Multifunctional biomedical materials capable of integrating optical functions are highly desirable for many applications, such as advanced intra-ocular lens (IOL) implants. Therefore, poly(ethylene glycol)-diacrylate (PEG-DA) hydrogels are used with different photoinitiators (PI). In addition to standard UV PI Irgacure, Erythrosin B and Eosin Y are used as PI with high sensitivity in the optical range of the spectrum. The minimum PI concentrations for producing new hydrogels with PEG-DA and different PIs were determined. Hydrogel films were obtained, which were applicable for light-based patterning and, hence, the functionalization of surface and volume. Cytotoxicity tests confirm cytocompatibility of hydrogels and compositions. Exploiting the correlation of structure and function allows biomedical materials with multifunctionality.

In this work a novel, relatively simple, and fast method for patterning of gold nanoparticles (Au NPs) on poly(ethylene glycol) (PEG)-based hydrogels is presented. In the hereby exploited reactive micro-contact printing (reactive-μ-CP) process, the surface of a micro-relief patterned PDMS-stamp is first functionalized with an amino-silane self-assembled monolayer (SAM), which is then inked with Au NPs. The stamp is subsequently brought into conformal contact with thiol-functionalized PEG-based hydrogel films. Due to the strong gold-thiol interactions the Au NPs are adequately and easily transferred onto the surfaces of these soft, multifunctional PEG hydrogels. In this way, defined μ-patterns of Au NPs on PEG hydrogels are achieved. These Au NPs patterns allow specific biomolecular interactions on PEG surfaces, and cell adhesion has been studied. Cells were found to effectively adhere only on Au NPs micro-patterns and to avoid the anti-adhesive PEG background. Besides the cell adhesion studies, these Au NPs μ-patterns can be potentially applied as biosensors in plasmon-based spectroscopic devices or in medicine, e.g., for drug delivery systems or photothermal therapies.

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.