Chronic wounds are affecting increasingly larger portions of the general population and their treatment has essentially remained unchanged for the past century. This lack of progress is due to the complex problem that chronic wounds are simultaneously infected and inflamed. Both aspects need to be addressed together to achieve a better healing outcome. Hence, we hereby demonstrate that the stable nitroxide radical (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) can be plasma polymerized into smooth coatings (TEMPOpp), as seen via atomic force microscopy, X-ray photoelectron spectroscopy and ellipsometry.Upon contact with water, these coatings leach nitroxides into aqueous supernatant, as measured via EPR. We then exploited the known cell-signalling qualities of TEMPO to change the cellular behaviour of bacteria and human cells that come into contact with the surfaces. Specifically, the TEMPOpp coatings not only suppressed biofilm formation of the opportunistic bacterium Staphylococcus epidermidis but also dispersed already formed biofilm in a dose-dependent manner; a crucial aspect in treating chronic wounds that contain bacterial biofilm. Thus the coatings' microbiological efficacy correlated with their thickness and the thickest coating was the most efficient. Furthermore, this dose-dependent effect was mirrored in significant cytokine reduction of activated THP-1 macrophages for the four cytokines TNF-a, IL-1b, IL-6 and IP-10. At the same time, the THP-1 cells retained their ability to adhere and colonize the surfaces, as verified via SEM imaging. Thus, summarily, we have exploited the unique qualities of plasma polymerized TEMPO coatings in targeting both infection and inflammation simultaneously; demonstrating a novel alternative to how chronic wounds could be treated in the future.
Hydrogels, and not only natural polysaccharide hydrogels, are substances capable of absorbing large amounts of water and physiological fluids. In this study, we set out to optimize the process for preparing polyvinyl alcohol (PVA) hydrogels. Subsequently, we doped PVA foils with cellulose powder, with poly(ethylene glycol) (PEG) or with gold nanoparticles in PEG colloid solutions (Au). The foils were then modified in a plasma discharge to improve their biocompatibility. The properties of PVA foils were studied by various analytical methods. The use of a suitable dopant can significantly affect the surface wettability, the roughness, the morphology and the mechanical properties of the material. Plasma treatment of PVA leads to ultraviolet light-induced crosslinking and decreasing water absorption. At the same time, this treatment significantly improves the cytocompatibility of the polymer, which is manifested by enhanced growth of human adipose-derived stem cells. This positive effect on the cell behavior was most pronounced on PVA foils doped with PEG or with Au. This modification of PVA therefore seems to be most suitable for the use of this polymer as a cell carrier for tissue engineering, wound healing and other regenerative applications.
The stable nitroxide radical TEMPO [(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl] has a multitude of applications in fields ranging from energy storage to biomedical applications and many more. However, to date, the processes of incorporating nitroxide radicals into thin-film coatings are laborious and not cost-effective, which hinders their wider use in many applications. In contrast, the authors have recently demonstrated the facile method of plasma polymerization of TEMPO into thin-film coatings that retain the stable nitroxide radicals. In this work, we are using three types of mass spectroscopic methods (plasma-mass spectrometry, time of flight secondary ion mass spectrometry, and high-performance liquid chromatography-mass spectrometry) and electron spin resonance to track the fate of the TEMPO molecule from monomer flask through the plasma and inside the resulting coatings. The results of this study demonstrate that TEMPO is a versatile monomer that can be used across different plasma reactors and reliably retain the stable nitroxide radical in the resulting thin-film coatings if certain process conditions are observed, namely, higher process pressures and lower powers.
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