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Richard Stutz

Publications and source records attributed to Richard Stutz.

4 recordsLinked to original sources

High-speed microcontact printing.

We have demonstrated microcontact printing (muCP) of self-assembled monolayers in the millisecond regime. The contact formation and separation of the stamp and substrate was studied with high-speed video recordings. Using high ink concentrations and contact times as short as 1 ms, we printed monolayers of hexadecanethiol on Au, which served as a selective etch resist. High-speed muCP yields defect-free monolayers that are independent of the dimensions of the printed patterns, have high contrast between printed and unprinted areas, and enable perfect reproducibility of prints.

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Microcontact printing of proteins inside microstructures.

Microfluidic devices are well suited for the miniaturization of biological assays, in particular when only small volumes of samples and reagents are available, short time to results is desirable, and multiple analytes are to be detected. Microfluidic networks (MFNs), which fill by means of capillary forces, have already been used to detect important biological analytes with high sensitivity and in a combinatorial fashion. These MFNs were coated with Au, onto which a hydrophilic, protein-repellent monolayer of thiolated poly(ethyleneglycol) (HS-PEG) was self-assembled, and the binding sites for analytes were present on a poly(dimethylsiloxane) (PDMS) sealing cover. We report here a set of simple methods to extend previous work on MFNs by integrating binding sites for analytes inside the microstructures of MFNs using microcontact printing (muCP). First, fluorescently labeled antibodies (Abs) were microcontact-printed from stamps onto planar model surfaces such as glass, Si, Si/SiO2, Au, and Au derivatized with HS-PEG to investigate how much candidate materials for MFNs would quench the fluorescence of printed, labeled Abs. Au coated with HS-PEG led to a fluorescence signal that was approximately 65% weaker than that of glass but provided a convenient surface for printing Abs and for rendering the microstructures of the MFNs wettable. Then, proteins were inked from solution onto the surface of PDMS (Sylgard 184) stamps having continuous or discontinuous micropatterns or locally inked onto planar stamps to investigate how the aspect ratio (depth:width) of microstructures and the printing conditions affected the transfer of protein and the accuracy of the resulting patterns. By applying a controlled pressure to the back of the stamp, Abs were accurately microcontact-printed into the recessed regions of MFNs if the aspect ratio of the MFN microstructures was lower than approximately 1:6. Finally, the realization of a simple assay between Abs (used as antigens) microcontact-printed in microchannels and Abs from solution suggests that this method could become useful to pattern proteins in microstructures for advanced bioanalytical purposes.

Antibodies↗

Printing chemical gradients.

We describe a method to exploit the mass-transfer limitations of microcontact printing for the fabrication of surfaces with well-defined, arbitrarily shaped composition variations. An analysis of the transport processes reveals that the printing of hexadecanethiol (HDT) from poly(dimethylsiloxane) is purely diffusion-controlled. Stamps with geometries that enhance surface-normal diffusion paths therefore allow not only the contours, but also the local density of self-assembled monolayers to be controlled. We use stamps with variable thickness and uniform ink concentration to print HDT density gradients on gold, depleting the stamps during the process. In the second step, a perfluorinated thiol fills the vacancies in the partial monolayer to form a two-component gradient that we analyze by means of X-ray photoelectron spectroscopy and spectroscopic ellipsometry. Linear and radial gradients are shown here as examples for a wide range of geometries that can be fabricated with high precision using the method.

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Diffusion of alkanethiols in PDMS and its implications on microcontact printing (muCP).

n-Alkanethiols HS-(CH2)n-CH3 such as hexadecanethiol (HDT, n = 15), octadecanethiol (ODT, n = 17), and eicosanethiol (ECT, n = 19) have been shown to provide highly protective etch resists on microcontact-printed noble metals. As the quality of the printed pattern strongly depends on the mobility of the ink compound, we focused on understanding the diffusion behavior of HDT, ODT, and ECT in poly(dimethylsiloxane) (PDMS) stamps. We used a commercial PDMS material (Sylgard184), which is commonly used for microcontact printing (muCP), and a custom-synthesized one with a higher modulus. On the basis of linear-diffusion experiments, which maintained realistic printing conditions, we showed that the ink transport in the stamp follows Fick's law of diffusion. We then determined the diffusion coefficient by analytical and numerical modeling of the diffusion experiments. Numerical calculations were carried out with the finite-difference method applying more realistic boundary conditions (ink adsorption). Values for the diffusion coefficients of the three ink compounds in the two different PDMS materials all are on the order of (4-7) x 10(-7) cm2 s(-1). The scope and limits of the mathematical models are discussed. To demonstrate the potential of such models for microcontact printing, we simulate multiple printing cycles of an inked stamp and compare the results with experimental data.

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