Molecular Printboards on Silicon Oxide: Lithographic Patterning of Cyclodextrin Monolayers with Multivalent, Fluorescent Guest Molecules

Abstract

Three compounds bearing multiple adamantyl guest moieties and a fluorescent dye have been synthesized for the supramolecular patterning of beta-cyclodextrin (CD) host monolayers on silicon oxide using microcontact printing and dip-pen nanolithography. Patterns created on monolayers on glass were viewed by laser scanning confocal microscopy. Semi-quantitative analysis of the patterns showed that with microcontact printing approximately a single monolayer of guest molecules is transferred. Exposure to different rinsing procedures showed the stability of the patterns to be governed by specific supramolecular multivalent interactions. Patterns of the guest molecules created at CD monolayers were stable towards thorough rinsing with water, whereas similar patterns created on poly(ethylene glycol) (PEG) reference monolayers were instantly removed. The patterns on CD monolayers displayed long-term stability when stored under N(2), whereas patterns at PEG monolayers faded within a few weeks due to the diffusion of fluorescent molecules across the surface. Assemblies at CD monolayers could be mostly removed by rinsing with a concentrated CD solution, demonstrating the reversibility of the methodology. Patterns consisting of different guest molecules were produced by microcontact printing of one guest molecule and specific adsorption of a second guest molecule from solution to non-contacted areas, giving well-defined alternating assemblies. Fluorescent features of sub-micrometer dimensions were written using supramolecular dip-pen nanolithography.

Gestaltung der Siliciumoxidoberfläche durch selbstorganisierte Monoschichten

“…[268] Die immobilisierten Kolloide fungierten als Katalysator für die stromlose Abscheidung von Kupfer, wodurch Kupferlinien von wenigen Mikrometern auf einer isolierenden Oberfläche entstanden. Kürzlich stellten Reinhoudt et al den supramolekularen mCP vor, [269][270][271] [272] In der Nanotransferlithographie wird ein mit Gold beschichteter PDMSStempel zur Übertragung dünner, aber stabiler Goldschichten auf die Monoschicht verwendet (Schema 5). In einer Abbildung 8.…”

“…Cyclodextrin-Wirt-Monoschichten wurden durch mCP geeigneter Gastmoleküle mit einem Muster versehen. [269,270] Schema 5. Durch Nanotransferdruck hergestellte Metallstrukturen auf adhäsiven SAMs.…”

“…Reinhoudt et al stellten die supramolekulare DPN vor, bei der eine AFMSpitze mit geeigneten Gastmolekülen eingefärbt ist und eine Wirtmonoschicht aus b-Cyclodextrin als Substrat fungiert. [270] Auf Wirt-Gast-Wechselwirkungen basierende Muster mit Strukturen von weniger als 500 nm Größe Schema 6. Konstruktive Nanolithographie mittels spitzeninduzierter Elektrooxidation und anschließen-der Selbstorganisation auf der geschriebenen Schablone.…”

Near-field propagation in planar nanostructured arrays

“…Scanning probe lithography represents a general and sufficiently flexible technique offering the requisite precision; 23 a well-proven and particularly promising method for molecular patterning and nanoimprinting is dip-pen nanolithography. 24 The exact choice of method for printing and layering the donor and acceptor arrays will to some extent determine the optimum form of patterning for each array lattice, and it remains to be seen how this structure will be taken forward as an alternative to more conventional devices.…”

Orthogonal Supramolecular Interaction Motifs for Functional Monolayer Architectures

“…Huskens and Reinhoudt et al introduced the concept of "molecular printboards", for the stable positioning and assembly of guest functionalized dendrimers, [43] nanoparticles, [44] proteins, [45] and fluorescent small molecules [46] onto CD SAMs. Molecular patterns of (bio)molecules have also been prepared on these molecular printboards by using lithographic techniques such as microcontact printing and dip-pen nanolithography.…”