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The present study reports on the long‐term drug release and mechanical properties of bioactive dental filling materials based on chlorhexidine diacetate (CHX) or octinidine (di)hydrochloride (ODH) incorporated in a composite based on dimethacrylates or an ormocer. CHX or ODH were added to a nano‐hybrid ormocer (O) and a nano‐hybrid composite (C) with the amount of 2 wt% to achieve four matrix‐drug combinations: O‐CHX, O‐ODH, C‐CHX, and C‐ODH. Drug extraction and release were measured using high‐performance liquid chromatography with diode‐array detection (HPLC‐DAD), while drug distribution was assessed by using energy dispersive X‐ray spectroscopy (EDX). Drug release in water at 37°C was observed over 87 d. To determine the material properties, the water absorption, water solubility, flexural strength and hardness were measured and compared to the reference materials. Persistent drug release over 87 d was observed for both ODH‐based systems and both ormocer‐systems, with the longest duration of activity seen for the O‐ODH combination. Persistent drug release was achieved via the loosening of the polymer network indicated via decreasing polymerization enthalpies, enhanced water absorption, and water solubility. As a consequence, the flexural strengths of the materials were reduced. However, surface hardness was hardly reduced. ODH seems to be more adequate than CHX for the design of bioactive dental filling materials based on nano‐hybrid ormocer and composites.
The aim of this work was to investigate the elution of residual monomers as a function of the manufacturing process, which are CAD/CAM manufacturing, self-curing and 3D printing. The experimental materials used consisted of the base monomers TEGDMA, Bis-GMA and Bis-EMA and 50 wt.% fillers. Additionally, a 3D printing resin without fillers was tested. The elution of the base monomers into the different media (water, ethanol and ethanol/water (75/25 vol. %)) at 37 °C over a period of up to 120 d as well as the degree of conversion (DC) by FTIR were investigated. No monomer elution could be detected in water. Most residual monomers in both other media were released from the self-curing material whereas the 3D printing composite released relatively little. The CAD/CAM blanks released hardly any quantitatively detectable amounts of monomers. Relative to the base composition, TEGDMA eluted less than Bis-GMA and Bis-EMA. DC did not correlate with residual monomer release; thus, leaching was determined not only by the amount of residual monomers present but by further factors as possibly network density and structure. The CAD/CAM blanks and the 3D printing composite showed similar high DC but lower residual monomer release from the CAD/CAM blank, likewise the self-curing composite and the 3D printing resin exhibited similar DC but different monomer elution. In terms of residual monomer elution and DC, the 3D printing composite seems promising as a new material class for the use as temporary dental crowns and bridges.
Graphical Abstract
The main purpose of new stent technologies is to overcome unfavorable material-related incompatibilities by producing bio- and hemo-compatible polymers with anti-inflammatory and anti-thrombogenic properties. In this context, wettability is an important surface property, which has a major impact on the biological response of blood cells. However, the influence of local hemodynamic changes also influences blood cell activation. Therefore, we investigated biodegradable polymers with different wettability to identify possible aspects for a better prediction of blood compatibility. We applied shear rates of 100 s−1 and 1500 s−1 and assessed platelet and monocyte activation as well as the formation of CD62P+ monocyte-bound platelets via flow cytometry. Aggregation of circulating platelets induced by collagen was assessed by light transmission aggregometry. Via live cell imaging, leukocytes were tracked on biomaterial surfaces to assess their average velocity. Monocyte adhesion on biomaterials was determined by fluorescence microscopy. In response to low shear rates of 100 s−1, activation of circulating platelets and monocytes as well as the formation of CD62P+ monocyte-bound platelets corresponded to the wettability of the underlying material with the most favorable conditions on more hydrophilic surfaces. Under high shear rates, however, blood compatibility cannot only be predicted by the concept of wettability. We assume that the mechanisms of blood cell-polymer interactions do not allow for a rule-of-thumb prediction of the blood compatibility of a material, which makes extensive in vitro testing mandatory.
Oleamide is used as a lubricant in the manufacturing and application of polypropylene (PP) medical devices. Samples of PP were prepared with 0, 1500, and 15 000 ppm oleamide content as lubricant. The samples were either left non-sterile, sterilized with ethylene oxide (ETO), γ-radiation (γ) or autoclaved (A) and stored for up to 4 weeks. To determine the oleamide bulk-to-surface distribution depending on sterilization method and storage time an extraction method and a washing technique were applied. The oleamide content was determined by gas chromatography (GC-FID) and compared with the coefficient of friction (COF). The COF dependent on the measured lubricant content at the surface. The content of lubricant on the surface depends on the type of sterilization: ETO increased the lubricant content to some extent, γ-sterilization and autoclaving reduced it. After storage, no migration of the lubricant to the surface could be detected.
This study investigates the suitability of Piezoelectric Direct Discharge Plasma as a tool for wetting behaviour modification of PEEK and dentin, and compares the results of this method with low-pressure plasma treatment and phosphoric acid etching. Static contact angle measurements were made, roughness was assessed using tactile measurement, and AFM and SEM images were taken. An optimum operating distance of ≤15 mm was determined for the plasma based on the water contact angle. Furthermore, it was demonstrated that despite only a fraction of the power, the PDD plasma also produces hydrophilic and nanostructured PEEK surfaces with a 38° water contact angle in the same plasma time. In contrast, the gold standard of dental surface modification of dentin—phosphoric acid etching—showed no measurable contact angle due to the exposed dentin tubules. Treatment with PDD plasma reduces the water contact angle of dentin from 65° to 43° and is not negative affected by water. Wet, PDD plasma-treated dentin samples show a water contact angle of only 26.5°. The dentin tubules exposed by chemical etching led to a significantly increased roughness. No comparable effect could be demonstrated for plasma treatment on dentin, but based on the contact angle measurements, a chemically strongly activated surface with strongly polar interaction behaviour can be assumed. The additional use of the PDD plasma technique to improve wetting could therefore have a positive effect on the adhesive bond between human dentin and polymeric dental restorative materials or, depending on the adhesive system, replace the etching process altogether.
Despite the increasing importance of recycling, the medical sector is hardy engaged at this time due to regulatory issues. The aim of this study was to evaluate the influence of γ‐radiation sterilization (48–52 kGy) on the repetitive injection molding of a polypropylene copolymer for medical applications. For this purpose, the material was analyzed after injection molding and irradiation. To evaluate the irradiation and reprocessing influence, optical, rheological, and mechanical properties were investigated in addition to chromatography. The latter comprised the quantitative determination of Irgafos 168 and the qualitative comparison of volatile degradation products formed, including the radiolysis product 1,3‐di‐tert‐butylbenzene. The influence of irradiation on the content of Irgafos 168, volatile organic compounds, and 1,3‐di‐tert‐butylbenzene was greatest after the first irradiation, with a decrease of Irgafos 168 content by 40%. The yellowness index and melting enthalpy were influenced by irradiation and processing, but showed no direct relationship to the individual process steps. The zero viscosity correlated directly with gas chromatography–mass spectrometry results and decreased by 80% after the first irradiation. In addition, the elongation at break was reduced by 95% after the second irradiation. The influence of irradiation on the studied characteristics was high, whereas the influence of repetitive processing did not show any measurable differences