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Steffen Onclin

Publications and source records attributed to Steffen Onclin.

6 recordsLinked to original sources

Engineering silicon oxide surfaces using self-assembled monolayers.

Although a molecular monolayer is only a few nanometers thick it can completely change the properties of a surface. Molecular monolayers can be readily prepared using the Langmuir-Blodgett methodology or by chemisorption on metal and oxide surfaces. This Review focuses on the use of chemisorbed self-assembled monolayers (SAMs) as a platform for the functionalization of silicon oxide surfaces. The controlled organization of molecules and molecular assemblies on silicon oxide will have a prominent place in "bottom-up" nanofabrication, which could revolutionize fields such as nanoelectronics and biotechnology in the near future. In recent years, self-assembled monolayers on silicon oxide have reached a high level of sophistication and have been combined with various lithographic patterning methods to develop new nanofabrication protocols and biological arrays. Nanoscale control over surface properties is of paramount importance to advance from 2D patterning to 3D fabrication.

Journal Article↗

Molecular printboards on silicon oxide: lithographic patterning of cyclodextrin monolayers with multivalent, fluorescent guest molecules.

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.

Acrylonitrile↗

Molecular boxes on a molecular printboard: encapsulation of anionic dyes in immobilized dendrimers.

Fifth-generation poly(propylene imine) dendrimers, modified with 64 apolar adamantyl groups, have been immobilized on cyclodextrin host monolayers ("molecular printboards") on glass by supramolecular microcontact printing. The immobilized dendrimers retain their guest-binding properties and function as "molecular boxes" that can be filled with fluorescent dye molecules from solution. Alternatively, part of the immobilized dendrimers were filled with dye molecules by cross-microcontact printing while the remaining, empty dendrimers were filled with a different dye from solution, resulting in alternating patterns of dye molecules. In addition, we demonstrate that encapsulation of dyes in immobilized dendrimers is reversible: immobilized molecular boxes can be filled with a dye, emptied, and subsequently refilled with a different dye.

Biotechnology↗

Directed self-assembly of functionalized silica nanoparticles on molecular printboards through multivalent supramolecular interactions.

Silica nanoparticles functionalized with beta-cyclodextrin (CD) host molecules (5) have been prepared by reacting carboxylic active ester-terminated silica nanoparticles (4) with CD heptamine. Silica nanoparticles functionalized with glucosamine (6), having similar surface properties as 5 but lacking the host-guest recognition motif, were used to perform blank experiments. The CD-functionalized silica nanoparticles 5 were determined by TEM to be 55 +/- 6 nm in size. They exhibited pH-dependent aggregation, which is explained by the presence of free amino and carboxylic acid groups on the particle surface, which was corroborated by zeta potential measurements. The functionalization with CD was further confirmed by host-guest studies in solution and at CD-functionalized silicon substrates. The addition of an adamantyl-terminated dendrimer, capable of multivalent host-guest binding with CD, led to strong aggregation of the CD particles 5, but not of the glucosamine-functionalized 6. Furthermore, 5 gave strong adsorption to CD monolayers on silicon onto which adamantyl-terminated dendrimers were adsorbed, whereas 6 did not. The good discrimination between dendrimer-covered and uncovered areas of the CD monolayer substrates allowed the directed self-assembly of the silica particles 5 onto dendrimer-patterned areas created by microcontact printing.

Glucosamine↗

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces.

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.

Journal Article↗