Untitled

Abstract

Dedicated to Professor Manfred T. Reetz on the occasion of his 60th birthdayThe exact positioning of molecules on surfaces has become essential for the development of molecular electronics [1] and biochip applications, [2] as well as for conducting single molecule experiments. Commonly, one of two possible routes is followed, either by chemically reacting molecules to surfaces or to anchoring molecules present at a surface, or by physisorption, that is, the use of nonspecific physical interactions between molecule and surface, and between molecules themselves. Covalent chemical modification usually requires synthetic effort, is hard to control at surfaces, and does not allow either self-correction or (intentional) desorption. Physisorption does allow self-correction, which is common for all self-assembly processes, but the thermodynamic and kinetic parameters governing adsorption and desorption are difficult to control. Moreover, neighboring molecule±molecule interactions are usually needed for obtaining stable and ordered layers, thus the formation of densely packed layers is a prerequisite. [3] Supramolecular interactions serve as an intermediate case with the possibility of employing advantages from both routes. Supramolecular interactions, such as those observed in host± guest complexes, are specific and directional, and a wealth of information is usually available on their binding strengths and kinetics. The application of molecules that allow the formation of multiple supramolecular interactions provides a tool to tune adsorption and desorption process parameters because thermodynamics and kinetics are, in principle, straightforwardly related to the number of interactions, and the strength and kinetics of an individual interaction.It is therefore our goal to apply host surfaces as ™molecular printboards∫ at which multivalent guest molecules can be positioned. Prerequisites will need to be identified to reach thermodynamically and/or kinetically stable assemblies that can be employed in nanotechnology. It is envisaged that one can control adsorption and desorption by environmental stimuli, for example, by competition with another host in solution. Herein we address the thermodynamic and kinetic ZUSCHRIFTEN (TUE) are gratefully acknowledged for supplying the adamantyl-terminated dendrimers. Frank Geurts (Akzo Nobel, Arnhem) is acknowledged for performing the XPS measurements, and Paul Koster for assistance with the grazing-angle FTIR measurements. Szczepan Zapotoczny is acknowledged for performing the AFM measurements. The Dutch Technology Foundation STW is gratefully acknowledged for funding the Simon Stevin Award project on Nanolithography.

Attachment of Streptavidin to β‐Cyclodextrin Molecular Printboards via Orthogonal Host–Guest and Protein–Ligand Interactions

“…The use of multivalent35 host–guest interactions allows the formation of kinetically stable assemblies, and thus local complex formation for example, by patterning, so that these surfaces can be viewed as “molecular printboards” 36. 37 By choosing the correct number and type of guest sites, it is possible to control thermodynamics, kinetics, and stoichiometry of the adsorption and desorption of multivalent molecules at such surfaces.…”

Redox‐Controlled Interaction of Biferrocenyl‐Terminated Dendrimers with β‐Cyclodextrin Molecular Printboards

“…[5] Molecular printboards are self-assembled monolayers (SAMs) of host molecules to which guest molecules can bind. [5][6][7] We designed molecular printboards based on SAMs on gold of heptathioether-functionalized b-cyclodextrin (b-CD), [8] which forms well-ordered and densely packed monolayers. We also prepared molecular printboards on glass.…”

Strongly Fluorescent, Switchable Perylene Bis(diimide) Host–Guest Complexes with Cucurbit[8]uril In Water

“…[49][50][51][52] In an effort to compare a noncovalent host-guest binding strategy with a covalent approach, PDI was flanked with PEG chains through a copper-catalyzed azide-alkyne cycloaddition (CuAAC) to form a PEG-PDI-PEG structure, as illustrated in Figure 2 a. [49][50][51][52] In an effort to compare a noncovalent host-guest binding strategy with a covalent approach, PDI was flanked with PEG chains through a copper-catalyzed azide-alkyne cycloaddition (CuAAC) to form a PEG-PDI-PEG structure, as illustrated in Figure 2 a.…”