Order and membrane organization in chlorhexidine-lipid mixtures /

Formulations of a general bactericidal agent, chlorhexidine, mixed with a phospholipid at different concentrations are investigated using ^H NMR spectroscopy on a chain-deuterated lipid analog. Lipid-chlorhexidine formulation is known to release the drug into an aqueous medium slowly, maintaining a comparable concentration of the drug for up to four times longer than a direct aqueous solution. The NMR data does not support the proposed liposomal entrapment of chlorhexidine in lipid compartments. Complex thermal history of the lipid-chlorhexidine preparations is investigated in detail. In preparation for a counterpart measurement, using ^H NMR of deuterated chlorhexidine mixed with protonated lipid, the synthesis of a deuterated analog of chlorhexidine is performed.

"Man of science, man of faith" : Lost, consumer agency and the fate/free will binary in the post-9/11 context

In 2004, Lost debuted on ABC and quickly became a cultural phenomenon. Its postmodem take on the classic Robinson Crusoe desert island scenario gestures to a variety of different issues circulating within the post-9II1 cultural consciousness, such as terrorism, leadership, anxieties involving air travel, torture, and globalization. Lost's complex interwoven flashback and flash-forward narrative structure encourages spectators to creatively hypothesize solutions to the central mysteries of the narrative, while also thematically addressing archetypal questions of freedom of choice versus fate. Through an examination of the narrative structure, the significance of technological shifts in television, and fan cultures in Lost, this thesis discusses the tenuous notion of consumer agency within the current cultural context. Furthermore, I also explore these issues in relation to the wider historical post-9/II context.

Characterisation and optimisation of the flavour of health-promoting, plantderived bitterants in functional beverages.

Flavour is a combination of taste, odour, and chemesthetic sensations. Close associations exist between these sensory modalities, and thus, the overall flavour of a food or beverage product can change when the intensity of one or more of these sensations is altered. Strategies to modify flavour are often utilized by the food industry, and are central to the engineering of new and reformulated products. For functional food and beverages, flavour modification is particularly important, as fortifying agents can elicit high levels of less than desirable sensations, such as bitterness and astringency. The application of various flavour modifying strategies can decrease the perceived intensity of these sensations, and in tum, improve the sensory profile of the product. This collection of studies describes the sensory characteristics of experimental functional beverages fortified with trans-resveratrol, (+)-catechin, and/or caffeine, and examines the impact of novel flavour modifying strategies on the perceived flavour of these beverages. In the first study, results demonstrate that the flavour profile of Cabemet Sauvignon wines fortified with 20 mglL and 200 mg/L of trans-resveratrol is not perceived as different compared to control wine (0 mglL). However, Riesling wine fortified with 200 mg/L is perceived as significantly higher in bitterness compared to 20 mglL and control. For some functional food formulations, alternative strategies for flavour modification are needed. Traditional methods, such as the addition of sucrose and sodium chloride, may decrease the perceived 'healthiness' of a product, and thus, may be sub-optimal. In a second study, high and low concentrations of five different bitter inhibiting compounds - 'bitter blockers' - (B-cyclodextrin, homoeridictyol sodium salt, carboxymethylcellulose - low viscosity, zinc sulfate, magnesium sulfate) were tested for their efficacy towards decreasing the bitterness of high and low concentrations of caffeine and (+)catechin - two health-relevant, plant-derived bitterants. B-cyclodextrin and homoeridictyol sodium salt were the most effective blockers at decreasing (+ )-catechin and caffeine, respectively. In addition to bitter blockers, additional flavour modifying strategies, either alone or in combination - may also be successful in functional food formulations. Both sucrose and rebaudioside A - a plant-derived sweetener - were effective at decreasing the bitterness of (+)catechin. When added to (+)-catechin along with B-cyc1odextrin, both sweeteners provided the most effective decrease in bitterness compared to binary, ternary, or quaternary mixtures of (+)catechin together with bitter blockers, sweeteners, andlor odourants. The perceived intensity of sensations elicited by sweeteners and odourants was not affected by the addition of bitter blockers, and thus, their impact within these complex matrices is minimal. In addition, withinmodal (taste-taste) compared to cross-modal (taste-odour) sensory interactions were more effective at decreasing the bitterness of (+ )-catechin. Overall, results from these studies demonstrate that certain novel, alternative flavour modifying approaches may be successful towards lowering the bitterness and astringency elicited by (+ )-catechin and caffeine in aqueous solutions.

Generator Matrix Based Search for Extremal Self-Dual Binary Error-Correcting Codes

Self-dual doubly even linear binary error-correcting codes, often referred to as Type II codes, are codes closely related to many combinatorial structures such as 5-designs. Extremal codes are codes that have the largest possible minimum distance for a given length and dimension. The existence of an extremal (72,36,16) Type II code is still open. Previous results show that the automorphism group of a putative code C with the aforementioned properties has order 5 or dividing 24. In this work, we present a method and the results of an exhaustive search showing that such a code C cannot admit an automorphism group Z6. In addition, we present so far unpublished construction of the extended Golay code by P. Becker. We generalize the notion and provide example of another Type II code that can be obtained in this fashion. Consequently, we relate Becker's construction to the construction of binary Type II codes from codes over GF(2^r) via the Gray map.

Upper Semicontinuous Extensions of Binary Relations.

Suzumura shows that a binary relation has a weak order extension if and only if it is consistent. However, consistency is demonstrably not sufficient to extend an upper semi-continuous binary relation to an upper semicontinuous weak order. Jaffray proves that any asymmetric (or reflexive), transitive and upper semicontinuous binary relation has an upper semicontinuous strict (or weak) order extension. We provide sufficient conditions for existence of upper semicontinuous extensions of consistence rather than transitive relations. For asymmetric relations, consistency and upper semicontinuity suffice. For more general relations, we prove one theorem using a further consistency property and another with an additional continuity requirement.

Évaluation et modélisation de l’impact de la coexposition de composés organiques volatils sur l’excrétion de leurs biomarqueurs urinaires

L’évaluation de l’exposition aux composés organiques volatils (COV) recourt couramment à l’analyse des métabolites urinaires en assumant qu’aucune interaction ne survient entre les composés. Or, des études antérieures ont démontré qu’une inhibition de type compétitive survient entre le toluène (TOL), l’éthylbenzène (EBZ) et le m-xylène (XYL). Le chloroforme, qui est également un solvant métabolisé par le CYP2E1, se retrouve souvent en présence des autres COV dans les échantillons de biosurveillance. La présente étude visait donc à évaluer si le chloroforme (CHL) peut lui aussi interagir avec ces COV et évaluer ces interactions au niveau de l’excrétion des biomarqueurs urinaires associés, soit l’o-crésol, l’acide mandélique et l’acide m-méthylhippurique pour TOL, EBZ et XYL respectivement. Afin d’obtenir des données humaines, cinq volontaires ont été exposés par inhalation à différentes combinaisons de COV (seuls et mélanges binaires ou quaternaires) où la concentration de chacun des composés était égale à 1/4 ou 1/8 de la valeur limite d’exposition (VLE) pour une durée de 6h. Des échantillons d’air exhalé, de sang et d’urine ont été récoltés. Ces données ont ensuite été comparées aux modèles pharmacocinétiques à base physiologique (PCBP) existants afin de les ajuster pour l’excrétion urinaire. Certaines différences ont été observées entre les expositions aux solvants seuls et les coexpositions, mais celles-ci semblent majoritairement attribuables aux remplacements de participants à travers les différentes expositions. Les valeurs de Vmax pour EBZ et CHL ont été optimisées afin de mieux prédire les niveaux sanguins de ces COV. À l’exception du modèle pour EBZ, tous les paramètres pour l’excrétion urinaire ont été obtenus à partir de la littérature. Les modèles adaptés dans cette étude ont permis de simuler adéquatement les données expérimentales.

INVESTIGATIONS ON THE SOLVENT EXTRACTION AND LUMINESCENCE OF LANTHANOIDS WITH MIXTURES OF HETEROCYCLIC β- DIKETONE S AND VARIOUS NEUTRAL OXO-DONORS

The thesis entitled “ Investigations on the solvent extraction and luminescence of lanthanoids with mixtures of heterocyclic β-diketone S and various neutral oxo-donors” embodies the results of investigations carried out on the solvent extraction of trivalent lanthanoids with various heterocyclic β-diketones in the presence and absence of neutral oxo-donors and also on the luminescent studies of Eu3+-heterocyclic β-diketonate complexes with Lewis bases. The primary objective of the present work is to generate the knowledge base, especially to understand the interactions of lanthanoid-heterocyclic β-diketonates with various macrocyclic ligands such as crown ethers and neutral organophosphorus extractants , with a view to achieve better selectivity. The secondary objective of this thesis is to develop novel lanthanoid luminescent materials based on 3-phenyl-4-aroyl-5-isoxazolones and organophosphorus ligands, for use in electroluminescent devices. In the beginning it describes the need for the development of new mixed-ligand systems for the separation of lanthanoids and the development and importance of novel luminescent lanthanoid- β-diketonate complexes for display devices. The syntheses of various para substituted derivatives of 4-aroyl-5-isoxazolones and their characterization by various spectroscopic techniques are described. It also investigate the solvent extraction behaviour of trivalent lanthanoids with 4-aroyl-5-isoxazolones in the presence and absence of various crown ethers such as 18C6, DC18C6, DB18C6 and B18C6. Elemental analysis, IR and H NMR spectral studies are used to understand the interactions of crown ethers with 4-aroyl-5-isoxazolonate complexes of lanthanoids. The synergistic extraction of trivalent lanthanoids with sterically hindered 1-phenyl-3-methyl-4-pivaloyl-5-pyrazolone in the presence of various structurally related crown ethers are studied. The syntheses, characterization and photyphysical properties of Eu3+-4-aroyl-5-isoxazolonate complexes in the presence of Lewis bases like trictylphosphine oxide or triphenylphosphine oxide were studied.

Photosensitivity of Laser Dye Mixtures in Polymer Matrix – A Photoacoustic Study

Laser induced photoacoustic (PA) technique is used in the study of photostability of polymethyl methacrylate (PMMA) films doped with Rhodamine 6G -Rhodamine B dye system. Energy transfer from a donor molecule to an acceptor molecule in a dye mixture affects the output of the dye system. Details of investigations on the role of laser power, modulation frequency and the irradiation wavelength on the photosensitivity of the dye mixture doped PMMA films are presented.

Photoacoustic studies on thermal parameters of liquid crystal mixtures

Complete thermal characterization of liquid crystal mixtures in the smectic phase consisting of various relative volume fractions of cholesterol and 1-hexadecanol have been carried out using the photoacoustic technique. Thermal diffusivity values of these liquid crystal mixtures are evaluated using the open cell photoacoustic technique whereas the thermal effusivity value is measured using the conventional photoacoustic technique. From the measured values of these transient thermophysical parameters, the thermal conductivity and heat capacity of the sample under investigation are calculated. Analyses of the results show that all the thermophysical parameters depend strongly on the volume fraction of the constituents. Results are interpreted in terms of enhanced hydrogen bonding and the consequent enhancement in cohesive thermal energy transport with increasing volume fraction of 1-hexadecanol

Photoacoustic studies on thermal parameters of liquid crystal mixtures

Complete thermal characterization of liquid crystal mixtures in the smectic phase consisting of various relative volume fractions of cholesterol and 1-hexadecanol have been carried out using the photoacoustic technique. Thermal diffusivity values of these liquid crystal mixtures are evaluated using the open cell photoacoustic technique whereas the thermal effusivity value is measured using the conventional photoacoustic technique. From the measured values of these transient thermophysical parameters, the thermal conductivity and heat capacity of the sample under investigation are calculated. Analyses of the results show that all the thermophysical parameters depend strongly on the volume fraction of the constituents. Results are interpreted in terms of enhanced hydrogen bonding and the consequent enhancement in cohesive thermal energy transport with increasing volume fraction of 1-hexadecanol

Photoacoustic studies on thermal parameters of liquid crystal mixtures

Complete thermal characterization of liquid crystal mixtures in the smectic phase consisting of various relative volume fractions of cholesterol and 1-hexadecanol have been carried out using the photoacoustic technique. Thermal diffusivity values of these liquid crystal mixtures are evaluated using the open cell photoacoustic technique whereas the thermal effusivity value is measured using the conventional photoacoustic technique. From the measured values of these transient thermophysical parameters, the thermal conductivity and heat capacity of the sample under investigation are calculated. Analyses of the results show that all the thermophysical parameters depend strongly on the volume fraction of the constituents. Results are interpreted in terms of enhanced hydrogen bonding and the consequent enhancement in cohesive thermal energy transport with increasing volume fraction of 1-hexadecanol

Use of photoacoustic effect for the detection of phase transitions in liquid crystal mixtures

We report on a laser induced photoacoustic study of the nematic-to-isotropic transition in certain commercial nematic liquid crystal mixtures, namely BL001, BL002, BL032 and BL035. A simple analysis of the experimental data using the Rosencwaig–Gersho theory shows that the heat capacities of all these compounds exhibit a sharp peak as the temperature of the sample is varied across the transition region. Also, substantial differences in the photoacoustic signal amplitudes in nematic and isotropic phases have been noticed for all the mixtures. The increased light scattering property of the nematic phase may be the reason for the enhanced photoacoustic signal amplitude in this phase.

Use of photoacoustic effect for the detection of phase transitions in liquid crystal mixtures

We report on a laser induced photoacoustic study of the nematic-to-isotropic transition in certain commercial nematic liquid crystal mixtures, namely BL001, BL002, BL032 and BL035. A simple analysis of the experimental data using the Rosencwaig–Gersho theory shows that the heat capacities of all these compounds exhibit a sharp peak as the temperature of the sample is varied across the transition region. Also, substantial differences in the photoacoustic signal amplitudes in nematic and isotropic phases have been noticed for all the mixtures. The increased light scattering property of the nematic phase may be the reason for the enhanced photoacoustic signal amplitude in this phase

Use of photoacoustic effect for the detection of phase transitions in liquid crystal mixtures

We report on a laser induced photoacoustic study of the nematic-to-isotropic transition in certain commercial nematic liquid crystal mixtures, namely BL001, BL002, BL032 and BL035. A simple analysis of the experimental data using the Rosencwaig–Gersho theory shows that the heat capacities of all these compounds exhibit a sharp peak as the temperature of the sample is varied across the transition region. Also, substantial differences in the photoacoustic signal amplitudes in nematic and isotropic phases have been noticed for all the mixtures. The increased light scattering property of the nematic phase may be the reason for the enhanced photoacoustic signal amplitude in this phase.