Introduction: A growing worldwide pandemic exists today that has large implications for the future of healthcare among the nations. Obesity is a growing disease that has multiple implications for morbidity and mortality including cardiovascular disease, stroke and diabetes. The obese and overweight population plagues nearly 46% of the world's population, and likely is preventable. We wanted to examine what role metabolic testing could play in prevention. Methods: A cross-sectional study composed of a 52-question Likert-based scale survey was constructed and distributed to healthcare providers. We hypothesized that there would be a generally accepted interest in establishing routine metabolic rate testing as a standard of care in primary care offices, much like that of colon cancer, breast cancer and hypertension screening. Seven individual study questions were derived from the primary study question to examine whether differences exist in the chosen demographics of age, occupation, fiscal policy and education. The dataset was first summarized descriptively and then for subgroup analysis the Wilcoxon Rank-Sum and the Kruskal-Wallis tests were used to determine data characteristics. Results: We broke the primary study question into a dichotomous outcome and when analyzed, showed that 100% of our sampling population was in favor of the implementation of routine metabolic rate testing. Subgroups were analyzed for differences within the demographic groupings using non-parametric statistical testing. Only six out of twenty-eight evaluations were considered significant which indicated that within that demographic grouping, there was statistical difference between the means of the variables evaluated. Age and occupation were the only demographics analyzed that contributed to some statistical significance in this study. Conclusion: While we cannot make any definitive conclusions about our subgroup analysis, we can state that overall, there is a general tendency for healthcare providers to express interest in establishing routine metabolic testing. Given the novelty of this concept, further studies will be needed to establish frequency, cost vs benefit analysis, healthcare status changes and implementation processes.

Uncoated defects in hot dip metal-coated steel products result from non-wetting of the steel surface by the molten alloy. The occurrence of uncoated defects is highly detrimental to product quality and production efficiency; uncoated defects compromise the appearance and anti-corrosion performance of hot dip metal-coated steel products and causes time delays in the application of subsequent surface treatments. Although many studies have been directed towards evaluating the effect of steel pre-heat temperature and oxidation on the formation of uncoated defects, fewer investigations have analysed how oil-derived residues remaining on steel surface following the cold rolling and furnace cleaning processes impact upon hot dip metallic coating quality. Furthermore, although a considerable amount of research has focussed on the process of deposit formation in lubricants used in other applications, the composition of oily residues remaining after the continuous annealing process, and the origins of these residues in the original rolling oil formulation, are poorly understood. The primary focus of the present work has been to gain an improved understanding of relationships between cold rolling oil composition, oil residue-formation characteristics and the occurrence of uncoated defects in 55Al-43.4Zn-1.6Si hot dip metallic coatings. Several key classes of rolling oil ingredients which decompose to leave high levels of thermally-stable residue have been identified. The thermal decomposition processes undergone by a variety ingredients within these classes have been studied under both oxidising and reducing conditions using Thermogravimetric Analysis (TGA) and Pressure Differential Scanning Calorimetry (PDSC) techniques, with chemical characterisation of the decomposition process and the resultant thermally-stable residue by infrared spectroscopy. Model blends of each ingredient in a typical cold rolling oil base ester have also been evaluated by TGA and PDSC to identify the impact of ingredient concentration and chemical structure on the amount of oily residue formed. The results of these investigations have been related to the impact of the ingredients on 55Al-43.4Zn-1.6Si hot dip metallic coating quality through the performance of industrial-scale hot dipping trials and hot dip simulation studies. In order to translate these results into a context more closely aligned with industrial conditions, the effect of processing variables, including furnace atmosphere and the availability/concentration of iron in contact with the rolling oil at the steel surface, on the decomposition process of a fully-formulated commercial cold rolling oil has also been investigated. The information gained can potentially be used to tailor operating conditions within the cold rolling/continuous hot dip metallic coating processes to enhance steel surface cleanliness. Finally, the deposit-forming tendencies of an array of different commercial cold rolling oils have been evaluated, leading to the development of a thermal analysis-based test for screening cold rolling oils with respect to their likely impact upon 55Al-43.4Zn-1.6Si hot dip metallic coating quality. This test, together with the understanding obtained on the effect of different rolling oil ingredients on hot dip metallic coating quality, can be used within the industry to formulate improved cold rolling oils.

La Supersymetrie est la theorie qui semble etre l'extension la plus naturelle du Modele Standard. Dans cette these nous presentons la recherche du sTop, hypothethique partenaire scalaire du quark Top, que nous avons effectuee dans le cadre du Modele Standard Supersymetrique Minimal (MSSM) en utilisant les donnees de l'experience DO prises lors de la Phase I du Tevatron, qui correspondent a une luminosite integree de $108$ pb$^{-1}$. Nous avons selectionne les evenements avec un electron, un muon et de l'energie transverse manquante dans l'etat final, qui peuvent etre le produit de desintegration d'une paire de sTops en 3 corps ($\tilde{t} \rightarrow b l \tilde{\nu}$), ou en 4 corps ($\tilde{t} \rightarrow b \oa l {\nu_l}$). En l'absence d'evenements candidats a ce signal, les resultats sont interpretes en terme de limites de section efficace de production du sTop et de regions d'exclusion dans l'espace des parametres ($m_{\tilde{t}},\moa$) ou ($m_{\tilde{t}},\msnu$). L'utilisation inedite au Tevatron de cet etat final pour la recherche du sTop nous a permis d'etablir des contraintes plus fortes que celles obtenues precedemment au LEP ou au Tevatron dans le canal $\tilde{t} \rightarrow b l \tilde{\nu}$, et les premieres limites jamais etablies dans le canal de desintegration a quatre corps. Pour le canal a 3 corps, en supposant que le sneutrino soit la particule supersymetrique la plus legere (LSP), la region exclue a $95\%$ de degre de confiance s'etend jusqu'a une masse de sTop de $142$ ($130$) GeV si la masse du sneutrino ($\msnu$) est de $43$ ($86$) GeV. Si le canal a 4 corps domine, et en supposant que le neutralino soit la LSP, les limites dependent de la masse du sneutrino. Si celle-ci est suffisamment legere (${m_{\tilde{\nu}}} \ \lapprox \ 100$ GeV) cette limite atteint une masse de sTop de $132$ GeV pour un neutralino de $60$ GeV. Pour ces recherches, la calorimetrie joue un role central d'un point de vue experimental. L'augmentation de la luminosite attendue dans la Phase II du Tevatron qui a demarre le $1^{er}$ Mars $2001$, et l'amelioration du detecteur qui a ete realisee ces trois dernieres annees permettront d'etendre ces domaines d'exclusion ou de decouvrir le sTop. Nous decrivons donc egalement dans cette these notre contribution a l'amelioration de la calorimetrie, tant sur la calibration electronique du calorimetre a Argon liquide du detecteur DO, que sur les logiciels de reconstruction de l'energie calorimetrique.

Calorimetry is one of the main techniques of thermal analysis. Most of physical or chemical modifications of material are associated with thermal effects whereby heat is absorbed (i.e., melting) or released (i.e., thermal decomposition). Typically, calorimetric experiments are performed with Differential Scanning Calorimetry (DSC), which measures the heat flux absorbed or released by the sample following the same temperature program as a reference material. In these experiments, measurements are typically carried out on a few milligrams of sample. However, for many applications one has to handle nanograms or even picograms of sample. One of such applications is relevant to studies of materials which can release a significant amount of energy during their decomposition (energetic materials). Calorimetry able to handle nanograms of sample could find potential applications in the field of explosives detection. Nanocalorimetry allows to heat small amounts of sample (a few nanograms to a few hundred picograms) at extreme heating rates, i.e. up to one million °C/s. The temperature increase can initiate several phenomena in energetic materials, therefore the calorimetry could be an appropriate technique to characterize and to detect energetic materials. The energetic materials used in this study are nitrocellulose (NC), hexogen (RDX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-ltexaazaisowurtzitane (CL-20) and penthrite (PETN). The manuscript presents our results on the nanocalorimeter calibration, on the thermal behaviour of the explosives studied with nanocalorimetry and also includes an evaluation of nanocalorimetry as a tool for explosives detection.

Nature has always served as a model for mimicking and inspiration to humans in their efforts to improve their life. Researchers have been inspired by nature to produce biomimetic materials with molecular recognition properties by design rather than evolution. Molecular imprinting is one way to prepare such materials. Such smart materials with new functionalities are at the forefront of the development of a relevant number of ongoing and perspective applications ranging from consumer to space industry. Molecularly imprinted polymers were developed by mimicking the natural enzymes or antibodies that serve as host for binding target molecules. These imprints were used as a recognition element to substitute natural biomolecules in biosensors. The concept behind molecular imprinting is to mold a material (with the desired chemical properties) around individual molecules. Upon removal of the molecular templates, one is left with regions in the molded material that fit the shape of the template molecules. Thus, molecular imprinting results in materials that can selectively bind to molecules of interest. Imprinted materials resulted in applications ranging from chemical separation to bioanalytics. In this work attempts were made particularly in the development of molecularly imprinted polymer based thermometric sensors. The main effort was focused towards the development of an covalently imprinted polymer that would be able to selectively bind fructosyl valine (Fru-Val), the N-terminal constituent of hemoglobin A1c ß-chains. Taking into account the known advantages of imprinted polymers, e.g. robustness, thermal and chemical stability, imprinted materials were successfully used as a recognition element in the sensor. One of the serious problems associated with the development of MIP sensors and which lies in the absence of a generic procedure for the transformation of the polymer-template binding event into a detectable signal has been addressed by developing the "thermometric" approach. In general the developed approach gives a new insight on MIP/Analyte interactions. / In dem Bestreben, ihr eigenes Leben zu verbessern, haben die Menschen stets die Natur nachgeahmt und sich von ihr inspirieren lassen. Die Natur hat Forscher zur Erzeugung smarter biomimetischer Stoffe mit molekularen Erkennungseigenschaften nach dem Vorbild der Evolution inspiriert. Eine der Methoden zur Herstellung solcher Substanzen ist das molekulare Prägen. Smarte Materialien mit neuen Eigenschaften stehen an der Spitze der Entwicklung potentieller Anwendungen vom Verbraucher bis hin zur Raumfahrtindustrie. Durch Nachahmung von natürlichen Enzymen oder Antikörpern wurden molekular geprägte Polymere (MIPs) entwickelt, die der Bindung von Zielmolekülen dienen. Diese geprägten Polymere (imprints) wurden anstelle von Biomolekülen als Erkennungselemente in Biosensoren eingesetzt. Das Konzept, das dem molekularen Prägen zugrunde liegt, besteht in der Formung eines Polymers (mit den entsprechenden chemischen Eigenschaften) um einzelne Zielmoleküle herum. Nach Entfernen dieser molekularen Template bleiben Abdrücke im Polymer übrig, die der Form der Templatmoleküle entsprechen. Mit Hilfe des molekularen Prägens kann man also Stoffe herstellen, die sich selektiv an bestimmte Moleküle binden können. Geprägte Polymere finden breite Anwendung, etwa in chemischen Aufreinigungsprozessen und der Bioanalytik. Hauptanliegen der vorliegenden Arbeit war es, thermometrische Sensoren auf der Basis molekular geprägter Polymere zu entwickeln. Die Anstrengungen richteten sich vor allem auf die Entwicklung eines kovalent geprägten Polymers, das in der Lage ist, selektiv Fruktosyl-Valin (Fru-Val), den N-terminalen Bereich von Hämoglobin A1c, zu binden. Aufgrund der bekannten Vorzüge geprägter Polymere – z. B. Robustheit und thermische und chemische Stabilität – wurden geprägte Polymere erfolgreich als Erkennungselement im Sensor angewendet. Eine der größten Herausforderungen bei der Entwicklung von MIP-Sensoren, das Fehlen eines generischen Verfahrens zur Umwandlung der Bindungsreaktion in ein nachweisbares Signal, wurde mit der Entwicklung der thermometrischen Methode in Angriff genommen. Diese Methode führt allgemein zu neuen Einsichten in die Interaktionen zwischen MIP und Analyt.

In the present work, the thermodynamic activites of ironoxide, denoted as "FeO" in the slag systems Al2O3-"FeO", CaO-"FeO", "FeO"-SiO2, Al2O3-"FeO"-SiO2, CaO-"FeO"-SiO2and "FeO"-MgO-SiO2were investigated by employing the gasequilibration technique at steelmaking temperatures. Thestrategy was to expose the molten slag mixtures kept inplatinum crucibles for an oxygen potential, determined by aCO/CO2-ratio. A part of the iron reduced from the "FeO"in the slag phase was dissolved into the Pt crucible. In order to obtain the activites of "FeO", chemical analysisof the quenched slag samples together with thermodynamicinformation of the binary metallic system Fe-Pt is required.Careful experimental work was carried out by employing asolid-state galvanic cell technique as well as calorimetricmeasurements in the temperature ranges of 1073-1273 K and300-1988 K respectively. The outcome of these experiments wasincorporated along with previous studies into a CALPHAD-type ofthermodynamic assessment performed with the Thermo-Calc™software. The proposed equilibrium diagram enabledextrapolation to higher temperatures. The experimentally obtained activites of "FeO" in thepresent work, along with earlier investigations were assessedwith the KTH slag model, THERMOSLAG©. New binaryparameters were evolved and incorporated in THERMOSLAG©.The present model calculations are compared with othercommercially available software such as F*A*C*T™andThermo-Calc™. The validity of the modified model wasinvestigated by measurements carried out in case of Al2O3-"FeO"-SiO2, CaO-"FeO"-SiO2and "FeO"-MgO-SiO2ternary slags. The potential of the model tocompute the activities in the case of multicomponent slags wasdemonstrated. A correlation between the activity of a metallic oxide in aternary slag system and the sulphide capacity of the slag wasinvestigated by using the solubility of sulphur in the binarysystems CaO-SiO2and Al2O3-CaO along with the sulphide capacity of the Al2O3-CaO-SiO2system. The estimated values of the activitieswere found to be in good agreement with the measured values.This correlation also gives the possibility to elucidate theapplicability of Henry's law to the activity of a metallicsulphide and to determine the order in the affinity of a cationto sulphur between two metallic oxides in a slag. Model calculations were performed with THERMOSLAG©, by using plant data from the ladle refiningprocess at OVAKO Steel, Hofors, Sweden. It was found thatoxygen estimations in the metal from the "FeO" analyses ofslags, obtained by conventional sampling and analysis methodwere less reliable. Reliable estimation of the oxygen levelsutilising the sulphur partition between the slag and the metalwere carried out using THERMOSLAG© software. <b>Keywords:</b>Thermodynamics, Activity, Galvanic cell,Calorimetry, Gas equilibration technique, Iron-platinum alloys,FeO, Slags, Modelling, Ladle

MosA is a protein found in <i>Sinorhizobium meliloti</i> L5-30 and has been suggested to be responsible for the biosynthesis of the rhizopine 3-O-methyl-scyllo-inosamine (3-MSI) from scyllo-inosamine (SI). However, we have shown MosA is a dihydrodipicolinate synthase (DHDPS) catalyzing the condensation of pyruvate with aspartate-β-semialdehyde (ASA). Since the DHDPS reaction occurs through a Schiff base aldol-type mechanism it was proposed that MosA could be an O-methyltransferase utilizing 2-oxo-butyrate (2-OB) as a novel methyl donor. This interesting yet unlikely possibility would explain MosA's role in the biosynthesis of 3-MSI without ignoring its similarity to DHDPS. Alternatively, MosA may have two catalytic domains one of which possesses a novel binding motif for S-Adenosyl methionine (SAM) to account for methyltransfer activity. In vitro demonstration of MosAs methyltransferase activity is required to resolve this apparent contradiction.<p>This dissertation describes the chemical synthesis of the rhizopines, investigation into whether MosA has a direct role in rhizopine biosynthesis and the thermodynamic characterization of compounds interacting with MosA as observed by isothermal titration calorimetry. <p>Initial investigation into MosAs methyltransferase activity began with 2-OBs interaction with the enzyme. Inhibition experiments determined 2-OB is a competitive inhibitor with respect to pyruvate of the DHDPS reaction of MosA. Furthermore, protein mass spectrometry of MosA in the presence of 2-OB and sodium borohydride indicated that a Schiff base enzyme intermediate was indeed being formed providing evidence that the proposed mechanism may exist. However, neither of the rhizopines had any effect on the DHDPS activity and HPLC assays determined that no 3-MSI was being produced by MosA in the presence of SI and 2-OB. Furthermore, HPLC assays failed to detect methyl transfer activity by MosA utilizing the SAM as a methyl donor. <p>Isothermal titration calorimetry provided thermodynamic characterization of the pyruvate and 2-OB Schiff base intermediates formed with MosA. In addition, ITC provided insight into the nature and thermodynamics of (S)-lysines inhibition of MosA. ITC failed to detect any interactions between the rhizopines or SAM with MosA. These results indicate that MosA is only a DHDPS and does not catalyze the formation of 3-MSI from SI as hypothesized in the literature.

A primary purpose of the present work was to develop an experimental technique using Differential Scanning Calorimetry (DSC) capable of elucidating phase formation during sintering of a 50 atomic percent Ni and 50 atomic percent Ti powder compact in order to increase the understanding of the sintering mechanisms that take place during solid state and reactive sintering. Using a variety of Nickel and Titanium powder sizes, effects due to powder size, peak temperature and hold time were studied in situ using DSC, which allowed for a number of qualitative and quantitative relationships to be developed. In studying the eutectoid decomposition of β-Ti using DSC, a simple model was developed (Eq. 4-7) to relate the measured enthalpy of this reaction to the area fraction observed microstructurally. This allowed for the determination of the standard enthalpy for the β-Ti eutectoid decomposition, which was found to be ΔHf = 64.8 J/g. This value, coupled with the measured eutectoid enthalpy, allowed for the determination of the weight fraction of β-Ti present as a function of hold time at 900°C. It was found that the β-Ti removal followed a two-stage parabolic decay. The rate constant for stage I was found to be kI = -0.0347 fβ/(mins)^1/2 and that for stage II, kII = - 0.0123 fβ/(mins)^1/2. A relationship between the enthalpy observed for the combustion reaction versus the fraction of β-Ti present at the time of combustion was also developed (Eq. 4-15). This represents the first published evidence that combustion actually depends on the β-Ti content, which in turn precipitates a melting event significant enough to initiate combustion.

A primary purpose of the present work was to develop an experimental technique using Differential Scanning Calorimetry (DSC) capable of elucidating phase formation during sintering of a 50 atomic percent Ni and 50 atomic percent Ti powder compact in order to increase the understanding of the sintering mechanisms that take place during solid state and reactive sintering. Using a variety of Nickel and Titanium powder sizes, effects due to powder size, peak temperature and hold time were studied in situ using DSC, which allowed for a number of qualitative and quantitative relationships to be developed. In studying the eutectoid decomposition of β-Ti using DSC, a simple model was developed (Eq. 4-7) to relate the measured enthalpy of this reaction to the area fraction observed microstructurally. This allowed for the determination of the standard enthalpy for the β-Ti eutectoid decomposition, which was found to be ΔHf = 64.8 J/g. This value, coupled with the measured eutectoid enthalpy, allowed for the determination of the weight fraction of β-Ti present as a function of hold time at 900°C. It was found that the β-Ti removal followed a two-stage parabolic decay. The rate constant for stage I was found to be kI = -0.0347 fβ/(mins)^1/2 and that for stage II, kII = - 0.0123 fβ/(mins)^1/2. A relationship between the enthalpy observed for the combustion reaction versus the fraction of β-Ti present at the time of combustion was also developed (Eq. 4-15). This represents the first published evidence that combustion actually depends on the β-Ti content, which in turn precipitates a melting event significant enough to initiate combustion.

MosA is a protein found in <i>Sinorhizobium meliloti</i> L5-30 and has been suggested to be responsible for the biosynthesis of the rhizopine 3-O-methyl-scyllo-inosamine (3-MSI) from scyllo-inosamine (SI). However, we have shown MosA is a dihydrodipicolinate synthase (DHDPS) catalyzing the condensation of pyruvate with aspartate-β-semialdehyde (ASA). Since the DHDPS reaction occurs through a Schiff base aldol-type mechanism it was proposed that MosA could be an O-methyltransferase utilizing 2-oxo-butyrate (2-OB) as a novel methyl donor. This interesting yet unlikely possibility would explain MosA's role in the biosynthesis of 3-MSI without ignoring its similarity to DHDPS. Alternatively, MosA may have two catalytic domains one of which possesses a novel binding motif for S-Adenosyl methionine (SAM) to account for methyltransfer activity. In vitro demonstration of MosAs methyltransferase activity is required to resolve this apparent contradiction.<p>This dissertation describes the chemical synthesis of the rhizopines, investigation into whether MosA has a direct role in rhizopine biosynthesis and the thermodynamic characterization of compounds interacting with MosA as observed by isothermal titration calorimetry. <p>Initial investigation into MosAs methyltransferase activity began with 2-OBs interaction with the enzyme. Inhibition experiments determined 2-OB is a competitive inhibitor with respect to pyruvate of the DHDPS reaction of MosA. Furthermore, protein mass spectrometry of MosA in the presence of 2-OB and sodium borohydride indicated that a Schiff base enzyme intermediate was indeed being formed providing evidence that the proposed mechanism may exist. However, neither of the rhizopines had any effect on the DHDPS activity and HPLC assays determined that no 3-MSI was being produced by MosA in the presence of SI and 2-OB. Furthermore, HPLC assays failed to detect methyl transfer activity by MosA utilizing the SAM as a methyl donor. <p>Isothermal titration calorimetry provided thermodynamic characterization of the pyruvate and 2-OB Schiff base intermediates formed with MosA. In addition, ITC provided insight into the nature and thermodynamics of (S)-lysines inhibition of MosA. ITC failed to detect any interactions between the rhizopines or SAM with MosA. These results indicate that MosA is only a DHDPS and does not catalyze the formation of 3-MSI from SI as hypothesized in the literature.