Double stimuli‐responsive membranes are prepared by modification of pH‐sensitive integral asymmetric polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer membranes with temperature‐responsive poly(N‐isopropylacrylamide) (pNIPAM) by a surface linking reaction. PS‐b‐P4VP membranes are first functionalized with a mild mussel‐inspired polydopamine coating and then reacted via Michael addition with an amine‐terminated pNIPAM‐NH2 under slightly basic conditions. The membranes are thoroughly characterized by nuclear magnetic resonance (1H‐NMR), Fourier transform infrared spectroscopy and X‐ray‐induced photoelectron spectroscopy. Additionally dynamic contact angle measurements are performed comparing the sinking rate of water droplets at different temperatures. The pH‐ and thermo‐double sensitivities of the modified membranes are proven by determining the water flux under different temperature and pH conditions.
Magnesium materials are of increasing interest in the development of biodegradable implants as they exhibit properties that make them promising candidates. However, the formation of gas cavities after implantation of magnesium alloys has been widely reported in the literature. The composition of the gas and the concentration of its components in these cavities are not known as only a few studies using non-specific techniques were done about 60 years ago. Currently many researchers assume that these cavities contain primarily hydrogen because it is a product of magnesium corrosion in aqueous media. In order to clearly answer this question we implanted rare earth-containing magnesium alloy disks in mice and determined the concentration of hydrogen gas for up to 10 days using an amperometric hydrogen sensor and mass spectrometric measurements. We were able to directly monitor the hydrogen concentration over a period of 10 days and show that the gas cavities contained only a low concentration of hydrogen gas, even shortly after formation of the cavities. This means that hydrogen must be exchanged very quickly after implantation. To confirm these results hydrogen gas was directly injected subcutaneously. Most of the hydrogen gas was found to exchange within 1h after injection. Overall, our results disprove the common misbelief that these cavities mainly contain hydrogen and show how quickly this gas is exchanged with the surrounding tissue.
This article provides a contribution towards the mechanistic understanding of surface phenomena observed during the corrosion of Mg-based substrates particularly in the low anodic polarization range. The concept considers the recent literature explaining cathodic hydrogen evolution from noble acting areas even during global anodic polarization. Heavy metal impurities in the ppm range or intermetallics are always present even in highly pure magnesium. Their potential effect was investigated here in more detail. The experimental results contribute to understanding the role of iron impurities in dark area formation and suggest a way for linking the observed phenomena to the recent literature. The shown enhanced cathodic activity of dark areas especially at the corrosion front and the superfluous hydrogen are linked to an iron re-deposition mechanism due to iron reduction. The proposed mechanism is based on the results obtained from innovative characterisation techniques using magnetic fields, diffraction experiments and transmission electron microscopy, which show the formation of iron rich zones, especially at the corrosion front offering "in statu nascendi" metallic Fe films acting as active cathodes for hydrogen reduction.
The present work investigates the corrosion behaviour, the element distribution in the corrosion layer and the cytocompatibility of alloy Mg-10Dy. The corrosion experiments were performed in a cell culture medium (CCM) under cell culture conditions close to the in vivo environment. The element distribution on the surface as well as in cross-sections of the corrosion layer was investigated using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy and X-ray diffraction. The cytocompatibility of alloy Mg-10Dy with primary human osteoblasts was evaluated by MTT, cell adhesion and live/dead staining tests. The results show that the corrosion layer was enriched in Dy, while the P and Ca content gradually decreased from the surface to the bottom of the corrosion layer. In addition, large amounts of MgCO3·3H2O formed in the corrosion layer after 28 days immersion. Both extracts and the Dy-enriched corrosion layer of alloy Mg-10Dy showed no cytotoxicity to primary human osteoblasts.
In our recent work (Höche et al. 2015) we proposed that non-faradaic dissolution of Fe impurities and subsequent re-deposition of thin film of pure ("in statu nascendi") iron enlarges cathodically active sites at Mg surface. The effect drastically accelerates corrosion of impurity containing Mg. In this work we assumed that if Fe re-deposition is prevented, the area of cathodic sites can be drastically decreased and hence corrosion of Mg can be suppressed. In this prove of concept work we used strong Fe 3+ complexing agents in order to remove dissolved iron from corrosion sites and prevent iron re-deposition. All used iron complexing agents efficiently lowered the corrosion rate of Mg. Direct correlation of complex stability with its inhibiting efficiency was established. It was shown that cyanide, salicylate, oxalate, methylsalicylate and thiocyanate efficiently reduce hydrogen evolution and suppress critical dark area formation.
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