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    Transparent Low Molecular Weight Poly(Ethylene Glycol) Diacrylate-Based Hydrogels as Film Media for Photoswitchable Drugs
    (Basel : MDPI, 2017-11-23) Pelras, Théophile; Glass, Sarah; Scherzer, Tom; Elsner, Christian; Schulze, Agnes; Abel, Bernd
    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).
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    Enhanced removal and toxicity decline of diclofenac by combining UVA treatment and adsorption of photoproducts to polyvinylidene difluoride
    (Basel : MDPI, 2020) Fischer, Kristina; Sydow, Stephan; Griebel, Jan; Naumov, Sergej; Elsner, Christian; Thomas, Isabell; Latif, Amira Abdul; Schulze, Agnes
    The occurrence of micropollutants in the environment is an emerging issue. Diclofenac, a non-steroidal anti-inflammatory drug, is one of the most frequently detected pharmaceuticals in the environment worldwide. Diclofenac is transformed by UVA light into different products with higher toxicity. The absorbance of the transformation products overlaps with the absorbance of diclofenac itself and inhibits the ongoing photoreaction. By adding polyvinylidene difluoride (PVDF), the products adsorb to the surface of PVDF. Therefore, phototransformation of diclofenac and total organic carbon (TOC) removal is enhanced and the toxicity decreased. At 15 min and 18 h of UVA treatment, removal of diclofenac and TOC increases from 56% to 65% and 18% to 54%, respectively, when PVDF is present. The toxicity of a UVA treated (18 h) diclofenac solution doubles (from 5 to 10, expressed in toxicity units, TU), while no toxicity was detectable when PVDF is present during UVA treatment (TU = 0). PVDF does not need to be irradiated itself but must be present during photoreaction. The adsorbent can be reused by washing with water or ethanol. Diclofenac (25 mg L−1) UVA light irradiation was monitored with high performance liquid chromatography (HPLC), UV-Vis spectroscopy and by analysing the decrease of TOC. The toxicity towards Vibrio fischeri was examined according to DIN EN ISO 11348-1: 2009-05. Density functional theory (DFT) was used to simulate the phototransformation products known in literature as well as further products identified via gas chromatography–mass spectrometry (GC-MS). The absorption spectra, reaction enthalpies (ΔH) and Gibbs free energy of reactions (ΔG) were calculated. The combination of UVA irradiation of diclofenac with adsorption of photoproducts to PVDF is unique and opens up new possibilities to enhance removal of pollutants from water.