mode using [IrCl(6)](3-) as a mediator. Local oxidation of the Fc-dendrimers by the microelectrode-generated [IrCl(6)](2-) resulted in an effective removal of the Fc-dendrimers from the host surface since the oxidation of Fc to the oxidized form (Fc+) leads to a concomitant loss of affinity for betaCD. Thus, SECM provided a way not only to image the surface, but also to control the binding of the Fc-terminated dendrimers at the molecular printboard. Additionally, the electrochemical desorption process could be monitored in time as the dendrimer patterns were gradually erased upon multiple scans.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Dendrimers / chemistry*
  • Ferrous Compounds / chemistry
  • Microscopy, Atomic Force
  • Microscopy, Electron, Scanning
  • Molecular Structure
  • Oxidation-Reduction
  • Polypropylenes / chemistry
  • beta-Cyclodextrins / chemistry

Substances

  • Dendrimers
  • Ferrous Compounds
  • Polypropylenes
  • beta-Cyclodextrins
  • poly(propyleneimine)
  • betadex