The main objective of the study was to determine the effects of enzymes on quality of breads baked in halogen lamp-microwave combination, microwave and conventional oven. It was also aimed to determine the optimum processing conditions in these ovens. In the first part of the study, as independent variables, baking time, baking temperature for conventional oven / microwave power for microwave oven and microwave power and halogen power for combination oven was used. Weight loss, specific volume, firmness and color of the breads were measured during the study. The optimum baking conditions were determined as 13 min at 200&deg / C in conventional oven, 0.75 min at 100% power in microwave oven, 10 min at 60% power in halogen lamp oven, and 3 min at 30% microwave power and 70% halogen lamp power in halogen lamp-microwave combination oven. In the case of combination oven, specific volume and color values of breads were comparable with the conventionally baked breads but weight loss and firmness of them were still higher. The effects of different enzymes (&amp / #945 / -amylase, xylanase, lipase &amp / protease) were studied to reduce the quality problems of breads baked in microwave and halogen lamp-microwave combination oven. The optimum baking conditions determined for each type of oven in the first part of the study were used in the investigation of the functions of enzymes on bread quality during baking and staling. As a control, no enzyme added breads baked at 200&deg / C for 13 min in conventional oven were used. All the enzymes were found to be effective in reducing initial firmness and increasing specific volume of breads baked in microwave and halogen lamp-microwave combination ovens. However, in conventional baking, the effects of enzymes on crumb firmness were seen mostly during storage. The usage of enzyme protease in the bread formulation resulted in breads with higher volume and darker color in all of the ovens. All of the enzymes were found to be effective to retard the staling of breads baked in conventional, microwave and halogen lamp-microwave combination ovens.

Halogen bonding (XB), the interaction between electron deficient halogen compounds and electron donors, is an established non-covalent interaction in the solid and gaseous phases. Understanding of XB in the solution phase is limited. This thesis describes experimental studies of XB interactions in solution, and the application of XB interactions in anion recognition. Chapter 1 is a brief review of current understanding of XB interaction: theoretical models, studies of XB in solid and gaseous phases and examples in biological systems are discussed. At the end of this chapter, halogen bonding in the solution phase is discussed, along with applications of halogen bonding in organic syntheses. In chapter 2, linear free energy relationships involving the thermodynamics of halogen bonding of substituted iodoaromatics are studied. The utility of substituent constants and calculated molecular electrostatic potential values as metrics of halogen bond donor ability are discussed. Density Functional Theory (DFT) calculations are shown to have useful predictive values for trends in halogen bond strength for a range of donor-acceptor pairs. Chapter 3 describes the development of new multidentate anion receptors based on halogen bonding. Bidentate and tridentate receptors were found to exhibit significantly higher binding constants than simple monodentate donors. These receptors show selectivity for halide anions over oxyanions. Using 19F NMR spectra at different temperature, the enthalpies and entropies of anion bindings for monodentate and tridentate receptors were determined. The results indicate a positive entropy contribution to anion binding for both mono and tridentate receptors in acetone solvent. Finally in chapter 4, some mesitylene based receptors with 3-halopyridinium and 2-iodobenzimidazolium donors are introduced. The receptors perform halide anion recognition in aqueous solvent system through charge-assisted XB interactions. These findings can allude to utility in organic synthesis, supramolecular chemistry and drug design.

Studies were performed to characterize the physical nature of the air-ice interface, and to clarify its role in processes that occur there. A glancing-angle Raman probe was developed to monitor hydrogen bonding at atmospheric interfaces; we saw enhanced hydrogen-bonding on ice compared to on water. Using glancing-angle laser-induced fluorescence (LIF), we determined that small acids and bases dissociated to similar extents at air-water and air-ice interfaces, but aromatic compounds were less well solvated at air-ice interfaces, resulting in self-association even at low surface coverages. We measured uptake kinetics of organic compounds using LIF and Raman spectroscopy. The uptake kinetics can be adequately fit by a single-exponential growth equation, but in order to properly describe the self-association of aromatics observed at the air-ice interface, equations accounting for self-association should be incorporated into the uptake model. A simple model was developed for naphthalene which included terms for self-association; good fits to the observed growth of intensity from monomeric and self-associated naphthalene were obtained. Direct photolysis of aromatics was faster at air-ice interfaces than in bulk ice or aqueous solution. While red shifts in the absorption spectra of benzene and naphthalene at air-ice interfaces could explain their enhanced reactivity there, the enhanced anthracene photolysis kinetics on ice are likely due to enhanced absorption cross sections or photolysis quantum yields, or to a different photolysis mechanism there. Oxidation rates of aromatics by photo-formed hydroxyl radicals are suppressed at air-ice interfaces, but not in bulk ice. Similarly, gas-phase OH reacts rapidly with aromatics at air-water interfaces, but no reaction is observed at air-ice interfaces. Conversely, the reactivity of ozone toward phenanthrene is enhanced there. This is not due to temperature effects or to enhanced partitioning of ozone to ice. Ozonation of bromide is also more rapid at air-ice interfaces than at air-water interfaces at environmentally relevant bromide concentrations. This enhancement could be due to exclusion of bromide to the air-ice interface during freezing. The rapid reactions of ozone with bromide and phenanthrene at air-ice interfaces suggest that both reactions could be atmospherically important.

La famille des composés halogènes et inter-halogènes représentent des solides moléculaires adoptant des phases denses communes avec des solides moléculaires diatomiques comme l’azote et l’hydrogène. Parmi les transformations structurales et électroniques induites sous haute pression et observées dans ces solides, on note, entre autres, la dissociation moléculaire et la métallisation. De plus, l’étude des phases denses de l’iode a permis récemment l’observation d’une structure cristalline possédant une modulation dite incommensurable, c’est-à-dire une modulation possédant une périodicité différente de celle de la structure cristalline, jetant ainsi une lumière nouvelle sur le processus de dissociation moléculaire dans les solides halogènes. Dans ce mémoire, on propose d’étudier les changements structuraux dans monobromure d’iode (IBr), un composé inter-halogène possédant des propriétés structurales semblables à celles de deux composés halogènes, soit l’iode (I2) et le brome (Br2) sous leur forme solide. Des expériences de diffraction des rayons X de poudres en utilisant un rayonnement synchrotron ont été réalisées à température ambiante sur l’IBr en variant la pression jusqu’aux environs de 60 GPa. La nature chimique particulière du composé IBr a nécessité la mise au point de techniques de chargement d’échantillon destinées à préserver l’intégrité chimique de la substance utilisée. On rapporte également l’observation d’une phase de l’IBr présentant une modulation incommensurable. Les phases observées dans l’IBr permettent d’établir des parallèles avec les phases denses rapportées dans I2 et Br2 par le biais d’un modèle phénoménologique décrivant la séquence structurale des solides halogènes sous forme condensée.

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Gegenstand der Arbeit ist ein neuer Atomemissionsdetektor (AED) für die Gaschromatographie (GC), der µ-ESD. In der vorliegenden Arbeit wird der Aufbau und das Funktionsprinzip des µ-ESDs vorgestellt. Untersucht wurde die Eignung des Detektors zur elementselektiven Bestimmung von Cl, Br, F, S und C im nahen Infrarot nach Optimierung einiger Betriebsparameter. Weiterhin wurden Möglichkeiten zur Korrektur spektraler und chemischer Interferenzen diskutiert. Die Charakterisierung des Detektors erfolgte anhand wichtiger Detektoreigenschaften wie Selektivität und Empfindlichkeit. Ein abschließender Vergleich des µ-ESDs mit einem kommerziellen AED und einem Elektroneneinfangdetektor anhand von Untersuchungen an einigen Umweltproben ermöglichte eine Einschätzung der Leistungsfähigkeit des neuen Detektors. Im direkten Vergleich zum kommerziellen AED wurden neben analytischen auch wirtschaftliche Aspekte betrachtet.

Although the air-ice interface is atmospherically important, it is difficult to model accurately because exclusion and precipitation of solutes during freezing, deposition of atmospheric species, and heterogeneous/photochemical processes all affect its properties. In this thesis, glancing-angle spectroscopic methods were developed to study ice surfaces. Glancing-angle Raman spectroscopy showed that nitrate is not strongly excluded to the ice surface during freezing, in contradiction with expectations based on equilibrium thermodynamics. Glancing-angle laser-induced fluorescence showed that hydronium ions are not strongly excluded when dilute acidic solutions (HNO3 or HCl) are frozen. These results suggest that solutes are not universally excluded and that care should be taken in modelling surface concentrations on ice. Deposition of HCl(g) was found to result in different pH responses at the "pure" vs. "salty" ice surfaces. Changes at the "salty" ice surface were consistent with the existence of a brine layer at the air-ice interface while changes at the "pure" ice surface were distinctly different, indicating that it may not be appropriate to model it as a cold, liquid layer. Significantly, results also suggest that the sea ice surface is buffered against pH changes, with important implications for interpreting pH-dependent chemistry. The conversion of sea-salt derived halides to reactive halogen species can lead to dramatic changes in the oxidative capacity of the overlying atmosphere. At ambient pH and naturally occurring halide concentrations, the dark ozonation of NaBr and NaI solutions was found to proceed more quickly on frozen vs. aqueous substrates, consistent with a freeze-concentration enhancement in halide concentration at the surface. A photochemical mechanism for halogen release from artificial saline snow was evidenced. The presence of ozone and light in the actinic region leads to accelerated production of Br2 and BrCl and the release of Cl2, in a process enhanced by high surface area, acidity and additional gas phase Br2. The results provide strong evidence for snowpack "halogen explosion" chemistry in which gas phase halogens are recycled back into a concentrated brine layer at the snow grain surface.

Although the air-ice interface is atmospherically important, it is difficult to model accurately because exclusion and precipitation of solutes during freezing, deposition of atmospheric species, and heterogeneous/photochemical processes all affect its properties. In this thesis, glancing-angle spectroscopic methods were developed to study ice surfaces. Glancing-angle Raman spectroscopy showed that nitrate is not strongly excluded to the ice surface during freezing, in contradiction with expectations based on equilibrium thermodynamics. Glancing-angle laser-induced fluorescence showed that hydronium ions are not strongly excluded when dilute acidic solutions (HNO3 or HCl) are frozen. These results suggest that solutes are not universally excluded and that care should be taken in modelling surface concentrations on ice. Deposition of HCl(g) was found to result in different pH responses at the "pure" vs. "salty" ice surfaces. Changes at the "salty" ice surface were consistent with the existence of a brine layer at the air-ice interface while changes at the "pure" ice surface were distinctly different, indicating that it may not be appropriate to model it as a cold, liquid layer. Significantly, results also suggest that the sea ice surface is buffered against pH changes, with important implications for interpreting pH-dependent chemistry. The conversion of sea-salt derived halides to reactive halogen species can lead to dramatic changes in the oxidative capacity of the overlying atmosphere. At ambient pH and naturally occurring halide concentrations, the dark ozonation of NaBr and NaI solutions was found to proceed more quickly on frozen vs. aqueous substrates, consistent with a freeze-concentration enhancement in halide concentration at the surface. A photochemical mechanism for halogen release from artificial saline snow was evidenced. The presence of ozone and light in the actinic region leads to accelerated production of Br2 and BrCl and the release of Cl2, in a process enhanced by high surface area, acidity and additional gas phase Br2. The results provide strong evidence for snowpack "halogen explosion" chemistry in which gas phase halogens are recycled back into a concentrated brine layer at the snow grain surface.