This thesis aims to describe the system of financial reporting in the UK, certain aspects of the preparatory phase of the IFRS implementation process, main problems related to the implementation and impact of IFRS implementation on british companies.

Drug-facilitated sexual assaults are a public health and safety concern. Liquid chromatography paired with tandem mass spectrometry is theoretically capable of detecting the scope of drugs commonly encountered in these types of cases. An analytical method was developed for the quantitative analysis of 40 drugs designated by Academy Standards Board 121 “Standard for the Analytical Scope and Sensitivity for Forensic Toxicological Testing of Urine in Drug Facilitated Crime” (ASB 121). The targeted analytes spanned a range of drug classes including antidepressants, antihistamines, barbiturates, benzodiazepines, cannabinoids, stimulants, and opioids. The final method utilized supported liquid extraction, followed by liquid chromatography tandem mass spectrometry with electrospray ionization in simultaneous positive and negative mode. Multiple reaction monitoring allowed quantification of analytes along with stable isotope internal standards. Validation parameters assessed included linearity, bias, precision, limit of detection, lower limit of quantitation, interference, and ion suppression or enhancement. The utilized sample preparation method was able to extract 36 of the 40 target analytes and the developed analytical method was able to detect and quantify all analytes to the sensitivities required by ASB 121.

No / This paper contributes to our understanding of compliance with non-mandatory statements of best practice. Specifically, we examine the efficacy of agency-related mechanisms on the degree of disclosure compliance with the ASB Statement on interim reports. Using data drawn from a sample of 259 UK companies listed on the London Stock Exchange, we show that although overall disclosure compliance is high (74.5% of the items of information being disclosed), companies do not fully comply with the ASB Statement on interim reports. We employ an ordinary least square (OLS) regression model to establish whether selected company-specific and corporate governance characteristics (proxying for agency-related mechanisms) are related to the degree of disclosure compliance. Our results indicate that multiple listing, company size, interim dividend and new share issuance are positively associated with the degree of compliance. We also find that the degree of disclosure compliance is positively associated with auditor involvement, audit committee independence and audit committee financial expertise. These results have important implications for policy because they suggest that whilst agency-related mechanisms may motivate compliance with best practice non-mandatory statements, full compliance may be unattainable without regulations.

Phytosterols are steroid chemicals produced by plants for the purposes of membrane function and hormone production. Phytosterols can cause endocrine disruption in aquatic species at very low concentrations and are suspected of contributing to endocrine disruption linked to pulp and paper effluent. Wastewater from the pulp and paper industry is often treated biologically in aerated stabilization basins (ASBs) that expose phytosterols to a range of redox zones. Phytosterol removal in ASBs varies and stigmasterol has even been shown to increase across the treatment system. Little is known about the microbial processes that occur within ASBs and their effect on phytosterol removal. The objective of this research was to assess the biotransformation potential of phytosterols in a simulated ASB treatment system and to improve understanding of the processes that occur within the various redox zones and their impact on the removal of phytosterols. To assess the biotransformation of phytosterols under aerobic conditions, three assays were conducted using a stock aerobic culture fed with pulp and paper wastewater. The assays tested three conditions: phytosterols present as a sole added carbon source, phytosterols with dextrin as an added carbon source, and phytosterols with ethanol as a solubilizing agent and added carbon source. Phytosterol biotransformation was found to be limited by low phytosterol solubility. When solubilized, phytosterol removal occurred in two phases: an initial near-linear removal, followed by accelerated removal during the culture's stationary stage, possibly due to the release of extracellular cholesterol oxidase. The anoxic and anaerobic biotransformation of phytosterols was examined through a series of three semi-batch cultures maintained under nitrate-reducing, sulfate-reducing and fermentative/methanogenic conditions, all developed from stock cultures fed with pulp and paper wastewater. Phytosterol removal was significant in the nitrate-reducing culture, although microbial activity and phytosterol removal declined in later stages. Phytosterol removal was also observed in the sulfate-reducing culture, although there was a significant lag period before removal occurred. No phytosterol removal was observed in the fermentative/methanogenic culture. Phytosterol biotransformation was also examined in the context of a lab-scale ASB fed continuously with pulp and paper wastewater. The steady-state ASB effluent and sediment characteristics were examined over three hydraulic retention times (HRTs). Effluent quality was not significantly affected by a change in HRT but sediment characteristics were significantly affected and, at shorter HRTs, phytosterols accumulated in the sediment. Wastewater bioassays demonstrated the release of phytosterols during the breakdown of solids. This research improves the understanding of biological processes within ASBs and their effect on phytosterol removal.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-04-13T15:38:50Z No. of bitstreams: 1 versão final tese- versão da corrigida em 12-11-2014- para impressão e entrega.pdf: 3298946 bytes, checksum: 49c8459cd8f0cfb0e3f54792ca63367f (MD5) / Approved for entry into archive by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-05-10T16:19:14Z (GMT) No. of bitstreams: 1 versão final tese- versão da corrigida em 12-11-2014- para impressão e entrega.pdf: 3298946 bytes, checksum: 49c8459cd8f0cfb0e3f54792ca63367f (MD5) / Made available in DSpace on 2016-05-10T16:19:14Z (GMT). No. of bitstreams: 1 versão final tese- versão da corrigida em 12-11-2014- para impressão e entrega.pdf: 3298946 bytes, checksum: 49c8459cd8f0cfb0e3f54792ca63367f (MD5) / CAPES / Medidas relativas aos espectros de Absorção da Albumina Sérica Bovina com variação do comprimento de onda de varredura entre 300 a 500nm demonstraram um aumento nas intensidades da banda de absorção da ASB, após adição de aliquotas dos ligantes (β- lapachonas, cumarinas e Rutinas), sobretudo em 280nm, que é o comprimento de onda de absorção característico dos dois resíduos de triptofano presentes na ASB. Medidas de Dicroísmo Circular confirmam a presença das bandas de absorção características dos resíduos de triptofano, cujos máximos de absorção estão em 208 e 222nm nas diferentes temperaturas estudadas. As modificações obtidas nos espectros de Dicroísmo Circular da ASB a partir da adição de alíquotas das espécies ligantes deram origem ao efeito ocorrido na disposição planar original da α-hélice presente na estrutura secundária da ASB. A emissão fluorescente de ASB nas temperaturas de 298K, 303K, 310K e para os sistemas ASB/β-lapachonas e ASB/rutinas e 288K, 293K, 298K para o sistema ASB/Cumarinas, mostrou um efeito supressivo sobre o espectro de emissão da ASB, sobretudo em 345 nm, emissão do resíduo de triptofano da ASB, após a adição dos ligantes. Os valores para os parâmetros termodinâmicos ΔGo, ΔHo, ΔSo para os sistema ASB/β-lapachonas, ASB/4-metil-7-hidroxicumarinas e ASB/Rutinas não sofreram grandes variações como uma função do ligante. A partir destes valores pode-se concluir que o tipo de interação predominante entre ASB/ligante foi hidrofóbica. A sobreposição entre os espectros de absorção do supressor e de emissão da ASB possibilitou determinar para cada par ASB/supressor a distância crítica de interação e o raio de Foster, os quais mostraram a probabilidade da existência do fenômeno de Transferência da Energia Ressonante de Fluorescência (FRET) em todos os casos. No sistema ASB/β-lapachona e ASB/3-Ácido sulfônico β-lapachona obtivemos respectivamente para um valor médio relativo as três temperaturas de trabalho, temos: R0= 2,69 nm em relação a r = 3,02 e R0 = 2,32nm em relação a r = 3,32. Já para o par 7-hidroxicumarina e 4-metil-7- hidroxicumarina, temos: R0= 3,53 e r = 3,83nm; R0= 3,70 nm e r = 4,33 nm. Por fim, no par ASB/Rutina e ASB/Rutina-metilada: R0= 3,43nm e r = 3,41nm; R0 = 3,14nm e r = 4,03nm. / Measurements relating to the absorption spectra in the wavelength range of 300 to 500nm scan demonstrated an increase in intensity of the absorption band of ASB upon addition of aliquots of ligands (β-lapachonas, coumarins and Rutinas), mainly 280nm, is the wavelength of the absorption characteristic of the two tryptophan residues present in the ASB. Circular Dichroism measurements confirm the presence of characteristic absorption bands of tryptophan residues, which are maximum at around 208nm and 222nm at different temperatures. The changes in the spectra obtained Circular Dichroism of ASB from the addition of aliquots of ligand species gave rise to the effect occurred in planar array of original α-helix present in the secondary structure of ASB. The fluorescent emission of ASB at temperatures of 298K, 303K, and 310K for the ASB / ASB and β-lapachonas / routines and 288K, 293K, 298K for the ASB / Coumarins system, systems showed a suppressive effect on the emission spectrum of ASB , especially at 345 nm, emission of the tryptophan residue of ASB, after the addition of binders. The values for the thermodynamic parameters ΔGo, ΔHo, ΔSo system for ASB / β-lapachonas, ASB / 4-methyl-7-hydroxycoumarins and ASB / Rutinas underwent no significant variations as a function of the ligand. From these values it can seconcluir that the predominant interaction between ASB / binder is hydrophobic. The overlap between the absorption spectra of the suppressor and issued by ASB allowed to determine for each pair ASB / suppressor critical distance the radius of interaction and Foster, that indicate the probability of the existence of the phenomenon Resonant Energy Transfer Fluorescence (FRET) in all cases. In ASB / β- lapachone and ASB / 3-sulfonic acid β-lapachone system obtained respectively for an average value for the three operating temperatures, we have R0 = 2.69 nm against air = 3.02 and R0 = 2, 32nm relative air = 3.32. As for the pair 7-hydroxycoumarin and 4-methyl-7- hydroxycoumarin, we have: r = R0 = 3.53 3,83nm; R0 = 3.70 and r = 4.33 nm nm. Finally, the pair ASB / rutin and ASB / Rutina-methylated: R0 = r = 3,43nm 3,41nm; R0 = 3,14nm and r = 4,03nm.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-06-06T12:34:21Z No. of bitstreams: 1 2010 - Alessandra Medeiros Ribeiro .pdf: 4846590 bytes, checksum: 525d2754e1be01d1117fe6e9f3362d1f (MD5) / Made available in DSpace on 2017-06-06T12:34:21Z (GMT). No. of bitstreams: 1 2010 - Alessandra Medeiros Ribeiro .pdf: 4846590 bytes, checksum: 525d2754e1be01d1117fe6e9f3362d1f (MD5) Previous issue date: 2010-03-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior, CAPES, Brasil. / Spectroscopic studies for several comercial flavonoids (flavone (FVA), alphanaphthoflavone (?-NAF), beta-naphthoflavone (?-NAF), thioflavone (TFA), S,Sdioxythioflavone (SDF), flavanone (FNA) and quercetin (QUE)), natural flavonoids (biflavonoids such as agatisflavone (ATF), 7?-O-methylagatisflavone (OMA), amentoflavone (AMF) and (DOF)) and thiochromanone (TCR) were performed in different solvents (acetonitrile (ACN), ethanol (ETOH), cyclohexane (CEX), dichloromethane (DCM) and milli-Q water (AD)). Irradiation of TFA, SDF and TCR in acetonitrile, employing the nanosecond laser flash photolysis, lead to the formation of their corresponding triplet excited state. Fluorescence emission spectroscopy studies showed that commercial and natural flavonoids and thiochromanone are not fluorescent. UV/visible spectroscopy studies for QUE, ATF, OMA, AMF and DOF, in the same previous solvents, revealed that for these flavonoids the ground-state absorption spectrum in polar solvents, such as water or PBS (pH=7.4), is completely different than the obtained in dichloromethane. This difference is more pronounced for ATF. For DOF the absorption spectrum in water shows remarkable variations when compared to that in PBS. The interaction between BSA and the flavonoids QUE, ATF, OMA, AMF and DOF in PBS solution, pH = 7.4, was studied by UV/visible spectroscopy, fluorescence emission spectroscopy, circular dicroism and molecular modelling. From these studies it was clearly demonstrated that the interaction observed was directly dependent on the flavonoid concentration and almost independent on temperature variation. The ground state absorption spectrum for BSA showed a hypsochromic effect on the absorption band around 208 nm, corresponding to the n?* transition of the BSA ?-helix structure, as a function of flavonoid concentration. Similar behavior was observed for the absorption at 280 nm, corresponding to the tryptophan absorption in BSA. The fluorescence emission spectrum for BSA in the presence of QUE, ATF, OMA, AMF and DOF, in PBS, at T = 22?C, 27?C, 32?C, 37?C and 42?C, shows a blue-shift on the protein emission as a function of flavonoid concentration. These results suggest that the BSA chromophore is in a more hydrophobic environment when compared with that sensed by the protein in the absence of the flavonoid. In this case, quenching of BSA fluorescence (tryptophan residues) was clearly observed with the high values obtained for the quenching rate constant kq (? 1013 to 1014 L/mol.s) indicating a static quenching process. The distance (r) observed for the tryptophan residues and the flavonoids was smaller than 7 nm, which indicates that there is a reasonable probability for a non-radiative energy transfer process between tryptophan and the flavonoids, based on the F?rster theory for energy transfer. Circular dicroism results at T = 25?C, 37?C and 42?C revealed a significant decrease on the ?-helix percentage for BSA at 208 nm and 222 nm, corresponding to the n?* transition for the secondary structure of BSA, as a function of flavonoid concentration. These effects can be attributed to the formation of a complex BSA/flavonoid which can induce conformational variations on the BSA structure. Molecular modelling indicates that the main regions for the interaction between flavonoids and ASB are located in hydrophobic cavities on the sub-domains IB and IIA, which contain tryptophan residues (Trp-158 and Trp-237). A large hydrophobic cavity containing the Trp-237 is present in the sub-domain IIA, which is responsible for the formation of the complex flavonoid-BSA through a strong interaction flavonoid-tryptophan. / Estudos espectrosc?picos para diversos flavon?ides comerciais (flavona (FVA), alfanaftoflavona (?-NAF), beta-naftoflavona (?-NAF), tioflavona (TFA), S,S-di?xidotioflavona (SDF), flavanona (FNA) e quercetina (QUE)), flavon?ides naturais (biflavon?ides como agatisflavona (ATF), 7?-O-metilagatisflavona (OMA), amentoflavona (AMF) e diidroochnaflavona (DOF)) e tiocromanona (TCR), foram realizados em diferentes solventes (acetonitrila (ACN), etanol (ETOH), cicloexano (CEX), diclorometano (DCM) e ?gua millliQ (AD)). A irradia??o de TFA, SDF e TCR, em acetonitrila, por fot?lise por pulso de laser de nanossegundo, levou ? forma??o de seus respectivos estados excitados triplete. Por espectroscopia de fluoresc?ncia, verificou-se que os flavon?ides comerciais e naturais, e a tiocromanona n?o apresentam emiss?o de fluoresc?ncia. Por espectroscopia de absor??o no ultravioleta/vis?vel (UV-Vis) para QUE, ATF, OMA, AMF e DOF, nestes solventes, percebeu-se que os espectros em presen?a de solventes polares, como AD, foram bem diferentes dos espectros em DCM, principalmente, para ATF, e os espectros em solu??o de tamp?o PBS (pH = 7,4) foram semelhantes aos em AD, exceto para DOF, apresentando mudan?as substanciais. A intera??o entre ASB e os flavon?ides (QUE, ATF, OMA, AMF e DOF) em solu??o tamponada (PBS, pH = 7,4) foi estudada por espectroscopia no ultravioleta/vis?vel, espectroscopia de emiss?o de fluoresc?ncia, dicro?smo circular e modelagem molecular sendo diretamente dependente da concentra??o adicionada de flavon?ides e muito pouco dependente com a varia??o da temperatura. No UV-Vis ocorreu deslocamento para o azul das bandas de absor??o pr?ximas a 208 nm (correspondente a ASB, referente ?s transi??es n?* da estrutura ?-h?lice da albumina) e 280 nm (correspondente ao triptofano da ASB), em fun??o do aumento de concentra??o dos flavon?ides. Na espectroscopia de fluoresc?ncia (T = 22?C, 27?C, 32?C, 37?C e 42?C) houve deslocamento para o azul na emiss?o da prote?na com o aumento da concentra??o dos flavon?ides, sugerindo que o crom?foro da ASB est? em um ambiente mais hidrof?bico em rela??o ?quele quando para ASB livre. Neste caso, observou-se supress?o da fluoresc?ncia de ASB (res?duos de triptofano), como consequ?ncia de um processo de supress?o est?tica como demonstrado pelos altos valores observados para kq (? 1013 a 1014 L/mol.s). A dist?ncia entre os res?duos de triptofano e os flavon?ides (r) foi menor que 7 nm, um indicativo da grande probabilidade de ocorrer transfer?ncia de energia entre ASB e flavon?ides, de acordo com a teoria de transfer?ncia de energia n?o-radiativa de F?rster (Teoria de F?rster). No dicro?smo circular (T = 25?C, 37?C e 42?C) foi verificada uma diminui??o do % de ?-h?lice da ASB em 208 nm e 222 nm (regi?es de transi??o n?* da estrutura secund?ria ?-h?lice da ASB no espectro de absor??o UV), devido ao aumento de concentra??o dos flavon?ides. Esses efeitos podem ser atribu?dos ? forma??o de um complexo flavon?ide-ASB que pode estar induzindo varia??es conformacionais na ASB. Por modelagem molecular, atrav?s do programa docking, percebeuse que as regi?es principais para a liga??o dos flavon?ides com os s?tios de liga??o da ASB est?o localizadas em cavidades hidrof?bicas nos subdom?nios IB e IIA (consistentes com os s?tios I e II) e os res?duos de triptofano (Trp-158 e Trp-237) de ASB est?o nesses subdom?nios, respectivamente. Existe uma grande cavidade hidrof?bica presente no subdom?nio IIA, onde os flavon?ides podem se ligar com o res?duo de triptofano Trp-237 (melhor s?tio de liga??o), formando o complexo flavon?ide-ASB.