Micropatterning of Au NPs on PEG Hydrogels Using Different Silanes To Control Cell Adhesion on the Nanocomposites.

Amino-silanization of silica-based substrates has proven to be effective in guiding the immobilization of citrate-stabilized Au NPs in a good, homogeneous fashion. This accomplishment has formed the basis of fabricating micropatterns of Au NPs on such substrates by patterning of oxidized silicon wafers with (3-aminopropyl)trimethoxysilane (amino-silane) using the microcontact printing (µCP) process. This micropattern of amino-silane is used to specifically adsorb Au NPs. To avoid unspecific adsorption to the nonsilanized areas on the silicon wafers, the nonstamped areas were backfilled with self-assembled monolayers of organosilanes, for example, with methyl- or perfluoro-end-groups. Finally, after having fabricated a micropattern of Au NPs on silicon wafers, the Au NP patterns were transferred onto poly(ethylene glycol) hydrogels by our newly developed procedures, and on these nanocomposite materials, controlled cell adhesion has been achieved. Furthermore, these materials are great candidates for plasmon-based biosensor applications and also for various medical applications, such as for drug delivery systems or photothermal therapies.

Influence of Network Structure on the Crystallization Behavior in Chemically Crosslinked Hydrogels.

The network structure of hydrogels is a vital factor to determine their physical properties. Two network structures within hydrogels based on eight-arm star-shaped poly(ethylene glycol)(8PEG) have been obtained; the distinction between the two depends on the way in which the macromonomers were crosslinked: either by (i) commonly-used photo-initiated chain-growth polymerization (8PEG⁻UV), or (ii) Michael addition step-growth polymerization (8PEG⁻NH3). The crystallization of hydrogels is facilitated by a solvent drying process to obtain a thin hydrogel film. Polarized optical microscopy (POM) results reveal that, while in the 8PEG⁻UV hydrogels only nano-scaled crystallites are apparent, the 8PEG⁻NH3 hydrogels exhibit an assembly of giant crystalline domains with spherulite sizes ranging from 100 to 400 µm. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses further confirm these results. A model has been proposed to elucidate the correlations between the polymer network structures and the crystallization behavior of PEG-based hydrogels.

Novel Wet Micro-Contact Deprinting Method for Patterning Gold Nanoparticles on PEG-Hydrogels and Thereby Controlling Cell Adhesion.

In the present work we introduce a novel method to create linear and rectangular micro-patterns of gold nanoparticles (Au NPs) on poly(ethylene glycol) (PEG) hydrogels. The strategy consists of removing Au NPs from defined regions of the silicon wafer by virtue of the swelling effect of the hydrogel. Using this method, which we denote as "Wet Micro-Contact Deprinting", well-defined micro-patterns of Au NPs on silicon can be created. This resulting pattern is then transferred from the hard substrate to the soft surface of PEG-hydrogels. These unique micro- and nano-patterned hydrogels were cultured with mouse fibroblasts L929 cells. The cells selectively adhered on the Au NPs coated area and avoided the pure PEG material. These patterned, nanocomposite biointerfaces are not only useful for biological and biomedical applications, such as tissue engineering and diagnostics, but also, for biosensor applications taking advantage of surface plasmon resonance (SPR) or surface enhanced Raman scattering (SERS) effects, due to the optical properties of the Au NPs.