The replacement of potentially toxic photoinitiators is of increasing interest regarding the synthesis of biomaterials by photopolymerization. Therefore, we present a new method for the preparation of UV polymerized hydrogels with TiO2 as a photoinitiator. Titania is known to be an excellent photoactive compound which is non-toxic, inert, and cheap. The so-formed hydrogels possess excellent mechanical properties, a high swelling ratio, and high thermal stability. Furthermore, no TiO2 is released from the hydrogels. Thus, the material is highly suitable for medical applications. Additionally, the present TiO2 in the hydrogels remains photoactive as demonstrated by degradation of methylene blue. This enables the application of TiO2-hydrogels in photodynamic therapy.
Hydrogels have shown a great potential as materials for drug delivery systems thanks to their usually excellent bio-compatibility and their ability to trap water-soluble organic molecules in a porous network. In this study, poly(ethylene glycol)-based hydrogels containing a model dye were synthesized by ultraviolet (UV-A) photopolymerization of low-molecular weight macro-monomers and the material properties (dye release ability, transparency, morphology, and polymerization kinetics) were studied. Real-time infrared measurements revealed that the photopolymerization of the materials was strongly limited when the dye was added to the uncured formulation. Consequently, the procedure was adapted to allow for the formation of sufficiently cured gels that are able to capture and later on to release dye molecules in phosphate-buffered saline solution within a few hours. Due to the transparency of the materials in the 400–800 nm range, the hydrogels are suitable for the loading and excitation of photoactive molecules. These can be uptaken by and released from the polymer matrix. Therefore, such materials may find applications as cheap and tailored materials in photodynamic therapy (i.e., light-induced treatment of skin infections by bacteria, fungi, and viruses using photoactive drugs).
Ion adsorbing ultrafiltration membranes provide an interesting possibility to remove toxic ions from water. Furthermore, it is also possible to recover valuable elements. In this work, we demonstrate two easy strategies to modify polyacrylonitrile membranes with anion and cation adsorbing groups. The membranes were modified to have positively charged amine groups or negatively charged carboxyl groups. The success of the reactions was confirmed using IR spectroscopy and zeta-potential measurements. The membranes carrying negatively charged groups provided a negative zeta-potential and had an isoelectric point at pH 3.6, while the membranes carrying positively charged groups had a positive zeta-potential in the analyzed pH range. Since only the surface of the polymer was modified, the pore size and permeance of the membranes were not drastically affected. The membranes prepared by both modification strategies had a pure water permeance higher than 1000 L/(m2 h bar) and a water contact angle of 44.3 and 57.2°, respectively. Therefore, the membranes can be operated at low pressures with reasonable flux. Additionally, SEM images showed that the membranes were still open-pored. Adsorption tests using a positively and a negatively charged dye as well as a toxic cation and an anion were performed to analyze the adsorption behavior. Both membranes were able to adsorb the oppositely charged dyes as well as the copper and chromate ions. Therefore, these membranes are good candidates to purify water streams containing hazardous ions.
Anion‐adsorbing membranes provide an interesting possibility to remove toxic arsenate and chromate from drinking water. A promising way to prepare anion‐exchange materials is to introduce positively charged amine groups on polymers. In this study, polyacrylonitrile (PAN) ultrafiltration membranes were modified with amine functionalities on the membranes. The success of the modifications was demonstrated using infrared spectroscopy and zeta potential measurements. Additionally, the arsenate adsorption was analyzed. The modified membrane showed arsenate adsorption 5 times higher than the pristine PAN membrane.
Photodynamic treatment is a promising tool for the therapy of multidrug-resistant bacteria. In this study, we highlight photosensitizer-loaded hydrogels as an application system for infected wounds. The poly(ethylene glycol) diacrylate-based and electron beam-polymerized hydrogels were mechanically stable and transparent. They were loaded with two photoactive, porphyrin-based drugs – tetrakis(1 methylpyridinium-4-yl)porphyrin p-toluenesulfonate (TMPyP) and tetrahydroporphyrin – p toluenesulfonate (THPTS). The hydrogels released a sufficient amount of the photosensitizers (up to 300 μmol l−1), relevant for efficiency. The antimicrobial effectivity of loaded hydrogels was investigated in a tissue-like system as well as in a liquid system against a multiresistant Escherichia coli. In both systems, light induced eradication was possible. In contrast, hydrogels alone showed only minor antimicrobial activity. Furthermore, the loaded hydrogels were successfully tested against seven multidrug-resistant bacterial strains, namely Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumonia, Acinetobacter baumannii, Pseudomonas aeruginosa, Escherichia coli and Achromobacter xylosoxidans. The eradication of these pathogens, except A. xylosoxidans, was successfully demonstrated. In general, TMPyP-loaded hydrogels were more effective than THPTS-loaded ones. Nevertheless, both photosensitizers displayed effectivity against all investigated bacteria strains. Taken together, our data demonstrate that photosensitizer-loaded hydrogels are a promising new tool to improve the treatment of wounds infected with problematic bacterial pathogens.
In this study, we highlight hydrogels prepared by electron-beam polymerization. In general, the electron-beam-polymerized hydrogels showed improved mechanical and optical transmittances compared to the conventional UV-cured hydrogels. They were more elastic and had a higher crosslinking density. Additionally, they were transparent over a broader wavelength range. The dependence of the mechanical and optical properties of the hydrogels on the number of single differential and total irradiation doses was analyzed in detail. The hydrogels were prepared for usage as a drug delivery material with methylene blue as a drug model. In the first set of experiments, methylene blue was loaded reversibly after the hydrogel synthesis. Electron-beam-polymerized hydrogels incorporated twice as much methylene blue compared to the UV-polymerized gels. Furthermore, the release of the model drug was found to depend on the crosslinking degree of the hydrogels. In addition, electron-beam polymerization enabled the irreversible binding of the drug molecules if they were mixed with monomers before polymerization.