Photoinduced chitosan-PEG hydrogels with long-term antibacterial properties.

Photochemical processes offer the possibility of preparing functional hydrogels under green conditions that are compatible with both synthetic and natural polymers. In this study, chitosan-based poly(ethylene) glycol (PEG) were successfully synthesized under light irradiation in aqueous medium. Kinetic studies under irradiation showed that less than 2 min were necessary to obtain fully cross-linked networks. Thermomechanical analyses and swelling experiments indicated that introduction of chitosan overall weakens the hydrogel network but can create domains of higher thermal stability than the PEG-alone structure. The resulting chitosan-PEG hydrogels demonstrated a tremendous inhibition (100%) of bacterial growth (Escherichia coli and Staphylococcus aureus). After 6 months' ageing, one of the hydrogels preserved a high antifouling activity against Escherichia coli. This interesting result, which could be correlated with the network features, demonstrates the strong potential of these photochemical methods to obtain robust bio-functional materials.

Stimuli-responsive thiol-epoxy networks with photo-switchable bulk and surface properties.

In the present work, the versatile nature of o-nitrobenzyl chemistry is used to alter bulk and surface properties of thiol-epoxy networks. By introducing an irreversibly photocleavable chromophore into the click network, material properties such as wettability, solubility and crosslink density are switched locally by light of a defined wavelength. The synthesis of photo-responsive thiol-epoxy networks follows a photobase-catalyzed nucleophilic ring opening of epoxy monomers with photolabile o-nitrobenzyl ester (o-NBE) groups across multi-functional thiols. To ensure temporal control of the curing reaction, a photolatent base is employed releasing a strong amidine-type base upon light exposure, which acts as an efficient catalyst for the thiol epoxy addition reaction. The spectral sensitivity of the photolatent base is extended to the visible light region by adding a selected photosensitizer to the resin formulation. Thus, in the case of photoactivation of the crosslinking reaction the photorelease of the base does not interfere with the absorbance of the o-NBE groups. Once the network has been formed, the susceptibility of the o-NBE groups towards photocleavage reactions is used for a well-defined network degradation upon UV exposure. Sol-gel analysis evidences the formation of soluble species, which is exploited to inscribe positive tone micropatterns by photolithography. Along with the localized tuning of network structure, the irreversible photoreaction is exploited to change the surface wettability of thiol-epoxy networks. The contact angle of water significantly decreases upon UV exposure due to the photo-induced formation of hydrophilic cleavage products enabling the inscription of domains with different surface wettability by photolithography.

Eosin-mediated synthesis of polymer coatings combining photodynamic inactivation and antimicrobial properties.

Polymer coatings exhibiting photodynamic bacterial inactivation properties have been successfully engineered. Such coatings were obtained by photoinduced crosslinking of a PEG-diacrylate monomer associated with the eosin Y dye which was used as both a radical photoinitiator and an antibacterial agent. A dual curing process was followed by combining compatible and solvent-free polymerization mechanisms, i.e. Aza-Michael reaction and free-radical polymerization in the presence of amines. The kinetics evolution of the photopolymerization process was followed using in situ Fourier transform infrared spectroscopy, allowing for the elucidation of the underlying mechanistic pathways. The influence of eosin Y and amines on the thermal and mechanical properties of the films was evidenced and discussed in terms of crosslinking chemistry. The antibacterial properties of the coatings against two different strains (Escherichia coli and Staphylococcus aureus) were evaluated on short and long terms, revealing that eosin confers both photodynamic inactivation and antimicrobial properties to the films. These coatings are therefore particularly promising for disposable medical devices.