Cigdem Yesildag

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.

In the present work, a soft lithographic process is used to create nanometer-sized line patterns of gold nanoparticles (Au NPs) on PEG-based hydrogels. Hereby nanometer-sized wrinkles on polydimethylsiloxane (PDMS) are first fabricated, then functionalized with amino-silane and subsequently coated with Au NPs. The Au NPs are electrostatically bound to the surface of the wrinkled PDMS. In the next step, these relatively loosely bound Au NPs are transferred to PEG based hydrogels by simple contacting, which we denote “nano-contact transfer”. Nano-patterned Au NPs lines on PEG hydrogels are thus achieved, which are of interesting potential in nano-photonics, biosensor applications (using SERS) and to control nanoscopic cell adhesion events.

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.

We report on a versatile and easy approach to micro-pattern gold nanoparticles (Au NPs) on 8-arm poly(ethylene glycol)-vinyl sulfone thiol (8PEG-VS-SH) hydrogels, and the application of these patterned Au NPs stripes in controlling cell adhesion. Firstly, the Au NPs were patterned on silicon wafers, and then they were transferred onto reactive, multifunctional 8PEG-VS-SH hydrogels. The patterned, micrometer-sized Au NPs stripes with variable spacings ranging from 20 μm to 50 μm were created by our recently developed micro-contact deprinting method. For this micro-contact deprinting approach, four different PEG-based stamp materials have been tested and it was found that the triblock copolymer PEG-PPG-PEG-(3BC) stamp established the best transfer efficiency and has been used in the ongoing work. After the successful creation of micro-patterns of Au NPs stripes on silicon, the patterns can be transferred conveniently and accurately to 8PEG-VS-SH hydrogel films. Subsequently these Au NPs patterns on 8PEG-VS-SH hydrogels have been investigated in cell culture with murine fibroblasts (L-929). The cells have been observed to adhere to and spread on those nano-patterned micro-lines in a remarkably selective and ordered manner.