Multivalent dendrimers at molecular printboards: influence of dendrimer structure on binding strength and stoichiometry and their electrochemically induced desorption

C.A. Nijhuis, Fang Yu, Wolfgang Knoll, Jurriaan Huskens, David Reinhoudt

Research output: Contribution to journalArticleAcademicpeer-review

84 Citations (Scopus)

Abstract

A fundamental understanding of multivalency can have a profound influence on bottom-up nanofabrication. For this purpose, three different types of ferrocenyl (Fc) functionalized dendrimers of generations 1-5 with various spacer groups were adsorbed at self-assembled monolayers (SAMs) of heptathioether-functionalized -cyclodextrin (CD) on gold. The dendrimers formed kinetically stable supramolecular assemblies at the CD host surface having up to eight multivalent supramolecular interactions, but could be efficiently removed from the host surface by electrochemical oxidation of the Fc end groups. Dendrimer desorption and re-adsorption could be repeated a number of times without significant decomposition of the system. The stoichiometries of the dendrimers at the surface were determined using cyclic voltammetry (CV). These were quantitatively confirmed for the lower generations by surface plasmon resonance (SPR) titrations of the dendrimers to the CD SAM. Measuring CV and SPR simultaneously gave crucial mechanistic information on the electrochemically induced desorption of the dendrimers from the host surface. The redox-active dendrimers effectively blocked the host surface for binding other molecules, e.g. adamantyl-functionalized dendrimers, but electrochemically induced release of the blocking layer revealed the host surface to which the adamantyl dendrimers could then bind.
Original languageUndefined
Pages (from-to)7866-7876
JournalLangmuir
Volume21
Issue number17
DOIs
Publication statusPublished - 2005

Keywords

  • METIS-225117
  • IR-53011

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