Preparation of thermoplastics composites using engineering thermoplastics and plant fibers or fillers is a technical challenge because the processing temperature of the thermoplastics is generally above the temperature of degradation of plant fibers of fillers. There have been numerous attempts for processing high melting point engineering thermoplastics like Nylon-6 with plant natural fibers and fillers. Low temperature processing methods, fiber modification or addition of additives which drops polymer melting point are some of proposed solutions for this problem. The objective of this thesis was to develop a formulation using wheat straw (WS) as a reinforcing fiber for Nylon-6. The concentration of WS was 15 wt-%. The thermoplastic composites were prepared by mixing grinded wheat straw and Nylon-6 using a laboratory scale twin-screw extruder; follow by preparation of samples using injection moulding. The strategy investigated in this thesis was utilization of additives to lower the melting point or to decrease the viscosity of Nylon-6. Lithium chloride salt (LiCl) and N-Butyl benzene Sulfon amide plasticizer (N-BBSA) were used as process additives to decrease melting point and to reduce the processing temperature and time. The addition of the wheat straw (15 wt-%) to the Nylon-6 increased modulus by 26.9 % but decreased the strength by 9.9 %. Effect of different level of these two additives on mechanical, thermal, physical properties and processability of the composite runs were studied. Addition of 4 wt-% LiCl was found to decrease the melting point from 222 °C to 191 °C, to increase modulus by 14 % in comparison to Nylon-6/wheat straw (15 wt-%). However, it decreased the processability and strength by 12.7 %. Plasticizer was investigated to easing processability and decreasing the degradation by reducing the residence time in the extruder, it does not affect the melting point of Nylon-6. The addition of 4 wt-% of plasticizer (N-BBSA) increased modulus and strength only by 2.6 % and 3 %, respectively, in comparison to Nylon-6/wheat straw (15 wt-%) composites. The results of mechanical properties were used as a benchmark for comparisons among samples with different formulations (levels of additives) to find out levels of LiCl and N-BBSA for the best mechanical properties. It was found that samples with 2 wt-% LiCl and 2 wt-% of N-BBSA had 29.3 % higher tensile modulus than neat Nylon-6, while its strength was almost same as neat Nylon-6 and 6.3 % higher than Nylon-6/WS (15 wt-%). These results were used to correlate the mechanical properties as a function of percentage of salt and plasticizer in the formulation. Differential scanning calorimetry (DSC) was used to evaluate the percentage of crystallinity and the melting point of the thermoplastic phase and thermal gravimetric analysis (TGA) was used to measure the thermal stability of different formulation. The kinetics of crystallization and degradation were evaluated using results from DSC and TGA, respectively. The activation energy for thermal degradation and the percentage of crystallinity of the thermoplastic composites were correlated to mechanical properties using linear regression. It was found that fiber degradation had a significant effect on strength but the effects of percentage of crystallinity on composites strength were insignificant. On the other hand, the percentage of crystallinity affects stiffness and impact strength. The ductility was a function of both crystallinity and thermal stability.

In der vorliegenden Arbeit wurden Untersuchungen zur mikrobiellen Aktivität von Pseudomonas putida DSM12735 durchgeführt. Als Messgröße diente die mikrobielle Wärmeleistung, basierend auf dem Stoffumsatz durch die Mikroorganismen. Ziel war es, die Vor- und Nachteile der verwendeten Kalorimeter herauszuarbeiten. Dafür wurden klassische Batch-Wachstumskurven aufgenommen. Ein weiteres Ziel bestand darin, eine Methode zur schnellen kalorimetrischen Detektion der mikrobiellen Aktivität insbesondere für die stationäre Phase zu entwickeln. In dieser Phase findet kein signifikanter Stoffumsatz statt. Durch das gezielte Auslösen einer zweiten Wachstumsphase und damit einem Stoffumsatz wird die mikrobielle Aktivität kalorimetrisch wieder messbar. Eingesetzt wurden folgende Kalorimeter: der Thermal Activity Monitor 2277 (TAM) mit den Kalorimetern Micro Reaction System 2250-4 ml und 2250-20 ml (kurz: TAM-4ml, TAM-20ml), das IC-Chip-Kalorimeter FCC22 (Institut für Physikalische Chemie, TU Freiberg) und das Kalorimeter Micro-DSC II (MDSC).

The complex interaction between cement and chemical/mineral admixtures in concrete mixtures sometimes leads to unpredictable concrete performance in the field which is generally defined as concrete incompatibilities. Cement paste rheology measurements instead of traditional workability tests (i.e., slump cone test) can have great potential in detecting those incompatibilities in concrete before the concrete is placed, which can, in turn, avoid related workability problems and setting time as well as heat evolution abnormalities. The objectives of the present study were to examine the applicability of the dynamic shear rheometer (DSR) to measure cement paste rheology, and to identify cement and mineral/chemical admixture incompatibilities, based on the determined rheological parameters. The DSR was modified and optimized for cement paste rheology measurements. Two different modes of operations (i.e., static and dynamic methods) with the modified DSR were investigated to measure representative rheological parameters as well as to identify cement and chemical/mineral admixture incompatibility. The conventional plastic viscosity and yield stress are measured in static mode and storage modulus curve, as a function of time, is measured in dynamic mode. The rate of change of plastic viscosity (RPV) as another static rheological parameter and the modeled magnitude parameter ?, from the dynamic rheological method, showed great potentialities as acceptance criteria to identify incompatible mixtures. The heat of hydration data from isothermal conduction calorimeter tests and setting time results for the studied mixtures have strongly supported the rheology based observations as supporting tools. Based on the main tests results, the acceptance criteria were set up using the rheological parameters in accordance with heat of hydration data. This will ultimately help material suppliers, concrete producers, and other users to detect problematic combinations of concrete ingredients before a given concrete mixture is placed.

Application of thermogravimetric analysis to the renewable energy sources is a novel study and it has been becoming attractive by the researchers in recent years. In this thesis, thermal and kinetic properties of biodiesel as new energy source, diesel and canola oil have been analyzed by using very popular thermogravimetric analysis methods which are / Differential Scanning Calorimetry (DSC) and Thermogravimetry (TGA/DTG). The main aim of the study is to observe the combustion and pyrolysis behaviour of methanol route biodiesel and diesel blends at different blending rates. Additionally, combustion and pyrolysis behaviour of canola oil, the origin of biodiesel have been analysed to observe the transesterification reaction effect on biodiesel. Therefore, biodiesel, diesel, canola oil and blends of diesel and biodiesel at different percentages are exposed to isothermal heating under nitrogen and air atmosphere with a constant heating rate of 5, 10 and 15

Durch Biotemplating mit bakteriellen Oberflächenproteinen, sogenannten S-Layer Proteinen können Metallcluster mit einer definierten Größe und Verteilung auf verschiedensten Oberflächen abgeschieden werden. Damit eröffnet sich die Möglichkeit der gezielten Präparation heterogener Katalysatoren. Mit der Kalorimetrie sollen die katalytischen Eigenschaften von mit Platin belegten S-Layer Präparationen am Beispiel der Kohlenmonoxidoxidation vorgestellt werden. Es werden geträgerte Katalysatoren und katalytisch aktive Schichten untersucht. Der Fokus liegt bei den Katalysatorschüttungen auf der Charakterisierung der katalytischen Eigenschaften und resultierend daraus auf einer Optimierung der Präparation. Für die Untersuchungen der katalytisch aktiven Schichten muss im Unterschied zu den Katalysatorschüttungen eine neuartige miniaturisierte Anordnung auf der Basis von Pt 1000 Widerstandsthermometern entwickelt werden. Dabei werden auch Parameter, die für eine spätere sensorische Applikation von Bedeutung sind, untersucht.

Die vorliegende Arbeit befasst sich mit experimentellen Untersuchungen zur physikalisch-chemischen und strukturellen Charakterisierung von neuartigen supramolekularen Kristalleinschlussverbindungen am Beispiel der Clathrate der Wirtverbindung 2,2’-bis(9-hydroxy-9-fluorenyl)biphenyl mit Aceton (polar) sowie Chloroform (unpolar). Durch die Kombination von Röntgenstrukturanalysen mit systematischen Messungen thermodynamischer Größen wie Löslichkeit, Einschluss-, Zersetzungs-, Lösungs- und Kristallisationsenthalpien konnten neue Erkenntnisse bezüglich der Struktur-Eigenschaftsbeziehungen sowie zur Rolle der Wirt-Gast Wechselwirkungen in den existierenden Einschlussverbindungen abgeleitet werden. Die Einschlussbildung bzw. Kristallisation verläuft für alle untersuchten Clathratphasen exotherm. Dies bedeutet, dass die Einschlussverbindungen gegenüber dem reinem Wirt energetisch stark begünstigt sind. Der bestimmende Beitrag hierfür resultiert aus der Bildung eines optimal gepackten Kristallgitters, während spezifische Wirt-Gast Wechselwirkungen nur eine untergeordnete Rolle spielen. Das Zersetzungsverhalten der verschiedenen Clathratphasen kann widerspruchsfrei aus der Packungsstruktur der Kristalle erklärt werden.

Heme-based gas sensor proteins have the ability to sense diatomic molecules such as O2 (FixL, EcDos or HemAT), CO (CooA, a CO-sensing protein of Rhodospirillum rubrum) and NO (guanylate cyclase) molecules and subsequently regulate numerous important biological processes in prokaryotic and eukaryotic organisms. The sensing function of these proteins is initiated by the binding of an effector (i.e., O2, CO, etc5) to the heme iron which then leads to a cascade of conformational events which gives rise to changes in kinase activity, DNA-binding activity, etc... In order to better understand the mechanism heme-based signaling, time resolved photothermal methods as well as transient optical techniques were utilized to obtain thermodynamic profiles for ligand binding/release in heme based signaling proteins including HemAT from Bacillus subtilis (aerotactic transducer), FixL from Sinorhizobium meliloti (regulation of the nitrogen fixation) and CooA from Rhodospirillum rubrum (transcriptional activator). In addition, a number of model systems were examined to understand the underlying thermodynamic processes involved in heme ligation. The variation of volume and enthalpy changes associated with spin state change of the iron from high-spin to low-spin where examined using the spin crossover Fe(III)(salten)(mepepy) complex. In addition, the experimental determination of the volume change due to electrostriction events were using Ru(II)(L)3 and the Debye-Hückel equation. Finally, different model heme proteins were studied to understand how a signal is conformationaly transmitted within a heme protein matrix. Sandbar shark hemoglobin was examined as an example of a non-signaling an allosteric protein. Two different peroxidases (horseradish and soybean) which have a direct channel between the heme pocket and the solvent involving no barrier energetic for the photodissociated ligand leaving the heme pocket were examined as example of non-signaling, non-allosteric proteins. The results show that each protein has a unique thermodynamic profile to conformationaly transmit signals subsequent to photodissociation of CO, even within the same class of protein (i.e. PAS domains, globins, etc...).

Simple gel formulations may be applied to enhance the systemic and local exposure of potential compounds. The aim of this thesis is the development and characterization of controlled release formulations based on thermo-reversible poloxamer gels, which are suitable for novel drug delivery applications.  In particular co-solvents (DMSO, ethanol), mucoadhesive polymers (chitosan, alginate) and salts (sodium tripolyphosphate, CaCl2) have been used to enhance the applications of poloxamer 407 (P407) formulations in preclinical animal studies. The impact of these additives on the micellization and gelation properties of P407 aqueous solutions was studied by calorimetric methods, nuclear magnetic resonance spectroscopy (NMR) and “tube inversion” experiments. The drug release behavior of hydrophobic and hydrophilic drugs was characterized by using a membrane/membrane-free experimental setup. Finally, preliminary pharmacokinetic studies using a mouse model were conducted for screening of selected inhibitors of bacterial type III secretion and for evaluation of different formulations including P407 gel. All additives, used here, reduced the CMTs (critical micelle temperature) of dilute P407 solutions, with the exception of ethanol. The gelation temperature of concentrated P407 solutions was lowered in the presence of CaCl2, DMSO, TPP and alginate. 1H MAS (Magic Angle Spinning) NMR studies revealed that DMSO influences the hydrophobicity of the PPO segment of P407 polymers. Low concentrations of DMSO did not show any major effect on the drug release from P407 gels and may be used to improve the exposure of lead compounds in poloxamer gels. A newly developed in situ ionotropic gelation of chitosan in combination with TPP in P407 gels showed an enhanced resistance to water and reduced the release rates of model drugs. From preliminary pharmacokinetic studies in mice it was revealed that poloxamer formulations resulted in an increased plasma half-life of the lead compound.

Preparation of thermoplastics composites using engineering thermoplastics and plant fibers or fillers is a technical challenge because the processing temperature of the thermoplastics is generally above the temperature of degradation of plant fibers of fillers. There have been numerous attempts for processing high melting point engineering thermoplastics like Nylon-6 with plant natural fibers and fillers. Low temperature processing methods, fiber modification or addition of additives which drops polymer melting point are some of proposed solutions for this problem. The objective of this thesis was to develop a formulation using wheat straw (WS) as a reinforcing fiber for Nylon-6. The concentration of WS was 15 wt-%. The thermoplastic composites were prepared by mixing grinded wheat straw and Nylon-6 using a laboratory scale twin-screw extruder; follow by preparation of samples using injection moulding. The strategy investigated in this thesis was utilization of additives to lower the melting point or to decrease the viscosity of Nylon-6. Lithium chloride salt (LiCl) and N-Butyl benzene Sulfon amide plasticizer (N-BBSA) were used as process additives to decrease melting point and to reduce the processing temperature and time. The addition of the wheat straw (15 wt-%) to the Nylon-6 increased modulus by 26.9 % but decreased the strength by 9.9 %. Effect of different level of these two additives on mechanical, thermal, physical properties and processability of the composite runs were studied. Addition of 4 wt-% LiCl was found to decrease the melting point from 222 °C to 191 °C, to increase modulus by 14 % in comparison to Nylon-6/wheat straw (15 wt-%). However, it decreased the processability and strength by 12.7 %. Plasticizer was investigated to easing processability and decreasing the degradation by reducing the residence time in the extruder, it does not affect the melting point of Nylon-6. The addition of 4 wt-% of plasticizer (N-BBSA) increased modulus and strength only by 2.6 % and 3 %, respectively, in comparison to Nylon-6/wheat straw (15 wt-%) composites. The results of mechanical properties were used as a benchmark for comparisons among samples with different formulations (levels of additives) to find out levels of LiCl and N-BBSA for the best mechanical properties. It was found that samples with 2 wt-% LiCl and 2 wt-% of N-BBSA had 29.3 % higher tensile modulus than neat Nylon-6, while its strength was almost same as neat Nylon-6 and 6.3 % higher than Nylon-6/WS (15 wt-%). These results were used to correlate the mechanical properties as a function of percentage of salt and plasticizer in the formulation. Differential scanning calorimetry (DSC) was used to evaluate the percentage of crystallinity and the melting point of the thermoplastic phase and thermal gravimetric analysis (TGA) was used to measure the thermal stability of different formulation. The kinetics of crystallization and degradation were evaluated using results from DSC and TGA, respectively. The activation energy for thermal degradation and the percentage of crystallinity of the thermoplastic composites were correlated to mechanical properties using linear regression. It was found that fiber degradation had a significant effect on strength but the effects of percentage of crystallinity on composites strength were insignificant. On the other hand, the percentage of crystallinity affects stiffness and impact strength. The ductility was a function of both crystallinity and thermal stability.

Ice structuring proteins (ISPs) naturally exist in many foods consumed as part of the human diet including plants or fish. ISPs from winter wheat grass have gained interest in the pharmaceutical and food industries as a non-toxic, natural and cost-effective product, which is easy to prepare as a crude extract. However, they have not been purified reproducibly and studied in detail to elucidate their structures, mechanism of actions and difference(s). ISPs from the apoplast region of cold acclimated winter wheat leaves were extracted through vacuum infiltration and purified using heat and ethanol precipitations, size exclusion and anionic exchange fast protein liquid chromatography techniques. The ISPs showed both significant inhibition of ice growth and thermal hysteresis activities. The non-acclimated apoplastic extracts from winter wheat leaves contained similar proteins without any abovementioned activities. The ISPs contained disulfide bridges, similar to thaumatin-like proteins (TLPs) and partially similar to ISPs from winter rye leaves and carrot. ISPs remained active after thermal treatment (i.e., pasteurization conditions) and over a wide range of pH (3-12). There are very few quantitative assays to measure the activity of antifreeze proteins (AFPs, or Ice Structuring Proteins, ISPs), which often suffer from various inaccuracies and inconsistencies. Some methods rely only on unassisted visual assessment. When microscopy is used to measure ice crystal size, it is critical that standardized procedures be adopted, especially when image analysis software is used to quantify sizes. Differential Scanning Calorimetry (DSC) has been used to measure the thermal hysteresis activity (TH) of AFPs. In this study, DSC was used isothermally to measure enthalpic changes associated with structural rearrangements as a function of time. Differences in slopes of thermograms between winter wheat ISP or AFP type I containing samples, and those without ISP or AFP type I were demonstrated. ISP or AFP type I containing samples had much higher slopes compared to those without ISP or AFP type I. Samples with higher concentration of ISP or AFP type I showed higher slope values. The proteinaceous activity of ISPs or AFP type I was confirmed by demonstrating changes in samples with and without proteases. A proposed mechanism of this method is discussed.