Biocompatible fluorinated wrinkled hydrogel films with antimicrobial activity.

Surface-modified hydrogel films were designed to control the bacterial colonization on their surface and to promote cell proliferation through the gradual insertion of highly hydrophobic functional monomers. These hydrogel films were deposited via spin-coating technique, using muscovite mica as a substrate. These samples were then exposed to different external stimuli to produce wrinkled patterns. The relationship between the monomers which compose the hydrogel, was varied to alter the hydrophobic/hydrophilic balance of the final composite. Contact angle and confocal Raman spectroscopy measurements were carried out to characterize the surface and the bulk of the hydrogel film. Cell proliferation and antimicrobial tests were performed using premyoblastic murine cells (C2C12-GFP) and RAW 264.7 (ATCC® TIB-71) macrophagic cell lines, and also for bacteria strains, Staphylococcus aureus and Escherichia coli. The results indicate that the inclusion of the TFPMA produces an increase in cell proliferation, together with a decrease in living bacterial colonies after 48 h, both for Gram-positive or Gram-negative species.

Micrometric Wrinkled Patterns Spontaneously Formed on Hydrogel Thin Films via Argon Plasma Exposure.

The generation of microstructured patterns on the surface of a specific polymeric material could radically improve their performance in a particular application. Most of the interactions with the environment occur at the material interface; therefore, increasing the exposed active surface considerably improves their range of application. In this article, a simple and reliable protocol to form spontaneous wrinkled patterns using a hydrogel layer is reported. For this purpose, we took advantage of the doctor blade technique in order to generate homogenous films over solid substrates with controlled thickness and large coverage. The hydrogel wrinkle formation involves a prepolymerization step which produces oligomers leading to a solution with increased viscosity, enough for doctor blade deposition. Subsequently, the material was exposed to vacuum and plasma to trigger wrinkled pattern formation. Finally, a UV-polymerization treatment was applied to fix the undulations on top. Interestingly, the experimental parameters allowed us to finely tune the wrinkle characteristics (period, amplitude, and orientation). For this study, two main aspects were explored. The first one is related to the role of the substrate functionalization on the wrinkle formation. The second study correlates the deswelling time and its relationship with the dimensions and distribution of the wrinkle pattern. In the first batch, four different 3-(trimethoxysilyl)propyl methacrylate (TSM) concentrations were used to functionalize the substrate in order to enhance the adhesion between hydrogel film and the substrate. The wrinkles formed were characterized in terms of wrinkle amplitude, wavelength, pattern roughness, and surface Young modulus, by using AFM in imaging and force spectroscopy modes. Moreover, the chemical composition of the hydrogel film cross-section and the effect of the plasma treatment were analyzed with confocal Raman spectroscopy. These results demonstrated that an oxidized layer was formed on top of the hydrogel films due to the exposure to an argon plasma.

Design and fabrication of biocompatible wrinkled hydrogel films with selective antibiofouling properties.

In this article, we explored the selective antibiofouling capacity acquired by functional wrinkled hydrogel films via a fine tuning of their chemical structure through the gradual insertion of hydrophobic radical groups in their network. The hydrogel consists of three main components: hydroxyethyl methacrylate (HEMA, amphiphilic monomer), trifluoroethyl methacrylate (TFMA, hydrophobic monomer), and poly(ethylene glycol) diacrylate (PEGDA, hydrophilic crosslinking agent). Interestingly, the manipulation of the chemical composition affects both, surface morphology and physicochemical characteristics of the patterns, inducing transitions between different surface microstructures, i.e. from wrinkles to creases, to folds, and to crumples. Contact angle measurements show that the insertion of TFMA produces a slight decrease in surface wettability, remaining however highly hydrophilic. By using confocal Raman spectroscopy, important information about wrinkle formation mechanism could be obtained. The procedure presented in this article involves two consecutive thermal and photopolymerization steps, generating a "pseudo" two-layer system, which contracts at different extents when is exposed to external stimuli, leading to the formation of wrinkled surfaces. Finally, bacterial and cellular adhesion/proliferation studies were carried out, evidencing that the amount of TFMA included clearly reduce the bacterial adhesion while mammalian cells are able to still proliferate.