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The development of new materials that mimic cartilage and its function is an unmet need that will allow replacing the damaged parts of the joints, instead of the whole joint. Polyvinyl alcohol (PVA) hydrogels have raised special interest for this application due to their biocompatibility, high swelling capacity and chemical stability. In this work, the effect of post-processing treatments (annealing, high hydrostatic pressure (HHP) and gamma-radiation) on the performance of PVA gels obtained by cast-drying was investigated and, their ability to be used as delivery vehicles of the anti-inflammatories diclofenac or ketorolac was evaluated. HHP damaged the hydrogels, breaking some bonds in the polymeric matrix, and therefore led to poor mechanical and tribological properties. The remaining treatments, in general, improved the performance of the materials, increasing their crystallinity. Annealing at 150 °C generated the best mechanical and tribological results: higher resistance to compressive and tensile loads, lower friction coefficients and ability to support higher loads in sliding movement. This material was loaded with the anti-inflammatories, both without and with vitamin E (Vit.E) or Vit.E + cetalkonium chloride (CKC). Vit.E + CKC helped to control the release of the drugs which occurred in 24 h. The material did not induce irritability or cytotoxicity and, therefore, shows high potential to be used in cartilage replacement with a therapeutic effect in the immediate postoperative period.
Appropriate mechanical properties and fast endothelialization of synthetic grafts are key to ensure long-term functionality of implants. We used a newly developed biostable polyurethane elastomer (TPCU) to engineer electrospun vascular scaffolds with promising mechanical properties (E-modulus: 4.8 ± 0.6 MPa, burst pressure: 3326 ± 78 mmHg), which were biofunctionalized with fibronectin (FN) and decorin (DCN). Neither uncoated nor biofunctionalized TPCU scaffolds induced major adverse immune responses except for minor signs of polymorph nuclear cell activation. The in vivo endothelial progenitor cell homing potential of the biofunctionalized scaffolds was simulated in vitro by attracting endothelial colony-forming cells (ECFCs). Although DCN coating did attract ECFCs in combination with FN (FN + DCN), DCN-coated TPCU scaffolds showed a cell-repellent effect in the absence of FN. In a tissue-engineering approach, the electrospun and biofunctionalized tubular grafts were cultured with primary-isolated vascular endothelial cells in a custom-made bioreactor under dynamic conditions with the aim to engineer an advanced therapy medicinal product. Both FN and FN + DCN functionalization supported the formation of a confluent and functional endothelial layer.
Introduction: Bioresorbable collagenous barrier membranes are used to prevent premature soft tissue ingrowth and to allow bone regeneration. For volume stable indications, only non-absorbable synthetic materials are available. This study investigates a new bioresorbable hydrofluoric acid (HF)-treated magnesium (Mg) mesh in a native collagen membrane for volume stable situations. Materials and Methods: HF-treated and untreated Mg were compared in direct and indirect cytocompatibility assays. In vivo, 18 New Zealand White Rabbits received each four 8 mm calvarial defects and were divided into four groups: (a) HF-treated Mg mesh/collagen membrane, (b) untreated Mg mesh/collagen membrane (c) collagen membrane and (d) sham operation. After 6, 12 and 18 weeks, Mg degradation and bone regeneration was measured using radiological and histological methods. Results: In vitro, HF-treated Mg showed higher cytocompatibility. Histopathologically, HF-Mg prevented gas cavities and was degraded by mononuclear cells via phagocytosis up to 12 weeks. Untreated Mg showed partially significant more gas cavities and a fibrous tissue reaction. Bone regeneration was not significantly different between all groups. Discussion and Conclusions: HF-Mg meshes embedded in native collagen membranes represent a volume stable and biocompatible alternative to the non-absorbable synthetic materials. HF-Mg shows less corrosion and is degraded by phagocytosis. However, the application of membranes did not result in higher bone regeneration.
Drug-induced liver toxicity is one of the most common reasons for the failure of drugs in clinical trials and frequent withdrawal from the market. Reasons for such failures include the low predictive power of in vivo studies, that is mainly caused by metabolic differences between humans and animals, and intraspecific variances. In addition to factors such as age and genetic background, changes in drug metabolism can also be caused by disease-related changes in the liver. Such metabolic changes have also been observed in clinical settings, for example, in association with a change in liver stiffness, a major characteristic of an altered fibrotic liver. For mimicking these changes in an in vitro model, this study aimed to develop scaffolds that represent the rigidity of healthy and fibrotic liver tissue. We observed that liver cells plated on scaffolds representing the stiffness of healthy livers showed a higher metabolic activity compared to cells plated on stiffer scaffolds. Additionally, we detected a positive effect of a scaffold pre-coated with fetal calf serum (FCS)-containing media. This pre-incubation resulted in increased cell adherence during cell seeding onto the scaffolds. In summary, we developed a scaffold-based 3D model that mimics liver stiffness-dependent changes in drug metabolism that may more easily predict drug interaction in diseased livers.
Globalization has increased the number of road trips and vehicles. The result has been an intensification of traffic accidents, which are becoming one of the most important causes of death worldwide. Traffic accidents are often due to human error, the probability of which increases when the cognitive ability of the driver decreases. Cognitive capacity is closely related to the driver’s mental state, as well as other external factors such as the CO2 concentration inside the vehicle. The objective of this work is to analyze how these elements affect driving. We have conducted an experiment with 50 drivers who have driven for 25 min using a driving simulator. These drivers completed a survey at the start and end of the experiment to obtain information about their mental state. In addition, during the test, their stress level was monitored using biometric sensors and the state of the environment (temperature, humidity and CO2 level) was recorded. The results of the experiment show that the initial level of stress and tiredness of the driver can have a strong impact on stress, driving behavior and fatigue produced by the driving test. Other elements such as sadness and the conditions of the interior of the vehicle also cause impaired driving and affect compliance with traffic regulations.
Thermoplastic polymers like ethylene-octene copolymer (EOC) may be grafted with silanes via reactive extrusion to enable subsequent crosslinking for advanced biomaterials manufacture. However, this reactive extrusion process is difficult to control and it is still challenging to reproducibly arrive at well-defined products. Moreover, high grafting degrees require a considerable excess of grafting reagent. A large proportion of the silane passes through the process without reacting and needs to be removed at great expense by subsequent purification. This results in unnecessarily high consumption of chemicals and a rather resource-inefficient process. It is thus desired to be able to define desired grafting degrees with optimum grafting efficiency by means of suitable process control. In this study, the continuous grafting of vinyltrimethoxysilane (VTMS) on ethylene-octene copolymer (EOC) via reactive extrusion was investigated. Successful grafting was verified and quantified by 1H-NMR spectroscopy. The effects of five process parameters and their synergistic interactions on grafting degree and grafting efficiency were determined using a face-centered experimental design (FCD). Response surface methodology (RSM) was applied to derive a causal process model and define process windows yielding arbitrary grafting degrees between <2 and >5% at a minimum waste of grafting agent. It was found that the reactive extrusion process was strongly influenced by several second-order interaction effects making this process difficult to control. Grafting efficiencies between 75 and 80% can be realized as long as grafting degrees <2% are admitted.
Here, we study resin cure and network formation of solid melamine formaldehyde pre-polymer over a large temperature range viadynamic temperature curing profiles. Real-time infrared spectroscopy is used to analyze the chemical changes during network formation and network hardening. By applying chemometrics (multivariate curve resolution,MCR), the essential chemical functionalities that constitute the network at a given stage of curing are mathematically extracted and tracked over time. The three spectral components identified by MCR were methylol-rich, ether linkages-rich and methylene linkages-rich resin entities. Based on dynamic changes of their characteristic spectral patterns in dependence of temperature, curing is divided into five phases: (I) stationary phase with free methylols as main chemical feature, (II) formation of flexible network cross-linked by ether linkages, (III) formation of rigid, ether-cross-linked network, (IV) further hardening via transformation of methylols and ethers into methylene-cross-linkages, and (V) network consolidation via transformation of ether into methylene bridges. The presented spectroscopic/chemometric approach can be used as methodological basis for the functionality design of MF-based surface films at the stage of laminate pressing, i.e., for tailoring the technological property profile of cured MF films using a causal understanding of the underlying chemistry based on molecular markers and spectroscopic fingerprints.
Despite strong political efforts in Europe, industrial small- and medium sized enterprises (SMEs) seem to neglect adopting practices for energy effciency. By taking a cultural perspective, this study investigated what drives the establishment of energy effciency and corresponding practices in SMEs. Based on 10 ethnographic case studies and a quantitative survey among 500 manufacturing SMEs, the results indicate the importance of everyday employee behavior in achieving energy savings. The studied enterprises value behavior related measures as similarly important as technical measures. Raising awareness for energy issues within the organization, therefore, constitutes an essential leadership task that is oftentimes perceived as challenging and frustrating. It was concluded that the embedding of energy efficiency in corporate strategy, the use of a broad spectrum of different practices, and the empowerment and involvement of employees serve as major drivers in establishing energy effciency within SMEs. Moreover, the findings reveal institutional influences on shaping the meanings of energy effciency for the SMEs by raising attention for energy effciency in the enterprises and making energy effciency decisions more likely. The main contribution of the paper is to offer an alternative perspective on energy effciency in SMEs beyond the mere adoption of energy-effcient technology.
The chemical synthesis of polysiloxanes from monomeric starting materials involves a series of hydrolysis, condensation and modification reactions with complex monomeric and oligomeric reaction mixtures. Real-time monitoring and precise process control of the synthesis process is of great importance to ensure reproducible intermediates and products and can readily be performed by optical spectroscopy. In chemical reactions involving rapid and simultaneous functional group transformations and complex reaction mixtures, however, the spectroscopic signals are often ambiguous due to overlapping bands, shifting peaks and changing baselines. The univariate analysis of individual absorbance signals is hence often only of limited use. In contrast, batch modelling based on the multivariate analysis of the time course of principal components (PCs) derived from the reaction spectra provides a more efficient tool for real time monitoring. In batch modelling, not only single absorbance bands are used but information over a broad range of wavelengths is extracted from the evolving spectral fingerprints and used for analysis. Thereby, process control can be based on numerous chemical and morphological changes taking place during synthesis. “Bad” (or abnormal) batches can quickly be distinguished from “normal” ones by comparing the respective reaction trajectories in real time. In this work, FTIR spectroscopy was combined with multivariate data analysis for the in-line process characterization and batch modelling of polysiloxane formation. The synthesis was conducted under different starting conditions using various reactant concentrations. The complex spectral information was evaluated using chemometrics (principal component analysis, PCA). Specific spectral features at different stages of the reaction were assigned to the corresponding reaction steps. Reaction trajectories were derived based on batch modelling using a wide range of wavelengths. Subsequently, complexity was reduced again to the most relevant absorbance signals in order to derive a concept for a low-cost process spectroscopic set-up which could be used for real-time process monitoring and reaction control.
Heat pumps are a vital element for reaching the greenhouse gas (GHG) reduction targets in the heating sector, but their system integration requires smart control approaches. In this paper, we first offer a comprehensive literature review and definition of the term control for the described context. Additionally, we present a control approach, which consists of an optimal scheduling module coupled with a detailed energy system simulation module. The aim of this integrated two part control approach is to improve the performance of an energy system equipped with a heat pump, while recognizing the technical boundaries of the energy system in full detail. By applying this control to a typical family household situation, we illustrate that this integrated approach results in a more realistic heat pump operation and thus a more realistic assessment of the control performance, while still achieving lower operational costs.