Introduction: Changes in eating habits and incorporation of physical activities remain to be the main methods in treating obesity. To set an adequate calorie intake, which would lead to weight loss, it is necessary to determine energy needs of an individual. For that energy intake and energy expenditure need to be determinate. However, energy expenditure is difficult to determine since it is contributed of three components. Basal, respectively resting metabolic rate (RMR), which is affected by a body composition, has the greatest influence on a total energy expenditure. Indirect calorimetry (IC) is considered to be a gold standard to determine RMR. When RMR is calculated by prediction equations instead, such as Harris-Benedict (H-B) equation, energy needs are overestimate or underestimate for people with abnormal body composition. Objectives: The aim of this study is to analyse data of RMR obtained using IC in connection to body composition. The main aim is to determine how fat free mas (FFM) and fat mass (FM) are affecting RMR in obese patients. There is also a comparation of RMR measured by the IC and RMR calculated using H-B equation as a part of this study, while IC is considered to be a reference method. Methods: Patients new to ambulance of obesitology at General University Hospital in Prague...

Adiabatic calorimetry provides accurate and precise specific heat (Cp) data. From this data, thermodynamic functions may be calculated. Cu2OCl2, melanothallite, became of interest as part of a study of a particular thermochemical cycle. The experimental specific heat data and the calculated thermodynamic functions are reported here. Free energies of formation, calculated from the thermodynamic functions, suggest the particular cycle of interest with this compound as an intermediate is not feasible; uncertainty as to the accuracy of CuO and CuCl2 data used in the calculations indicate further study may be necessary. Upon collection of the specific heat data, an antiferromagnetic transition was observed at 70 K; this led to examination of the magnetic heat capacity and entropy of the transition in melanothallite. The entropy of the transition was estimated to be 18.1 % and 7.5 % of 2Rln2 by two methods. A theoretical calculation using an Ising model produced a result of 39 %. This is consistently low when compared to the entropies of the antiferromagnetic transitions of CuO and CuCl2. This suggests geometric frustration. This thesis reports the thermodynamic functions calculated from the specific heat; the examination of the magnetic entropy; and repairs to an adiabatic apparatus involved in the collection of this data.

Aqueous electrolyte solutions at temperature and pressure conditions near the critical point of water are difficult to describe using traditional equations of state based upon the excess Gibbs energy. Models based upon the residual Helmholtz energy have proven more effective. Anderko and Pitzer1 developed a residual Helmholtz energy model (AP) for aqueous electrolyte solutions in which the electrolyte is assumed to be fully associated. The model has been effectively used in describing densities and vapor-liquid equilibria for simple electrolyte systems. The model is less effective for describing enthalpic properties such as heats of dilution. Oscarson and coworkers2, 3 modified the AP model for NaCl solutions by adding a term accounting for the change in Helmholtz energy as a result of aqueous dissociation reactions. This new model, called the RI model, is more accurate than the AP model at conditions where the NaCl dissociates more fully into ions. Liu et. al4, 5 modified the RI model by adding a term to describe interactions between ions in solution and by regressing new model parameter values. This new model, called the RIII model, is more accurate than both the AP model and the RI model and may be used to predict species concentrations in solution as a result of aqueous phase reactions. The RIII model has substantial thermodynamic inconsistencies, however, and is poorly suited for describing mixed solute solutions. This dissertation presents the RIV model which is an electrolyte solution model for solutions in the ranges of 350 °C to 400 °C and 18 MPa to 40 MPa. The RIV model has been applied to aqueous NaCl solutions and aqueous LiCl solutions. The RIV model is a modification of the AP model and includes aqueous phase reactions implicitly through fundamental species interactions. The RIV model is thermodynamically consistent. It is capable of describing densities and heats of dilution. Density predictions from the RIV model are less accurate than the AP model predictions (6.66 % error vs. 3.51 % error) but are reasonable. The heats of dilution predictions from the RIV model are much more accurate than those from the AP model (25.16 % error vs. 78.78 % error). Predictions of the ionic species concentration from the RIV model are likely to be poor as indicated by the poor agreement between experimental values and calculated values of equilibrium constants valid at infinite dilution. In order to provide the necessary data from which to regress the parameters of the RIV model, experimental heat of dilution values were determined using flow calorimetry techniques. These values are also reported in this dissertation.

The Academy of Nutrition and Dietetics has developed an evidence analysis library (EAL) for Nutrition and Dietetics professionals. The EAL is updated by members through workgroups consisting of experts in their fields, most often in response to unanswered questions. One such question is: what kinds of activities can be done during the rest period of an indirect calorimetry test in a healthy population? The objective of our study was to determine if listening to self-selected relaxing music or reading on an electronic device or a magazine effects resting energy expenditure (REE) as measured by an indirect calorimetry test in a healthy population. Answering this question would help indirect calorimetry test administrators know if these simple activities can be done during an indirect calorimetry test without significantly affecting REE but helping subjects remain awake. It would also help standardize the current protocol for indirect calorimetry administration. A randomized trial was conducted during an indirect calorimetry test, under three different conditions (resting, reading, listening to music). Six-five subjects (36 females and 29 males) were used in final data analysis. Inclusion criteria included healthy subjects between the ages of 18-50 years with a stable weight. Exclusion criteria included pregnant or lactating women or individuals who were taking medications known to affect metabolism. Reading, either a magazine or electronic device, resulted in a significant increase of 102.7 kcal/day when compared to resting (p<0.0001). There was no difference in REE when subjects read a magazine or on an electronic device. Listening to self-selected relaxing music increased REE by 27.6 kcal/day compared to rest (p=0.0072). Based on our results, we recommend subjects refrain from reading a magazine or electronic device during a test. Whether or not the smaller difference found while listening to music is practically significant would be a decision for the indirect calorimetry test administrators. Further research could be done to determine the effects other activities have on REE during an indirect calorimetry test. Such activities could include; watching television, texting, or playing passive game.

The dairy industry uses enzymes to make cheese, alter product flavor, and eliminate lactose. The activities of these enzymes have been measured in clear buffered solutions, but because of the limitations of spectrophotometric methods, enzyme activities have not been measured in opaque or colored dairy products where they are used. Isothermal titration calorimetry (ITC) can be used to determine reaction kinetics in opaque and colored solutions by measuring the heat rate from enzyme-catalyzed reactions as a function of time. This study used ITC to measure β-galactosidase activity in opaque solutions of milk, sweet whey, sweet whey permeate, acid whey, and acid whey permeate with two β-galactosidase (EC 3.2.1.23) isozymes derived from A. oryzae and K. lactis. The components of the dairy fluids alter the enzyme kinetics and reaction thermodynamics, and the reactions catalyzed by the two homologs differ as shown by differing thermodynamic profiles. The study demonstrates that ITC can be used to measure enzyme activity in opaque and colored dairy fluids and identify reactions by their thermodynamic properties. To ensure that ITCs are accurately recording heat data they must be calibrated regularly. However, potential problems have been identified with standard electrical calibration procedures; primarily being that the calibration is performed outside of the sample cell. This implies that any loss of heat from the theoretically adiabatic sample cell or loss of signal through led wires would be ignored by the electrical calibration. This research describes a new means for the chemical calibration of ITCs by performing acid-base titrations into the sample cell with KHP and TRIS base. This method for reaction was shown to be accurate to theoretical values across multiple temperatures and with different models of ITCs. Measurement errors due to diffusion of substrate are described along with means for limiting this factor. The method identified provides a procedure for maintaining the accuracy of ITCs by comparing their data to well-known thermodynamic values. It is anticipated that the simplicity and low-cost for running this calibration method will further standardize ITCs, help establish the ITC as a reliable method for measuring enzyme kinetics, and will make their maintenance simple enough for their use in quality assurance and industry settings.

Thermal and morphological studies of the segmented multiblock copolyesters containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol and dimethyl-1,4-cyclohexane dicarboxylate were carried out using differential scanning calorimetry, small angle X-ray scattering, wide angle X-ray diffraction and dynamic mechanical analysis. Molecular origins of the thermal transitions appearing in copolyesters were assigned by the copolyester analysis at different temperatures. The hard segments in copolyesters underwent short-range and long-range ordering (crystallization) during cooling or annealing above glass transition temperature, as concluded from thermal and wide angle X-ray diffraction analysis. Annealing process affected the ordering in hard segments and annealing temperatures of 160 °C and above led to increased microphase mixing. The small angle X-ray scattering studies confirmed the microphase separated morphology of copolyesters and supported the argument of increased microphase mixing in copolyesters annealed at higher temperatures. The amount of sulfonate containing co-monomer and its presence in either hard or soft microphase affected the morphology of the copolyesters. Introduction of the sulfonate groups led to increased microphase mixing in copolyesters as well as destruction of long-range order in the hard segments. / Master of Science

An isothermal calorimeter controlled by the Peltier effect has been designed and constructed in order to investigate reaction rates in solventwater mixtures. Because a thermal method was used a constant temperature environment was essential and this was achieved by using a water bath controlled to + 0.0010C. This callorinieter has been used to study the alkaline hydrolysis of methyl acetate in dimethylsulphoxide, and tetrahydrofuran - water mixtures at 15, 25 and 35 [degrees]C. The results of other investigations on similar reactions have been reviewed and an attempt has been made to correlate the electrostatic theories of Laidler and Eyring, and Amis and jaffe with these results. Finally, because it appears that specific solvent interactions play a major part in the reaction rates the role of water in the reaction mechanism has been examined. A mechanistic explanation has been proposed in order to correlate the rate of reaction with the composition of water-solvent mixtures which justifies the Laidler and Eyring treatment of solvent effects on ion-molecule reactions. / Bradford University

<p> The recrystallization behavior of three Al-Mg-Si-Cu alloys with varying iron and manganese additions was studied by differential power scanning calorimetry under nonisothermal annealing conditions. The influence of cold deformation on the precipitation sequence and its interaction with recrystallization was also investigated. The DSC experiments were complemented by hardness measurements and microstructural studies by optical and electron microscopy. The DSC signals, after optimization of the baseline, were used for the calculation of the kinetic parameters of the recrystallization process. Two different modeling approaches based on global JMAK kinetics were implemented. The first approach utilizes the classical isothermal JMAK expression directly, while the second approach introduces a path variable related to the thermal history of the material in the JMAK description. Model-independent estimates of the activation energy were also evaluated using the Flynn-Wall-Ozawa integral isoconversion method. </p> <p> The results show that the initial stages of recrystallization are not affected by the preceding precipitation processes and recrystallization always follows the precipitation of the Q' phase. However, during recrystallization enhanced coarsening of the Q' phase takes place leading to its transformation to the more stable Q phase. The Q phase exerts a Zener pinning pressures on the migrating boundaries preventing the formation of an equilibrium grain structure. Moreover, for high Fe and Mn additions, discontinuous precipitation of Mg2Si overlaps with the end of recrystallization and exerts an additional pinning pressure on the boundaries. Varying the Fe and Mn content significantly affects the recrystallization kinetics. PSN is promoted in alloys with the higher Fe and Mn content and the recrystallization temperature shifts to lower values. The modeling results show that the recrystallization process conforms to the classical JMAK type behavior. The course of the reaction was reproduced successfully by the path variable approach and the evaluated activation energies were in good agreement with the isoconversional model-independent estimates. However, when the classical JMAK expression was applied directly to non-isothermal measurements, a dependency of the recrystallization process on thermal history was observed. </p> / Thesis / Doctor of Philosophy (PhD)

Protein bars have become a popular option among consumers to increase protein content in their diets. Since there is a large market for protein bars, many factors must be considered when creating a protein bar that both satisfies consumers and has a long shelf-life. Hardening and textural changes in protein bars are some of the most common modes of shelf-life failure in this product category. When the typical product creation timeline from formulation to launch can be as short as 3-6 months and with added pressure from executives to quickly launch another new product afterwards, product development scientists simply do not have time to test the full shelf life of their product before release. For this reason, it is imperative that rapid methods for detecting bar hardness and predicting shelf life of bar formulations are developed. The objective of this research is to utilize calorimetric techniques to rapidly detect and identify bar hardening reactions. Six different protein bar formulations were studied, with each containing a combination of either whey protein isolate (WPI), milk protein isolate (MPI), or partially hydrolyzed whey protein isolate (HWPI), reducing-sugar, non-reducing sugar, and vegetable shortening. All bars were stored at 45°C and ambient humidity for 21 d. Isothermal microcalorimetry (IMC) was used to evaluate bar hardening-related reactions and was compared to objective and subjective hardness measurements. Hardness, color, water activity, moisture content, and sensory evaluation were measured at d 1, 7, 14, and 21. The results of this study indicate that isothermal calorimetry may be used to narrow down bar hardening reactions and points to Maillard browning as a main driver of hardening. These techniques may be used to predict bar shelf life, if Maillard browning is used as the basis for hardening. Furthermore, this research highlights the importance of ingredient selection during bar formulation to minimize hardening.

In systems biology, material balances, kinetic models, and thermodynamic boundary conditions are increasingly used for metabolic network analysis. It is remarkable that the reversibility of enzyme-catalyzed reactions and the influence of cytosolic conditions are often neglected in kinetic models. In fact, enzyme-catalyzed reactions in numerous metabolic pathways such as in glycolysis are often reversible, i.e., they only proceed until an equilibrium state is reached and not until the substrate is completely consumed. Here, we propose the use of irreversible thermodynamics to describe the kinetic approximation to the equilibrium state in a consistent way with very few adjustable parameters. Using a flux-force approach allowed describing the influence of cytosolic conditions on the kinetics by only one single parameter. The approach was applied to reaction steps 2 and 9 of glycolysis (i.e., the phosphoglucose isomerase reaction from glucose 6-phosphate to fructose 6-phosphate and the enolase-catalyzed reaction from 2-phosphoglycerate to phosphoenolpyruvate and water). The temperature dependence of the kinetic parameter fulfills the Arrhenius relation and the derived activation energies are plausible. All the data obtained in this work were measured efficiently and accurately by means of isothermal titration calorimetry (ITC). The combination of calorimetric monitoring with simple flux-force relations has the potential for adequate consideration of cytosolic conditions in a simple manner.