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Temperature Dependency of Morphological Structure of Thermoplastic Polyurethane using WAXS and SAXS
(2016)
Polyurethanes achieved an exceptional position among the most important organic polymers due to their highly specific technological application areas. Polyurethanes represent a polyaddition product of isocyanate and diols. In terms of their enormous industrial importance, the chemistry of isocyanates has been extensively studied.
3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n?1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.
The analysis of Δ9-tetrahydrocannabinol (THC) and its metabolites 11-hydroxy-Δ9-tetrahydrocannabinol (11-OH-THC), and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol (THC-COOH) from blood serum is a routine task in forensic toxicology laboratories. For examination of consumption habits, the concentration of the phase I metabolite THC-COOH is used. Recommendations for interpretation of analysis values in medical-psychological assessments (regranting of driver’s licenses, Germany) include threshold values for the free, unconjugated THC-COOH. Using a fully automated two-step liquid-liquid extraction, THC, 11-OH-THC, and free, unconjugated THC-COOH were extracted from blood serum, silylated with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), and analyzed by GC/MS. The automation was carried out by an x-y-z sample robot equipped with modules for shaking, centrifugation, and solvent evaporation. This method was based on a previously developed manual sample preparation method. Validation guidelines of the Society of Toxicological and Forensic Chemistry (GTFCh) were fulfilled for both methods, at which the focus of this article is the automated one. Limits of detection and quantification for THC were 0.3 and 0.6 μg/L, for 11-OH-THC were 0.1 and 0.8 μg/L, and for THC-COOH were 0.3 and 1.1 μg/L, when extracting only 0.5 mL of blood serum. Therefore, the required limit of quantification for THC of 1 μg/L in driving under the influence of cannabis cases in Germany (and other countries) can be reached and the method can be employed in that context. Real and external control samples were analyzed, and a round robin test was passed successfully. To date, the method is employed in the Institute of Legal Medicine in Giessen, Germany, in daily routine. Automation helps in avoiding errors during sample preparation and reduces the workload of the laboratory personnel. Due to its flexibility, the analysis system can be employed for other liquid-liquid extractions as well. To the best of our knowledge, this is the first publication on a comprehensively automated classical liquid-liquid extraction workflow in the field of forensic toxicological analysis.
We examined the cytotoxic effects of chaetocin on clear cell renal cell carcinoma (ccRCC) cells and the possibility to combine the effects of chaetocin with the effects of cytokine-induced killer cells (CIK) assayed by MTT assay and FACS analysis. Chaetocin is a thiodioxopiperazine produced by fungi belonging to the chaetomiaceae family. In 2007, it was first reported that chaetocin shows potent and selective ex vivo anti-cancer activity by inducing reactive oxygen species. CIK cells are generated from CD3+/CD56- T lymphocytes with double negative CD4-/CD8- phenotype that are isolated from human blood. The addition of distinct interleukins and antibodies results in the generation of CIK cells that are able to specifically target and destroy renal carcinoma cells. The results of this research state that the anti-ccRCC activity of chaetocin is weak and does not show a high grade of selectivity on clear cell renal cell carcinoma cells. Although the CIK cells show a high grade of selective anti-ccRCC activity, this effect could not be improved by the addition of chaetocin. So chaetocin seems to be no suitable agent for specific targeting ccRCC cells or for the combination therapy with CIK cells in renal cancer.
One of the most common problems in Regenerative Medicine is the regeneration of damaged bone with the aim of repairing or replacing lost or damaged bone tissue by stimulating the natural regenerative process. Particularly in the fields of orthopedic, plastic, reconstructive, maxillofacial and craniofacial surgery there is need for successful methods to restore bone. From a regenerative point of view two different bone replacement problems can be distinguished: large bone defects and small bone defects. Currently, no perfect system exists for the treatment of large bone defects.
Bone regeneration and replacement is a major focus in regenerative medicine since degenerative diseases and tumor surgery as well as accidents or dangerous recreational behavior is leading to an increasing need for bone reconstruction strategies. Especially for critical size bone defects, tissue engineering with mesenchymal stem cells is extensively studied because these cells are functioning as precursors for osteoblast in vivo. Nevertheless to reproduce the complex interaction of various factors in vitro is not an easy approach and further investigations have to be done. The status quo is summarized. A variety of growth and transcription factors are known to be involved in osteogenesis with bone morphogenetic proteins (BMPs) and the transcription factor Runx2 being the most extensively studied ones. But also PPAR γ and Osterix are generally regarded as the master regulators of osteoblast differentiation. Recently the large family of purinergic receptors has proven to be essential molecules in osteogenesis as well. In addition, scaffolding is needed to create a three-dimensional tissue. Recent developments in scaffold design are summarized, including natural and synthetic materials with or without the use of bioactive molecules constructed to mimic the natural environment. The status quo of scaffold fabrication methods such as 3D nanoprinting and their influence on cell-scaffold interactions is discussed. In this review we summarize the most interesting results and our related work focusing on two joined approaches: 1) the complex interaction of the most promising factors improving or accelerating osteogenic differentiation and ii) the development of scaffold materials with osteoconductive and osteoinductive properties.
Polyether and polyether/ester based TPU (thermoplastic polyurethanes) were investigated with wide-angle XRD (X-ray diffraction) and SAXS (small angle X-ray scattering). Furthermore, SAXS measurements were performed in the temperature range of 30 °C to 130 °C. Polyether based polymers exhibit only one broad diffraction signal in a region of 2 θ 15° to 25°. In case of polyurethanes with ether/ester modification, the broad diffraction signal arises with small sharp diffraction signals. SAXS measurements of polymers reveal the size and shape of the crystalline zones of the polymer. Between 30 °C and 130 °C the size of the crystalline zone changes significantly. The size decreases in most of investigated TPU. In the case of Desmopan 9365D an increase of the particle size was observed.
Recessive mutations in the MPV17 gene cause mitochondrial DNA depletion syndrome, a fatal infantile genetic liver disease in humans. Loss of function in mice leads to glomerulosclerosis and sensineural deafness accompanied with mitochondrial DNA depletion. Mutations in the yeast homolog Sym1, and in the zebra fish homolog tra cause interesting, but not obviously related phenotypes, although the human gene can complement the yeast Sym1 mutation. The MPV17 protein is a hydrophobic membrane protein of 176 amino acids and unknown function. Initially localised in murine peroxisomes, it was later reported to be a mitochondrial inner membrane protein in humans and in yeast. To resolve this contradiction we tested two new mouse monoclonal antibodies directed against the human MPV17 protein in Western blots and immunohistochemistry on human U2OS cells. One of these monoclonal antibodies showed specific reactivity to a protein of 20 kD absent in MPV17 negative mouse cells. Immunofluorescence studies revealed colocalisation with peroxisomal, endosomal and lysosomal markers, but not with mitochondria. This data reveal a novel connection between a possible peroxisomal/endosomal/lysosomal function and mitochondrial DNA depletion.
We investigated graphene structures grafted with fullerenes. The size of the graphene sheets ranges from 6400 to 640,000 atoms. The fullerenes (C60 and C240) are placed on top of the graphene sheets, using different impact velocities we could distinguish three types of impact. Furthermore, we investigated the changes of the vibrational properties. The modified graphene planes show additional features in the vibronic density of states.
Low-frequency vibrational excitations in zeolite ZSM-5 and its partially crystalline derivatives
(2004)
Molecular dynamics investigation of vibrational properties of zeolite ZSM-5-based amorphous material
(2003)
Matrix metalloproteinases (MMPs) are matrix-degrading enzymes that are over-expressed in joints of rheumatoid arthritis (RA) patients. However, the contribution of specific MMPs for the development of arthritic joints is unknown. This study is aimed at studying the role of matrix metalloproteinase-9 (MMP-9) in mice, using the K/BxN serum-transfer model of RA. Arthritis was induced in Balb/c mice by injecting K/BxN serum. Development of arthritis was followed in these mice by measuring ankle thickness and clinical index score. MMP-9 expression in the joints of mice killed at various time points during the disease progression was determined by gelatin zymography using ankle lysates. We found that MMP-9 expression increased with the severity of arthritis. Importantly MMP-9 deficient mice injected with K/BxN serum showed a milder form of arthritis in comparison to the control C57BL/6 mice injected with K/BxN serum. We therefore conclude that MMP-9 promotes arthritis in mice.
In der vorliegenden Arbeit wird ein neuartiges Verfahren zur Echtzeitüberwachung von Laserbohrprozessen vorgestellt. Die Untersuchungen werden an unterschiedlichen Materialien unter Einsatz eines passiv-gütegeschalteten Nd:YAG Lasers durchgeführt. Prozessbegleitend findet eine Aufzeichnung der akustischen Emissionen mit anschließender Analyse durch schnelle Fourier-Transformation statt. Hierdurch lassen sich der Durchbruch beim Bohren durch ein Material sowie der Materialübergang mehrschichtiger Systeme detektieren. Die akustischen Messungen werden durchAuswertung der Pulsfolge des Lasers mittels einer Fotodiode gestützt. Hierbei zeigt sich eine gute Übereinstimmung der im akustischen Spektrum dominanten Frequenz mit der jeweils im Laserburstauftretenden Pulsfrequenz. Das vorgestellte Verfahren ermöglicht eine Echtzeitüberwachung beim Laserbohren mittels kostengünstiger und einfacher Hardware. Zudem zeichnet es sich im Gegensatz zu bestehenden Verfahren durch eine hohe Robustheit gegen äußere Störeinflüsse aus, da eine frequenzbasierte Auswertung stattfindet.
Unkonventionelle Spreng- und Brandvorrichtungen sind Bedrohungen in den weltweiten Konfliktherden und werden bei terroristischen Aktivitäten verwendet. Der Schutz von Menschen und Material erfordert daher effektive Gegenmaßnahmen. Dazu gehört auch die Anforderung an Sicherheitskräfte oder militärisches Personal, unbekannte Substanzfunde mit geringem zeitlichem und logistischem Aufwand vor Ort als gefährdend oder unkritisch einzustufen. Um Explosivstoffe von nicht-explosiven Materialien zu unterscheiden, kann die bei Explosivstoffen initiierbare, stark exotherme Reaktion genutzt werden. Diese resultiert in Strahlungsemissionen sowie in lokaler Druck- und Temperaturerhöhung. Die Messung dieser Reaktionseffekte und die Anforderung an eine mobile, einfach zu bedienende und robuste Analytik werden durch ein System ermöglicht, das Proben im einstelligen mg-Bereich durch schnelles Erhitzen auf mikrostrukturierten Heizern zum chemischen Umsatz anregt. Die emittierte Strahlung wird mit Photodioden im Bereich des sichtbaren und nah-infraroten Lichts aufgenommen, ein Sensor registriert die Druckerhöhung in einer geschlossenen Versuchskammer. In einem zweiten Aufbau werden die gasförmigen Reaktionsprodukte über ein Sensorarray von vier kommerziellen Gassensoren geleitet und die Signalantworten der Halbleitergassensoren mittels Hauptkomponentenanalyse ausgewertet. Die Ergebnisse zeigen, dass die schnelle thermische Aktivierung für die untersuchten primären Explosivstoffe, Treibladungspulver, sowie Trinitrotoluol (TNT) reproduzierbar erfolgt. Nicht-Explosivstoffe werden dabei im untersuchten Umfang sicher als unkritisch erkannt. Die Auswertung der Gassensorsignale liefert eine Unterscheidung von Nitrat- und Peroxid-basierten Sprengstoffen sowie von nicht-explosiven Substanzen.
Durch Dotierung eines nematischen Flüssigkristalles mit einer chiralen Substanz wird eine helikal strukturierte Phase induziert, die in der Lage ist, einfallendes Licht wellenlängenselektiv zu reflektieren. Bei der Reaktion des Dotiermittels mit einem gasförmigen Analyten verändern sich die Ganghöhe dieser Struktur und damit die reflektierte Wellenlänge. Liegt diese im Bereich des sichtbaren Lichts, ist eine Farbänderung mit dem menschlichen Auge zu beobachten. Es ist dabei sinnvoll den Flüssigkristall z.B. in einem Polymer einzukapseln, um ihn vor mechanischen Einflüssen und Umwelteinflüssen zu schützen. Eine Möglichkeit zur Einkapselung ist das koaxiale Elektrospinnen. Vorteile sind unter anderem die Realisierung einer großen Oberfläche und einer sehr geringen Wanddicke der schützenden Schale, die die Diffusion von Gasen durch die Wand hindurch ermöglicht. Um die Funktionsfähigkeit eines solchen Sensors zu testen, wurde ein CO2-sensitiver Flüssigkristall verwendet. Dieser wurde in eine Schale aus Polyvinylpyrrolidon (PVP) versponnen und die Reaktion mit CO2 spektroskopisch analysiert.
The analytical pyrolysis technique hyphenated to gas chromatography–mass spectrometry (GC–MS) has extended the range of possible tools for the characterization of synthetic polymers and copolymers. Pyrolysis involves thermal fragmentation of the analytical sample at temperatures of 500–1400 °C. In the presence of an inert gas, reproducible decomposition products characteristic for the original polymer or copolymer sample are formed. The pyrolysis products are chromatographically separated using a fused-silica capillary column and are subsequently identified by interpretation of the obtained mass spectra or by using mass spectra libraries. The analytical technique eliminates the need for pretreatment by performing analyses directly on the solid or liquid polymer sample. In this article, application examples of analytical pyrolysis hyphenated to GC–MS for the identification of different polymeric materials in the plastic and automotive industry, dentistry, and occupational safety are demonstrated. For the first time, results of identification of commercial light-curing dental filling material and a car wrapping foil by pyrolysis–GC–MS are presented.
The criteria for assessing the quality of rubber materials are the polymer or copolymer composition and the additives. These additives include plasticizers, extender oils, carbon black, inorganic fillers, antioxidants, heat and light stabilizers, processing aids, cross-linking agents, accelerators, retarders, adhesives, pigments, smoke and flame retardants, and others. Determination of additives in polymers or copolymers generally requires the extraction of these substances from the matrix as a first step, which can be challenging, and the subsequent analysis of the extracted additives by gas chromatography (GC), GC–mass spectrometry (MS), high performance liquid chromatography (HPLC), HPLC–MS, capillary electrophoresis, thin-layer chromatography, and other analytical techniques. In the present work, nitrile rubber materials were studied using direct analytical flash pyrolysis hyphenated to GC and electrospray ionization MS in both scan and selected ion monitoring modes to demonstrate that this technique is a good tool to identify the organic additives in nitrile rubber.
Asymmetric threats require powerful surveillance technology which helps to preserve the security. Security checks which focus on Improvised Explosive Devices (IED’s) or the identification of persons carrying hazardous substances are the major task of our research within the HAMLeT+ (Hazardous Material Localization and Person Tracking) project. Further on, there is a pressing need for assisting the security personnel, either civil or military, by extending the detection capabilities and to deliver efficient and reliable, real time decision support for their task to percept threats. Military camp protection with heterogeneous net-worked sensors and comprehensive sensor data fusion could be such an element. The technology developments concentrate on the integration of different sensor types (video, tracking sensors, CBRNE sensors) in order to get a better and comprehensive understanding in a defined entry area. Data fusion is used to combine kinematic data of persons (where, when) with additional attribute information of them (what) in order to identify that single person carrying the attributes and to classify the threat. The project was initiated as a Supporting Activity funded by the EU within the PASR 2006 scheme. With regards to the specific task for military camp protection it was extended and redesigned. In HAMLeT+ several chemical sensors for hydrocarbons like fuels, alcohols or solvents were used. Such chemicals are available in bigger amounts on the free market. Using them e.g. as fire accelerants they can cause a huge damage. Therefore their detection or the detection of persons carrying such substances or having contaminations on their clothes is of great interest. Sensitive devices for the detection of these analytes are e.g. metal oxide sensors [1]. Our presentation illustrates experimental data, which were gathered with the experimental system HAMLeT+ during the NATO “Defense Against Terrorism (DAT)” campaign „COMMON SHIELDS” in August and September 2008.
We introduce our Lessons Learned from the NATO CNAD PoW “Defense Against Terrorism (DAT)” campaign „COMMON SHIELD” from August and September 2008, present our data and illustrate our experience, which were gathered with the experimental system HAMLeT+ (Hazardous Material Localization and Person Tracking Plus) for military camp protection. The focus of „COMMON SHIELD” was the network-centric operation and demon-stration of innovative technologies for Intelligence, Surveillance, Reconnaissance and Target Acquisition of Terrorists (ISRTA). With regard to the specific task for military camp protection, the original demonstrator HAMLeT [1], which was initiated as a Supporting Activity funded by the EU within the PASR 2006 scheme, was extended and redesigned as HAMLeT+. In HAMLeT+ several chemical sensors for hydrocarbons like fuels, alcohols or solvents were used. The identification of persons carrying hazardous substances and the classification of those substances are the major task of our research. Further on, there is a pressing need for assistance systems for the guards, to extend the spectra of detection capabilities and to receive efficient and reliable, real time decision support for the task to percept threats, which so far could not even be realized at an entry control facility. Security assistance by means of heterogeneous net-worked sensors and comprehensive sensor data fusion could be such an element for better protection. New technological developments concentrate on the integration of different sensor types (video, tracking sensors, CRE sensors) in order to get a better and comprehensive understanding of potential threats in a defined area. Multiple sensors data fusion can be used to combine complementary types of data e.g. kinematic data of objects (where, when) with additional attribute information (what) in order to identify those objects carrying the attributes of interest and give a classification of the potential threat.
A method for the identification of polymeric residues in recycled aluminium by using analytical pyrolysis at 700°C hyphenated to gas chromatography-mass spectrometry (Py-GC/MS) was presented for the first time. The polymeric residues in recycled aluminium were identified as a mixture of polyethylene, polystyrene and phenolic resin. The described method could be useful for the aluminium industry as a part of the quality control of the recycled aluminium production.
Die analytische Pyrolyse ist ein universelles Analysenverfahren für hochmolekulare organische Verbindungen. Unter Pyrolyse (griech.: Pyros = Feuer, Lyso = zersetzen) versteht man die chemische Umsetzung von Substanzen mittels Wärme. Bei der Pyrolyse von hochmolekularen Substanzen handelt es sich um eine thermische Zersetzung unter kontrollierten Bedingungen in niedermolekulare Verbindungen. Die niedermolekularen Pyrolyseprodukte werden dann den herkömmlichen Analysenverfahren unterworfen, welche Rückschlüsse auf chemische Zusammensetzung, Struktur und Eigenschaften der Ausgangsstoffe erlauben.
Gas chromatography with flame-ionization detection (FID) and gas chromatography-mass spectrometry (GC/MS) with electron impact ionization (EI) and chemical ionization (PCI and NCI) were successfully used for separation and identification of commercially available longchain primary alkyl amines. The investigated compounds were used as corrosion inhibiting and antifouling agents in a water-steam circuit of energy systems in the power industry. Solidphase extraction (SPE) with octadecyl bonded silica (C18) sorbents followed by gas chromatography were used for quantification of the investigated Primene JM-T™ alkyl amines in boiler water, condensate and superheated steam samples from the power plant. Amine formulations from Kotamina group favor formation of protective layers on internal surfaces and keep them free from corrosion and scale. Alkyl amines contained in those formulations both render the environment alkaline and limit the corrosion impact of ionic and gaseous impurities by formation of protective layers. Moreover, alkyl amines limit scaling on heating surfaces of boilers and in turbine, ensuring failure-free operation. Application of alkyl amine formulation enhances heat exchange during boiling and condensation processes. Alkyl amines with branched structure are more thermally stable than linear alkyl amines, exhibit better adsorption and effectiveness of surface shielding. As a result, application of thermostable long-chain branched alkyl amines increases the efficiency of anti-corrosive protection. Moreover, the concentration of ammonia content in water and in steam was also considerably decreased.
This book chapter describes application examples of gas chromatography/mass spectrometry and pyrolysis – gas chromatography/mass spectrometry in failure analysis for the identification of chemical materials like mineral oils and nitrile rubber gaskets. Furthermore, failure cases demanding identification of polymers/copolymers in fouling on the compressor wall of a car air conditioner and identification of fouling on the surface of a bearing race from the automotive industry are demonstrated. The obtained analytical results were then used for troubleshooting and remedial action of the technological process.
Analytical pyrolysis technique hyphenated to gas chromatography/mass spectrometry (Py-GC/MS) has extended the range of possible tools for characterization of synthetic polymers/copolymers. Pyrolysis involves thermal fragmentation of the analytical sample at elevated temperature between 500 and 1400 °C. In the presence of an inert gas, reproducible decomposition products characteristic for the original polymer/copolymer sample are formed. The pyrolysis products are chromatographically separated by using a fused silica capillary column and subsequently identified by interpretation of the obtained mass spectra or by using mass spectra libraries. The analytical technique eliminate the need for pre-treatment by performing analyses directly on the solid or liquid polymer sample.
In this paper, application examples of the analytical pyrolysis hyphenated to gas chromatography/mass spectrometry for the identification of different polymeric materials in the plastic and automotive industry, dentistry and occupational safety are demonstrated. For the first time results of identification of commercially light-curing dental filling material and a car wrapping foil by pyrolysis-GC/MS are presented.
Ultra-fast photopolymerization of experimental composites: DEA and FT-NIRS measurement comparison
(2015)
We present herein a new class of resin formulations for stereolithography, named FlexSL, with a broad bandwidth of tunable mechanical properties. The novel polyether(meth)acrylate based material class has outstanding material characteristics in combination with the advantages of being a biocompatible (meth)acrylate based processing material. FlexSL shows very promising results in several initial biocompatibility tests. This emphasizes its non-toxic behavior in a biomedical environment, caused mainly by the (meth)acrylate based core components. A short overview of mechanical and processing properties will be given in the end. The herein presented novel FlexSL materials show a significant lower cytotoxicity in contrast to commercial applied acrylic stereolithography resins. Further biocompatibility tests according to ISO 10993 protocols are planned. On the one hand, there are technical applications for this material (e.g. flaps, tubes, hoses, cables, sealing parts, connectors and other technical rubber-like applications), and on the other hand, broad fields of potential biomedical applications in which the FlexSL materials can be beneficial are obvious. Especially these could be small series production of medical products with special flexible material requirements. In addition, the usage for individual soft hearing aid shells, intra-operative planning services and tools like intra-op cutting templates and sawing guides is very attractive. The possibility to modify the FlexSL resins also for high-resolution applications makes it possible to manufacture now very flexible micro-prototypes with outstanding material characteristics and very fine structures with a minimum resolution of 20 mym and a layer thickness of minimal 5 myrn. These resin formulations are applicable and adjustable to other stereolithographic equipment available on the market.
Background: Bile acids, end products of the pathway for cholesterol elimination, are required for dietary lipid and fatsoluble vitamin absorption and maintain the balance between cholesterol synthesis in the liver and cholesterol excretion. They are composed of a steroid structure and are primarily made in the liver by the oxidation of cholesterol. Cholesterol is also highly abundant in the human ovarian follicle, where it is used in the formation of the sex steroids.
Methodology/Principal Findings: Here we describe for the first time evidence that all aspects of the bile acid synthesis pathway are present in the human ovarian follicle, including the enzymes in both the classical and alternative pathways, the nuclear receptors known to regulate the pathway, and the end product bile acids. Furthermore, we provide functional evidence that bile acids are produced by the human follicular granulosa cells in response to cholesterol presence in the culture media.
Conclusions/Significance: These findings establish a novel pathway present in the human ovarian follicle that has the capacity to compete directly with sex steroid synthesis.
In this work, preceramic papers containing 85 wt% Al2O3 were heat-treated at 1600 °C to obtain paper-derived ceramics. In order to increase the preceramic paper density prior to sintering, the papers were calendered at different roll temperatures and pressures. The influences of the calendering parameters on the microstructure and mechanical properties of the preceramic papers and the paper-derived ceramics were investigated. It was expected that especially the mechanical properties of the papers and derived ceramics would be improved by calendering.
Lignin ist bereits ein intensives Gebiet der Forschung, allerdings werden Verknüpfungen zwischen Quelle, Aufschlussmethode und Einsatz in der Literatur kaum beschrieben. In der vorliegenden Arbeit werden Lignine von verschiedenen Quellen (Weizenstroh, Buche, Nadelholz) und Aufschlussmethoden (AFEX, Wasserdampfaufschluss, Organosolv, Saure Hydrolyse) analytisch erfasst und hinsichtlich ihres Einsatzes in polymeren Materialien charakterisiert. Eine breite Auswahl an Methoden wurden eingesetzt, FT-IR- Spektroskopie, UV-Vis, 31P-NMR, GPC, Pyrolyse-GC/MS, sowie HPLC zur Bestimmung der Reinheit gemäß des NREL-Standard-Protokolls. Thermische Analysen, wie TGA und DSC zeigten Glasübergangstemperaturen um 120°C, sowie Zersetzungstemperaturen zwischen 340°C und 380°C. Die Ergebnisse weisen für das Organosolv-Buchenholz-Lignin hochreine Fraktionen auf, die bis dato noch nicht erreicht wurden. Die Ergebnisse dieser Arbeit identifizien die Organosolv-Buchenholz-Lignine als ein verwertbares Produkt im Hinblick auf die Anwendung in Polyurethanen sowie Phenol-Formaldehydharzen.
In this doctoral thesis the curing process of visible light-curing (VLC) dental composites and 3D printing rapid prototyping (RP) materials are investigated with the focus on dielectric analysis (DEA). This method is able to monitor the curing of resins in an alternating electric fringe field with adjustable frequencies and is often used for cure control of composites manufacturing in the aviation and automotive industry but hardly established in dental science or RP method development. It is capable of investigating very fast initiation and primary curing processes using high frequencies in the kHz-range. The aim of the Thesis is a better understanding of the curing processes with respect to curing parameters such as resin composition, viscosity, temperature, and for light-curing composites also light intensity and irradiation depth. Due to the nature of both dental and RP systems an application of specific experimental set-up had to be designed allowing for the generation of reproducible and valid results. Subsequently, different evaluation methods were developed to characterize the curing behavior of both material types. A special focus was paid to the determination of kinetic parameters from DEA measurements. Reaction rates of the curing of the corresponding thermosets were calculated and applied to the ion viscosity curves measured by DEA to evaluate reaction kinetic parameters. For the dental composites it could be clearly shown that the initial curing rate is directly proportional to light intensity and not to its square root as proposed by many others authors. A good description of the curing behaviour of 3DP RP materials was also achieved assuming a reaction order smaller than one. This data provides the base for the kinetic modeling of polymerization and curing processes proposed within the Thesis.
Hox genes are an evolutionary highly conserved gene family. They determine the anterior-posterior body axis in bilateral organisms and influence the developmental fate of cells. Embryonic stem cells are usually devoid of any Hox gene expression, but these transcription factors are activated in varying spatial and temporal patterns defining the development of various body regions. In the adult body, Hox genes are among others responsible for driving the differentiation of tissue stem cells towards their respective lineages in order to repair and maintain the correct function of tissues and organs. Due to their involvement in the embryonic and adult body, they have been suggested to be useable for improving stem cell differentiations in vitro and in vivo. In many studies Hox genes have been found as driving factors in stem cell differentiation towards adipogenesis, in lineages involved in bone and joint formation, mainly chondrogenesis and osteogenesis, in cardiovascular lineages including endothelial and smooth muscle cell differentiations, and in neurogenesis. As life expectancy is rising, the demand for tissue reconstruction continues to increase. Stem cells have become an increasingly popular choice for creating therapies in regenerative medicine due to their self-renewal and differentiation potential. Especially mesenchymal stem cells are used more and more frequently due to their easy handling and accessibility, combined with a low tumorgenicity and little ethical concerns. This review therefore intends to summarize to date known correlations between natural Hox gene expression patterns in body tissues and during the differentiation of various stem cells towards their respective lineages with a major focus on mesenchymal stem cell differentiations. This overview shall help to understand the complex interactions of Hox genes and differentiation processes all over the body as well as in vitro for further improvement of stem cell treatments in future regenerative medicine approaches.
A major challenge modern society has to face is the increasing need for tissue regeneration due to degenerative diseases or tumors, but also accidents or warlike conflicts. There is great hope that stem cell-based therapies might improve current treatments of cardiovascular diseases, osteochondral defects or nerve injury due to the unique properties of stem cells such as their self-renewal and differentiation potential. Since embryonic stem cells raise severe ethical concerns and are prone to teratoma formation, adult stem cells are still in the focus of research. Emphasis is placed on cellular signaling within these cells and in between them for a better understanding of the complex processes regulating stem cell fate. One of the oldest signaling systems is based on nucleotides as ligands for purinergic receptors playing an important role in a huge variety of cellular processes such as proliferation, migration and differentiation. Besides their natural ligands, several artificial agonists and antagonists have been identified for P1 and P2 receptors and are already used as drugs. This review outlines purinergic receptor expression and signaling in stem cells metabolism. We will briefly describe current findings in embryonic and induced pluripotent stem cells as well as in cancer-, hematopoietic-, and neural crest-derived stem cells. The major focus will be placed on recent findings of purinergic signaling in mesenchymal stem cells addressed in in vitro and in vivo studies, since stem cell fate might be manipulated by this system guiding differentiation towards the desired lineage in the future.
Detection of triacetone triperoxide using temperature cycled metal-oxide semiconductor gas sensors
(2015)
This review is divided into two interconnected parts, namely a biological and a chemical one. The focus of the first part is on the biological background for constructing tissue-engineered vascular grafts to promote vascular healing. Various cell types, such as embryonic, mesenchymal and induced pluripotent stem cells, progenitor cells and endothelial- and smooth muscle cells will be discussed with respect to their specific markers. The in vitro and in vivo models and their potential to treat vascular diseases are also introduced. The chemical part focuses on strategies using either artificial or natural polymers for scaffold fabrication, including decellularized cardiovascular tissue. An overview will be given on scaffold fabrication including conventional methods and nanotechnologies. Special attention is given to 3D network formation via different chemical and physical cross-linking methods. In particular, electron beam treatment is introduced as a method to combine 3D network formation and surface modification. The review includes recently published scientific data and patents which have been registered within the last decade.