Academic literature on the topic 'Acide oxamique'

The presence of small amounts of iron (>0.013% Fe) in sand creates problems in the manufacture of high quality glass. Removal by hot sulphuric acid is possible, but creates environmental problems, and is costly. Hence organic acids such as oxalic have been investigated since they are effective in removing iron, and can be degraded anaerobically. The aim of this work was to identify key intermediates in the anaerobic degradation of oxalate in an upflow anaerobic sludge blanket reactor (UASB) which was removing iron from solution in the sulphide form, and to determine the bacterial species involved. 2-bromoethanesulfonic acid (BES) and molybdenum were selected as suitable inhibitors for methanogenic and sulphate reducing bacteria (SRB) respectively. 40mM molybdenum was used to inhibit the SRB in a reactor with a 12hr HRT. Total SRB inhibition took place in 20 hrs, with a complete breakthrough of influent sulphate. The lack of an immediate oxalate breakthrough confirmed Desulfovibrio vulgaris subspecies oxamicus was not the predominant oxalate utilising species. Nevertheless, high concentrations of molybdenum were found to inhibit oxalate utilising bacteria in granular reactors but not in suspended population reactors; this observation was puzzling, and at present cannot be explained. Based on the intermediates identified, it was postulated that oxalate was degraded to formate by an oxalate utilising bacteria such as Oxalobacter formigenes, and the formate used by the SRBs to reduce sulphate. Acetate, as a minor intermediate, existed primarily as a source of cell carbon for oxalate utilising bacteria. Methanogenic inhibition identified that 62% of the CH4 in the reactor operated at 37°C originated from hydrogenotrophic methanogenesis, whilst this figure was 80% at 20°C. Possible irreversible effects were recorded with hydrogenotrophic methanogens.

The latest world malaria report revealed that human deaths caused by malaria are currently on the rise and presently stood at over 627,000 per year. In addition, more than 240 million people have the infection at any given time. These figures make malaria the topmost infectious disease and reiterate the need for continuous efforts for the development of novel chemotherapies. Malaria is an infectious disease caused majorly by the protozoan intracellular parasite Plasmodium falciparum and transmitted by mosquitoes. Reports abound on the central role of falcipains (cysteine protease enzymes) in the catabolism of hemoglobin for furnishing the plasmodium cells with amino acids that they require for development and survival in the hosts. Even though falcipains (FPs) have been validated as drug target molecules for the development of new antimalarial drugs, none of its inhibitory compounds have advanced beyond the early discovery stage. Therefore, there are renewed efforts to expand the collection of falcipain inhibitors. As a result, an interesting finding reported the discovery of a quinolinyl oxamide derivative (QOD) and an indole carboxamide derivative (ICD), with each compound demonstrating good potencies against the two essential FP subtypes 2 (FP-2) and 3 (FP-3). In this study, we utilized microsecond-scale molecular dynamics simulation computational method to investigate the interactions between FP-2 and FP-3 with the quinolinyl oxamide derivative and indole carboxamide derivative. The results revealed that quinolinyl oxamide derivative and indole carboxamide derivative bound tightly at the active site of both enzymes. Interestingly, despite belonging to different chemical scaffolds, they are coordinated by almost identical amino acid residues via extensive hydrogen bond interactions in both FP-2 and FP-3. Our report provided molecular insights into the interactions between FP-2 and FP-3 with quinolinyl oxamide derivative and indole carboxamide derivative, which we hope will pave the way towards the design of more potent and druglike inhibitors of these enzymes and will pave the way for their development to new antimalarial drugs.

Ces travaux de thèse portent sur la synthèse de polyuréthanes par génération in situ d’isocyanates, à travers différentes voies de moindre toxicité que la voie classique faisant appel à l’utilisation directe d’isocyanates. Dans un premier temps, la décarboxylation oxydante des acides oxamiques conduisant à la formation d’isocyanates a été réalisée par activation thermique grâce à l’utilisation d’un iodure hypervalent, jouant le rôle d’oxydant. Une étude cinétique sur des réactions modèles en présence d’alcool, associé à une modélisation numérique, ont notamment mis en évidence un effet catalytique de l’acide acétique, sous-produit de la réaction, sur la formation de liaisons uréthane. La formation de CO2 généré par cette réaction menant à la formation d’isocyanates, a ensuite été exploitée, pour la synthèse de mousses polyuréthanes réticulées. Les effets de différents paramètres, tels la nature des monomères ou la température de réaction, sur la morphologie et les propriétés des mousses obtenues ont ensuite été étudiés. Cette réaction d’activation des acides oxamiques a ensuite été réalisée par irradiation lumineuse en présence d’un photocatalyseur, permettant d’élaborer des films polyuréthanes. La modification des composés du mélange réactionnel a permis de développer des formulations homogènes, notamment en changeant la nature de l’iodure hypervalent utilisé. Enfin, la synthèse d’uréthanes et de polyuréthanes à partir de 1,4,2-dioxazol-5-ones a été explorée. Après une optimisation des conditions catalytiques permettant la génération d’isocyanates par ouverture de ces hétérocycles, le CO2 aussi formé a été exploité pour la production de mousses polyuréthanes
This PhD work focus on the synthesis of polyurethanes through the in situ generation of isocyanates, using pathways with lower toxicity compared to the classical approach involving the direct use of isocyanates. The oxidative decarboxylation of oxamic acids leading to the formation of isocyanates was, first, carried out by thermal activation using a hypervalent iodine as an oxidant. A kinetic study on model reactions in the presence of alcohol, combined with computational modeling, notably revealed a catalytic effect of acetic acid, a by-product of the reaction, on the formation of urethane bonds. The CO2 generated by this reaction, leading to the formation of isocyanates, was then exploited for the synthesis of cross-linked polyurethane foams. The effects of various parameters, such as the nature of the monomers or the reaction temperature, on the morphology and properties of the obtained foams were thereafter studied. This activation reaction of oxamic acids was then carried out by light irradiation in the presence of a photocatalyst, allowing the production of polyurethane films. Modifying the components of the reaction mixture enabled the development of homogeneous formulations, particularly by changing the nature of the hypervalent iodine used. Finally, the synthesis of urethanes and polyurethanes from 1,4,2-dioxazol-5-ones was explored. After optimizing the catalytic conditions for generating isocyanates through the opening of these heterocycles, the generated CO2 was exploited for the production of polyurethane foams

碩士
中原大學
化學研究所
91
ABSTRACT This thesis discusses the supramolecular chemistry of silver (Ⅰ) complexes containing polydentate nitrogeneous ligands. A series of silver (Ⅰ) complexes of the types {[Ag2(H2DpyO)2(pyOa)](BF4)} �V, 1 , {[Ag2(H2DpyO)2(pyOa)](ClO4)} �V, 2 , {[Ag2(H2DpyO)2(pyOa)](PF6)} �V, 3 and {[Ag2(H2DpyO)2(pyOa)(NO3)]} �V, 4 , have been prepared by reaction of AgX ( X = BF4-, ClO4-, PF6-, NO3-) with H2DpyO ( H2DpyO = N,N'-di(2-pyridyl)oxamide ) in EtOH / H2O , where pyOa is anion of N-pyridin-2-yl-oxalamic acid . The H2DpyO ligand in 1~4 are coordinated to the silver (Ⅰ) centers through two terminal pyridine nitrogen atoms, while the pyOa ligands are coordinated to silver (Ⅰ) centers through two oxygen atoms and the pyridine nitrogen atoms , forming ladder -type structures . The anions , BF4- , ClO4- and PF6- are not coordinated to the silver (Ⅰ) atoms in complexes 1~3. The ladders are interlinked to each other through a series of Ag…O , Ag…F interactions and Cpy-H…F-B , Cpy-H…O-Cl , Cpy-H…F-P hydrogen bondings , while the molecules are interlinked to each other through Cpy-H…O-N hydrogen bondings in complex 4.