Fragm. lat. III 15 - Liber Sextus Decretalium, cum apparatu (VI° 1.6.10 - 14)

Trägerband: Ms. Barth. 10; Vorbesitzer: Johannes Pincerna de Erbach; Bartholomaeusstift Frankfurt am Main

Flexible synthesis of enantiomerically pure 2,8-dialkyl-1,7-dioxaspiro[5.5]undecanes and 2,7-dialkyl-1,6-dioxaspiro[4.5]decanes from propargylic and homopropargylic alcohols

A new approach to enantiomerically pure 2,8-dialkyl-1,7-dioxaspiro[5.5]undecanes and 2,7-dialkyl-1,6-dioxaspiro [4.5] decanes is described and utilizes enantiomerically pure homopropargylic alcohols obtained from lithium acetylide opening of enantiomerically pure epoxides, which are, in turn, acquired by hydrolytic kinetic resolution of the corresponding racemic epoxides. Alkyne carboxylation and conversion to the Weinreb amide may be followed by triple-bond manipulation prior to reaction with a second alkynyllithium derived from a homo- or propargylic alcohol. In this way, the two ring components of the spiroacetal are individually constructed, with deprotection and cyclization affording the spiroacetal. The procedure is illustrated by acquisition of (2S,5R,7S) and (2R,5R,7S)-2-n-butyl-7-methyl-1,6-dioxaspiro[4.5]-decanes (1), (2S,6R,8S)-2-methyl-8-n-pentyl-1,7-dioxaspiro[5.5]undecane (2), and (2S,6R,8S)-2-methyl-8-n-propyl-1,7-dioxaspiro[5.5]undecane (3). The widely distributed insect component, (2S,6R,8S)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (4), was acquired by linking two identical alkyne precursors via ethyl formate. In addition, [H-2(4)]-regioisomers, 10,10,11,11-[H-2(4)] and 4,4,5,5-[H-2(4)] of 3 and 4,4,5,5-[H-2(4)]-4, were acquired by triple-bond deuteration, using deuterium gas and Wilkinson's catalyst. This alkyne-based approach is, in principle, applicable to more complex spiroacetal systems not only by use of more elaborate alkynes but also by triple-bond functionalization during the general sequence.

Isaías 24,1-6 na perspectiva da profecia apocalipsista resultante de um complexo processo sócio-teológico em transição

A dissertação objetiva estudar o papel que o apocalipsismo, desempenhou na história e no contexto da redação do oráculo isaiano em Isaías 24,1-6. A proposta é de que sua função foi de grande importância no processo de formação do judaísmo pós-exílico, fomentando uma nova reidentificação e reetnização dos israelitas-judaítas num contexto de frustração nacionalista e religiosa que gerou uma grande heterogeneidade teológica. Identificamos este contexto como sendo o ambiente em que se deu um complexo processo de transição sócio-teológica na história dos judaitas no período de dominação persa. O apocalipsismo, enquanto fenômeno religioso e sócio-histórico, se mostrou como resultado de uma realidade hostil e desumanizadora na qual a identidade teológico-cultural e os relacionamentos sócioeconômicos das pessoas foram extremamente ameaçados e violentados gerando uma contraposição aos desígnios de Yahweh expressos na aliança firmada por ele para com seu povo. Através da pesquisa e análise exegética de Isaías 24,1-6, a presente dissertação propõe que, a partir dessa realidade conflituosa, a profecia apocalipsista isaiana se manifesta contra as estruturas e suas articulações geradoras de segregação e desumanidade, lançando uma esperança no ato transformador por intermédio de Yahweh, o senhor da história, que possibilita um reverso histórico, a partir do qual será possível reconstruir relacionamentos favoráveis no âmbito social e espiritual.(AU)

Intermédiaires réactionnels de la fructose-1,6-biphosphate aldolase de Leishmania mexicana : comparaison avec l'enzyme de mammifère et recrutement de la région C-terminale

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Intermédiaires réactionnels de la fructose-1,6-biphosphate aldolase de Leishmania mexicana : comparaison avec l'enzyme de mammifère et recrutement de la région C-terminale

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

In this work Cu_1.4Mn_1.6O₄ (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu⁺/Cu²⁺ and Mn³⁺/Mn⁴⁺ couples exist in the CMO sample, and a maximum conductivity of 78 S cm⁻¹ is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc₂O₃ stabilized ZrO₂ (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm² at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm⁻² at 800 °C under H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that Cu_1.4Mn_1.6O₄ is a superior and promising cathode material for IT-SOFCs.

Acetilação do exopolissacarídeo (1→6)-β-D-glucana (lasiodiplodana): derivatização química e caracterização

Lasiodiplodan is an exocellular β-glucan with biological functionalities such as antioxidant, antiproliferative, hypocholesterolemic, protective activity against DNA damage induced by doxorubicin and hypoglycemic activity. Chemical derivatization of polysaccharide macromolecules has been considered as a potentiating mechanism for bioactivity. In this context, this work proposes the derivatization of lasiodiplodan by acetylation. Acetic anhydride was used as derivatizing agent and pyridine as catalyst and reaction medium. The derivatives obtained were evaluated by its water solubility, degree of substitution (DS), antioxidant potential, and characterized by infrared spectroscopy (FT-IR), thermal analysis, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Acetylated derivatives with different degrees of substitution (1.26; 1.03; 0.66 and 0.48) were obtained, and there was correlation between the concentration of derivatizing agent and DS. FT-IR spectroscopy analysis confirmed the insertion of acetyl groups into derivatized macromolecules (LAS-AC) through of specific bands concerning to carbonyl group (C = O) and increase in C-O vibration. SEM analysis indicated that native lasiodiplodan presents morphological structure in the form of thin films with translucent appearance and folds along its length. Derivatization led to morphological changes in the polymer, including aspects thickness, translucency and agglomeration. Thermal analysis indicated the native sample and derivative with DS 0.48 presented three weight loss stages. The first stage occurred until 125 ° C (loss of water) and there were two consecutive events of weight loss (200 ° C - 400 ° C) attributed to molecule degradation. Samples with DS 1.26; 1.03 and 0.66 demonstrated four weight loss stages. The first stage occurred until 130 ° C (loss of water), following by two consecutive events of weight loss (200 ° C - 392 ° C) attributed to degradation of the biopolymer. The fourth stage was between 381 ° C and 532 ° C (final decomposition) with exothermic peaks between 472 ° C and 491 ° C. X-ray diffraction patterns showed that native and acetylated lasiodiplodan have amorphous structure with semicrystalline regions. Derivatization did not contribute to increased solubility of the macromolecule, but potentiated its antioxidant capacity. Acetylation of lasiodiplodan allowed to obtaining a new macromolecule with higher antioxidant potential than the native molecule and with technological properties applicable in various industrial sectors.

Catalysts study of adipic acid synthesis from 1,6-hexanediol

Sustainable chemicals currently have a very limited market share due to current low production but biomass is expected to become one of the major renewable energy and fine chemicals sources in the coming years. Bearing in mind the compromise of all nations to climatic change remediation, the industries will need to use efficient catalysts and green processes to meet the requirements of emissions and efficiency. This project is expected to develop new catalysts to convert 1,6-hexanediol to adipic acid through a green approach based on the “nano-catalysis” and “green chemistry” concepts. Supported Au and Pd nanoparticles were used to study one-pot reaction of HDO oxidation to AA using O2 as a final oxidant and H2O as a solvent. Catalytic results showed that under low pressure O2 atmosphere and low temperature (< 120°C) AuNPs supported on basic-supports are more active than acid and amphoteric oxides. The effect of basic oxide (MgO) addition to MgF2 was studied. The study showed that doping of MgF2 with MgO increased significantly the activity of the catalyst. The best results were obtained with the Au/0.4MgF2-0.6MgO sample, which gave the selectivity to AA of 33% at HDO conversion of 62%.

Who fails to complete tuberculosis treatment? Temporal trends and risk factors for treatment interruption in a community-based directly observed therapy programme in a rural district of South Africa

SETTING: Hlabisa Tuberculosis Programme, Hlabisa, South Africa. OBJECTIVE: To determine trends in and risk factors for interruption of tuberculosis treatment. METHODS: Data were extracted from the control programme database starting in 1991. Temporal trends in treatment interruption are described; independent risk factors for treatment interruption were determined with a multiple logistic regression model, and Kaplan-Meier survival curves for treatment interruption were constructed for patients treated in 1994-1995. RESULTS: Overall 629 of 3610 surviving patients (17%) failed to complete treatment; this proportion increased from 11% (n = 79) in 1991/1992 to 22% (n = 201) in 1996. Independent risk factors for treatment interruption were diagnosis between 1994-1996 compared with 1991-1393 (odds ratio [OR] 1.9, 95% confidence interval [CT] 1.6-2.4); human immunodeficiency virus (HIV) positivity compared with HIV negativity (OR 1.8, 95% CI 1.4-2.4); supervised by village clinic compared with community health worker (OR 1.9, 95% CI 1.4-2.6); and male versus female sex (OR 1.3, 95% CI 1.1-1.6). Few patients interrupted treatment during the first 2 weeks, and the treatment interruption rate thereafter was constant at 1% per 14 days. CONCLUSIONS: Frequency of treatment interruption from this programme has increased recently. The strongest risk factor was year of diagnosis, perhaps reflecting the impact of an increased caseload on programme performance. Ensuring adherence to therapy in communities with a high level of migration remains a challenge even within community-based directly observed therapy programmes.

Chagas disease in an area of recent occupation in Cochabamba, Bolivia

INTRODUCTION: A descriptive, entomological and seroepidemiological study on Chagas disease was conducted in a place of recent occupation on the outskirts of Cochabamba, Bolivia: Avaroa/Primer de Mayo (population:3,000), where the socio-economic level is low and no control measures have been made available. METHODS: The immunofluorescent antibody test (IFAT) was used for IgG and IgM anti-Trypanosoma cruzi antibodies in filter paper bloodspot eluates from 128 subjects (73 females, 55 males) selected by systematic sampling. Concerning each subject age, gender, birthplace, occupation, duration of residence and building materials used in their houses were recorded. Vectors were captured both in domestic and peridomestic environments. RESULTS: Seropositive, 12.5% (16/128): females, 15.1% (11/73); males, 9.1% (5/55). Average time of residence: 6.1 years for the whole population sample and 7.4 years for the seropositive subjects. Most houses had adobe walls (76.7% , n= 30), galvanized iron rooves (86.7%) and earthen floors (53.4%) 80% of the walls had crevices. One hundred forty seven specimens of Triatoma infestans were captured, of which 104 (70.7%) were domestic, and 1 peridomestic Triatoma sordida. Precipitin host identification: birds, 67.5%; humans, 27.8%; rodents, 11.9%; dogs, 8.7%; cats, 1.6%. House infestation and density indices were 53.3 and 493.0 respectively. We found 21 (14.3%) specimens of T. infestans infected with trypanosomes, 18 (85.7%) of which in domestic environments. DISCUSSION: The elements for the vector transmission of Chagas disease are present in Avaroa/Primer de Mayo and the ancient custom of keeping guinea pigs indoors adds to the risk of human infection. In neighboring Cochabamba, due to substandard quality control, contaminated blood transfusions are not infrequent, which further aggravates the spread of Chagas disease. Prompt action to check the transmission of this infection, involving additionally the congenital and transfusional modes of acquisition, is required.

Estresse oxidativo e disfunção endotelial na doença renal crônica

FUNDAMENTO: A doença renal crônica (DRC) caracteriza-se pela alta prevalência de aterosclerose. Uma vez que o estresse oxidativo e a disfunção endotelial são promotores da aterosclerose, é interessante verificar se as duas condições estão associadas em pacientes com DRC, ainda sem doença cardiovascular (DCV) clínica. OBJETIVO: Avaliar as relações entre o estresse oxidativo e a função endotelial em pacientes com DRC estágio 5, sem DCV. MÉTODOS: Foram estudados 22 pacientes com DRC, não-diabéticos, não-fumantes, sem DCV e tratados por hemodiálise; além de 22 indivíduos normais. Em todos os indivíduos foram avaliados a reatividade vascular, dependente e independente de endotélio (ultra-som de alta resolução da artéria braquial), e o estresse oxidativo (níveis plasmáticos de substâncias reativas ao ácido tiobarbitúrico - TBARS). RESULTADOS: A reatividade vascular dependente de endotélio (6,0 ± 4,25% vs. 11,3 ± 4,46%, p <0,001) e a reatividade independente de endotélio (11,9 ± 7,68% vs. 19,1 ± 6,43%, p <0,001) foram reduzidas na DRC, enquanto o estresse oxidativo (2,63 ± 0,51 vs. 1,49 ± 0,43, p <0,001) foi aumentado. Os níveis de TBARS, quando utilizado na totalidade de indivíduos do estudo (pacientes e controles), correlacionaram-se com a reatividade vascular dependente de endotélio (r = -0,56, p<0,001) e com a pressão arterial sistólica (r = 0,48, p = 0,002). CONCLUSÃO: O estresse oxidativo é associado à disfunção endotelial. Pacientes com DRC apresentam aumento do estresse oxidativo e comprometimento da reatividade vascular. Os resultados sugerem ainda que o estresse oxidativo e a disfunção endotelial podem estar envolvidos na susceptibilidade exagerada da DRC às complicações cardiovasculares.

Valores de referência para o teste cardiopulmonar para homens e mulheres sedentários e ativos

FUNDAMENTO: Os valores de referência de teste cardiopulmonar (TCP) disponíveis no Brasil foram derivados de cicloergômetro, em população sedentária e relativamente pequena. OBJETIVO: Fornecer valores de referência para o TCP em brasileiros de ambos os sexos, sedentários e ativos. MÉTODOS: ENtre 2006 e 2008, 3.992 TCP de indivíduos saudáveis foram selecionados de nosso laboratório. Atletas, fumantes, portadores de qualquer patologia conhecida, usuários de medicação contínua e obesos foram excluídos. VO2 pico foi considerado VO2 máx. Analisamos também VO2 de limiar anaeróbico, ventilação máxima e pulso de oxigênio de acordo com sexo, faixa etária, sedentários e ativos. As faixas etárias foram assim divididas: G1 (15-24 anos), G2 (25-34), G3 (35-44), G4 (45-54), G5 (55-64) e G6 (65-74). RESULTADOS: De acordo com as faixas etárias, os valores médios de VO2 em ml/kg/min com os respectivos desvios-padrão foram: Homem ativo: G1-50,6 ± 7,3; G2-47,4 ± 7,4; G3-45,4 ± 6,8; G4-40,5 ± 6,5; G5-35,3 ± 6,2; G6-30,0 ± 6,1. Mulher ativa: G1-38,9 ± 5,7; G2-38,1 ± 6,6; G3-34,9 ± 5,9; G4-31,1 ± 5,4; G5-28,6 ± 6,1; G6-25,1 ± 4,4. Homem sedentário: G1-47,4 ± 7,9; G2-41,9 ± 7,2; G3-39,0 ± 6,8; G4-35,6 ± 7,7; G5-30,0 ± 6,3; G6-23,1 ± 6,3. Mulher sedentária: G1-35,6 ± 5,7; G2-34,0 ± 4,8; G3-30,0 ± 5,4; G4-27,2 ± 5,0; G5-23,9 ± 4,2; G6-21,2 ± 3,4. CONCLUSÃO: ESte artigo fornece valores de referência de VO2 máx, entre outros parâmetros, no Teste Cardiopulmonar realizados na esteira ergométrica em indivíduos de ambos os sexos, ativos e sedentários.