Inaug.-Diss.--Königsberg i. Pr. / Lebenslauf. Includes bibliographical references.

In this course of their work J. Risi and A. Labrie (1) found that guaiacol and vanillin were among the products derived from the sap of the sugar maple. By using a five percent sucrose solution and equal quantities of vanillin and guaiacol, a little calcium malate and manganese acetate, they obtained an amorphous powder possessing no odor of vanillin or guaiacol but having an odor greatly resembling the odor of the extracts of the sugar maple. This work is an investigation of the actual products of the reactions involved and the mechanism pertaining thereto. It is proposed to study this problem by carrying out the experiment of Risi and Labrie except that the constituents guaiacol, vanillin and sucrose will be used first one at a time, then two at a time and finally all together in an effort to determine the reaction and its mechanism. The following conclusions have been drawn from the work done: 1. The author has been unable to duplicate the work of Risi and Labrie by following their brief directions. 2. Several modifications of their procedure failed to produce the product described. 3. No change was found when each component was used alone in any of the modifications. 4. No change was found when the components were used two at a time in any of the modifications used. 5. No change was found using all three components in any of the modifications used. / M.S.

Introdução: O sangramento colorretal é considerado um sinal de alarme e não deve ser ignorado. A perda de sangue pode não ser identificada pelo paciente, o que caracteriza a presença de sangue oculto. Este diagnóstico pode ser confirmado por testes de Pesquisa de Sangue Oculto nas Fezes (PSOF), através de métodos químicos ou imunoquímicos de identificação da hemoglobina. O resultado positivo de um teste de PSOF requer investigação complementar com colonoscopia, exame invasivo, de alto custo e que exige preparo intestinal. Justifica-se, portanto, a aplicação de um teste diagnóstico mais sensível e específico. No presente estudo, foram avaliados quatro diferentes testes de PSOF em 176 pacientes submetidos à colonoscopia e seus resultados foram comparados. Objetivos: 1) avaliar o grau de concordância entre os testes de PSOF e a colonoscopia. 2) avaliar a sensibilidade, a especificidade e os valores de predição dos testes químico e imunoquímico de PSOF, em pacientes submetidos à colonoscopia. Métodos: Pacientes com indicação de realizar colonoscopia foram submetidos também à PSOF pelo método químico (o-toluidina) e pelo método imunoquímico, empregando três kits comerciais disponíveis no mercado. Os pacientes foram avaliados quanto à indicação do exame colonoscópico, resultado da colonoscopia e uso de alimentos e medicamentos que pudessem interferir no resultado dos testes fecais. Fundamentado nos achados endoscópicos, a colonoscopia foi categorizada em positiva ou negativa, de acordo com a possível fonte de sangramento colorretal. O grau de concordância entre os testes de PSOF foi avaliado pelo índice Kappa. Resultados: Dos 176 pacientes, houve predomínio do sexo feminino (64,8%), com média de idade de 55,5 anos. As indicações clínicas mais frequentes para realização de colonoscopia foram alteração do hábito intestinal, doença inflamatória intestinal, dor abdominal e anemia. Os principais achados foram pólipos < 1 cm, doença diverticular não complicada do cólon e exame normal. Quarenta e quatro (25%) colonoscopias foram categorizadas como positivas quanto à fonte de sangramento colorretal. Observou-se concordância (p<0,05) entre todos os testes avaliados e a colonoscopia. O teste da o-toluidina apresentou concordância pobre (Kappa 0,03), enquanto os demais testes apresentaram concordância moderada (Kappa entre 0,43-0,48). O teste da o-toluidina revelou menor sensibilidade, especificidade, valor preditivo positivo e valor preditivo negativo em comparação aos testes imunoquímicos. Conclusões: Os testes imunoquímicos apresentaram melhores índices de concordância com a colonoscopia, quando comparados ao teste da o-toluidina. Os testes imunoquímicos revelaram maior sensibilidade, especificidade e valores de predição na detecção de sangramento colorretal / Introduction: Colorectal bleeding is considered an alarm sign and should not be ignored. Blood loss can not be identified by the patient, which characterizes the presence of occult blood. This diagnosis can be confirmed by Faecal Occult Blood Testing (FOBT), through chemical or immunochemical methods. The positive outcome of a test requires complementary research FOBT with colonoscopy, an examination of invasive, costly and requires bowel preparation. It is justifiable, therefore, the application of diagnostic tests with better sensitivity and specificity. In the present study, we evaluated four different tests of PSOF in 176 patients undergoing colonoscopy and their results were compared. Objectives: 1) evaluate the degree of concordance between the PSOF tests and colonoscopy 2) assess the sensitivity, the specificity and the prediction values of the chemical and immunochemical FOBTs, in patients undergoing colonoscopy. Methods: Patients with indication of perform colonoscopy were subjected also to FOBT by the chemical method (toluidine test) and by the immunochemical method employing three commercial kits available in the market. Patients were evaluated regarding the indication of the colonoscopic examination, colonoscopy result, and use of foods and drugs that could interfere in the results of the faecal tests. Based on the endoscopic findings, the colonoscopy was rated as positive or negative, according to the possible colorectal bleeding source. The degree of accordance between FOBTs was evaluated by the Kappa index. Results: Among the 176 patients, there was a predominance of female gender (64.8%) with an average age of 55.5 years old. The most frequent clinical indication for colonoscopy were bowel habit changes, inflammatory bowel disease, abdominal pain and anemia. The main findings of colonoscopy were polyps <1 cm, uncomplicated colonic diverticular disease and normal exam. Forty-four (25%) colonoscopies were categorized as positive as to the possible source of colorectal bleeding. There was agreement (p<0.05) between all tests evaluated and the colonoscopy. The toluidine test presented poor accordance (Kappa 0.03), while the others showed moderate concordance (Kappa 0.43-0.48). The toluidine test showed less sensitivity, specificity, positive predictive value and negative predictive value compared to immunochemical tests. Conclusions: Immunochemical tests showed the best indexes of agreement with colonoscopy, when compared to the toluidine test. The immunochemical tests have shown greater sensitivity, specificity and predictive values in detecting colorectal bleeding

Introdução: O sangramento colorretal é considerado um sinal de alarme e não deve ser ignorado. A perda de sangue pode não ser identificada pelo paciente, o que caracteriza a presença de sangue oculto. Este diagnóstico pode ser confirmado por testes de Pesquisa de Sangue Oculto nas Fezes (PSOF), através de métodos químicos ou imunoquímicos de identificação da hemoglobina. O resultado positivo de um teste de PSOF requer investigação complementar com colonoscopia, exame invasivo, de alto custo e que exige preparo intestinal. Justifica-se, portanto, a aplicação de um teste diagnóstico mais sensível e específico. No presente estudo, foram avaliados quatro diferentes testes de PSOF em 176 pacientes submetidos à colonoscopia e seus resultados foram comparados. Objetivos: 1) avaliar o grau de concordância entre os testes de PSOF e a colonoscopia. 2) avaliar a sensibilidade, a especificidade e os valores de predição dos testes químico e imunoquímico de PSOF, em pacientes submetidos à colonoscopia. Métodos: Pacientes com indicação de realizar colonoscopia foram submetidos também à PSOF pelo método químico (o-toluidina) e pelo método imunoquímico, empregando três kits comerciais disponíveis no mercado. Os pacientes foram avaliados quanto à indicação do exame colonoscópico, resultado da colonoscopia e uso de alimentos e medicamentos que pudessem interferir no resultado dos testes fecais. Fundamentado nos achados endoscópicos, a colonoscopia foi categorizada em positiva ou negativa, de acordo com a possível fonte de sangramento colorretal. O grau de concordância entre os testes de PSOF foi avaliado pelo índice Kappa. Resultados: Dos 176 pacientes, houve predomínio do sexo feminino (64,8%), com média de idade de 55,5 anos. As indicações clínicas mais frequentes para realização de colonoscopia foram alteração do hábito intestinal, doença inflamatória intestinal, dor abdominal e anemia. Os principais achados foram pólipos < 1 cm, doença diverticular não complicada do cólon e exame normal. Quarenta e quatro (25%) colonoscopias foram categorizadas como positivas quanto à fonte de sangramento colorretal. Observou-se concordância (p<0,05) entre todos os testes avaliados e a colonoscopia. O teste da o-toluidina apresentou concordância pobre (Kappa 0,03), enquanto os demais testes apresentaram concordância moderada (Kappa entre 0,43-0,48). O teste da o-toluidina revelou menor sensibilidade, especificidade, valor preditivo positivo e valor preditivo negativo em comparação aos testes imunoquímicos. Conclusões: Os testes imunoquímicos apresentaram melhores índices de concordância com a colonoscopia, quando comparados ao teste da o-toluidina. Os testes imunoquímicos revelaram maior sensibilidade, especificidade e valores de predição na detecção de sangramento colorretal / Introduction: Colorectal bleeding is considered an alarm sign and should not be ignored. Blood loss can not be identified by the patient, which characterizes the presence of occult blood. This diagnosis can be confirmed by Faecal Occult Blood Testing (FOBT), through chemical or immunochemical methods. The positive outcome of a test requires complementary research FOBT with colonoscopy, an examination of invasive, costly and requires bowel preparation. It is justifiable, therefore, the application of diagnostic tests with better sensitivity and specificity. In the present study, we evaluated four different tests of PSOF in 176 patients undergoing colonoscopy and their results were compared. Objectives: 1) evaluate the degree of concordance between the PSOF tests and colonoscopy 2) assess the sensitivity, the specificity and the prediction values of the chemical and immunochemical FOBTs, in patients undergoing colonoscopy. Methods: Patients with indication of perform colonoscopy were subjected also to FOBT by the chemical method (toluidine test) and by the immunochemical method employing three commercial kits available in the market. Patients were evaluated regarding the indication of the colonoscopic examination, colonoscopy result, and use of foods and drugs that could interfere in the results of the faecal tests. Based on the endoscopic findings, the colonoscopy was rated as positive or negative, according to the possible colorectal bleeding source. The degree of accordance between FOBTs was evaluated by the Kappa index. Results: Among the 176 patients, there was a predominance of female gender (64.8%) with an average age of 55.5 years old. The most frequent clinical indication for colonoscopy were bowel habit changes, inflammatory bowel disease, abdominal pain and anemia. The main findings of colonoscopy were polyps <1 cm, uncomplicated colonic diverticular disease and normal exam. Forty-four (25%) colonoscopies were categorized as positive as to the possible source of colorectal bleeding. There was agreement (p<0.05) between all tests evaluated and the colonoscopy. The toluidine test presented poor accordance (Kappa 0.03), while the others showed moderate concordance (Kappa 0.43-0.48). The toluidine test showed less sensitivity, specificity, positive predictive value and negative predictive value compared to immunochemical tests. Conclusions: Immunochemical tests showed the best indexes of agreement with colonoscopy, when compared to the toluidine test. The immunochemical tests have shown greater sensitivity, specificity and predictive values in detecting colorectal bleeding

Ce mémoire de doctorat rassemble les travaux réalisés dans le cadre d’une étude analytique approfondie et systématique des substances à odeur boisée. Ces substances définissent une famille d’ingrédients unanimement appréciés pour leurs notes puissantes et recherchés par les parfumeurs pour composer les accords parmi les plus emblématiques de la profession. Les matières premières inscrites au programme de cette étude sont les essences de Gaïac, d’Araucaria, de Patchouli, de Cyprès Jaune d’Alaska, de Vétiver et d’Agarwood, ainsi que certains de leurs produits dérivés. La plupart de ces matières premières sont couramment utilisées par l’industrie du parfum. Leur spécificité provient de leur composition chimique très largement dominée par les dérivés sesquiterpéniques, conférant ainsi à ces extraits une complexité moléculaire indéniable. Les principaux objectifs de cette thèse de doctorat ont consisté à améliorer la connaissance de ces matières premières en termes de composition chimique, à déterminer autant que possible les composés odorants contribuant à leur odeur, et enfin d’explorer d’éventuelles voies de valorisation pour ces mêmes ingrédients à l’échelle industrielle.La méthodologie analytique développée tout au long de l’étude a nécessité l’utilisation combinée d’un large éventail de techniques chromatographiques, spectrométriques et spectroscopiques pour parvenir à caractériser ces matières premières au plus près et à réaliser l’isolement de leurs constituants inconnus. Ainsi, ces travaux s’articulent autour de quatre outils centraux : la chromatographie gazeuse bidimensionnelle intégrale couplée à la spectrométrie de masse (GC × GC–MS), la chromatographie gazeuse couplée à l’olfactométrie (GC–O), la chromatographie gazeuse semi-préparative (GC prép.) et la résonance magnétique nucléaire (RMN). Près de 190 composés ont été isolés et caractérisés dont 107 sont décrits pour la première fois comme constituants d’extraits naturels. / This Ph.D. dissertation sums up the work carried out as part of a thorough and systematic analytical study of woody-scented substances. These substances define a family of ingredients unanimously appreciated for their powerful notes, and sought by perfumers to compose some of the most emblematic accords in perfumery. The raw materials included in the frame of this study are the oils of Guaiac, Araucaria, Patchouli, Alaska Yellow Cypress, Vetiver, and Agarwood, as well as some of their by-products. Most of these raw materials are ingredients commonly used by the perfume industry. Their chemical specificity comes from their composition largely dominated by sesquiterpene derivatives, giving these extracts an undeniable molecular complexity. The main objectives of this Ph.D. thesis were to improve the knowledge of these raw materials in terms of chemical composition, to determine as much as possible the odorous compounds contributing to their odor, and finally to explore possible ways of valorization for these products on an industrial scale.The analytical methodology developed throughout this study required the combined use of a wide range of chromatographic, spectrometric, and spectroscopic techniques in order to characterize these raw materials as precisely as possible and achieve the isolation of their unknown constituents. Thus, our work revolved around four central tools: comprehensive two-dimensional gas chromatography-mass spectrometry (GC × GC-MS), gas chromatography-olfactometry (GC–O), preparative capillary-gas chromatography (pc-GC) and nuclear magnetic resonance (NMR). Almost 190 compounds have been isolated and characterized, 107 of which are described for the first time as constituents of natural extracts.