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Fate and Impact of Canola Oil in Aquatic Environments Under Aerobic ConditionsCampo, Pablo January 2009 (has links)
No description available.
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On the Formation of Cholesterol Autoxidation Products in Lipid Bilayers and Electrophilic Secosterols Derived TherefromSchaefer, Emily Lydia 04 September 2019 (has links)
Lipid peroxidation is believed to play a key role in the onset and progression of degenerative disease. Interestingly, although cholesterol is the most abundant lipid in the human body, our understanding of its autoxidation and subsequent decomposition is relatively limited. In fact, until recently, cholesterol-7-hydroperoxide was accepted as the only primary product of cholesterol autoxidation in organic solution, however, our group exhibited that the 4-, 5-, and 6-hydroperoxides are also formed. Although this work facilitated thorough investigation of the complexities of both H-atom abstraction and addition in cholesterol autoxidation in organic solution, it did not account for the dynamic environment of a cell membrane. Herein, we report on the product distribution of these primary autoxidation products in lipid bilayers and how antioxidant supplementation, H-bonding interactions, and concentration of polyunsaturated fatty acid (PUFA) substrate influence both the product distribution and efficiency of autoxidation.
Indeed, not only does H-bonding of the 3β-OH of cholesterol appear to shut-down C4 H-atom abstraction, the absence of kinetic chol-5α-OOH product is likely due to the poor potency of α- tocopherol (α-TOH), also as a result of H-bonding with phosphate head group of lipid membrane phospholipids. Therefore, within a lipid membrane the 7-hydroperoxide products predominate, consistent with literature precedent, however the factors involved are more complex than previously understood. Moreover, with the authentic cholesterol hydroperoxides in hand, we sought to determine
if the different regioisomers exhibit different cytotoxicity. Glutathione peroxidases (GPXs) are cytoprotective enzymes that reduce harmful hydroperoxides to benign alcohols in vivo. Using RSL3, a small-molecule inhibitor for GPX4, we were able to sensitize mammalian cells to ferroptotic cell death via administration of our exogenously prepared chol-OOHs. Surprisingly, we found that the toxicities of each of 7α-OOH, 6β-OOH and 5α-OOH were only marginally augmented by RSL3 treatment, suggesting that they do not substantially sensitize cells to ferroptosis, perhaps because their decomposition to lipid peroxidation chain-initiating species (i.e. alkoxyl radicals) is not particularly efficient. Instead their cytotoxicities may derive from other mechanisms, such as the induction of apoptosis. This inspired our investigation of the fate of lipid hydroperoxides in vivo, namely the secondary products of the predominant 7-hydroperoxide species.
Acid-catalyzed Hock fragmentation, known for the industrial synthesis of phenol and
acetone from cumene or implication in the generation of 4-hydroxynonenal (4-HNE), of 5α- and 6β-OOH has been shown by our group to produce highly electrophilic secosterol species; we sought to investigate the same decomposition mechanism for 7α-OOH in light of our investigations in the lipid membrane. Interestingly, we found that Hock fragmentation of 7α-OOH does not exhibit products resulting from the anticipated O-vinyl oxocarbenium intermediate, rather, the mechanism appears to funnel through an α-epoxy carbenium to produce unprecedented A-ring cleavage and epoxide products. Herein, we describe our thorough analysis of this chol-7α-OOH Hock fragmentation and attempts to investigate the presence of these products in biological samples, similar to previous analyses of similar products in atherosclerotic plaque extracts. The products isolated and characterized through this work have provided new mechanistic insight with regards to the primary and secondary oxidation products of cholesterol in vivo; through further development of these findings, we hope to provide a better understanding of the implications of cholesterol oxidation in the pathogenesis of atherosclerosis.
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\"Auto-oxidação da hemoglobina de Glossoscolex paulistus: efeito do pH, do cianeto e do surfactante aniônico SDS\" / \"Autoxidation of Glossoscolex paulistus hemoglobin: effect of pH, cianide and anionic surfactant SDS\"Leves, Alessandra Lima Poli 25 May 2006 (has links)
O arranjo oligomérico e as mudanças na estrutura polipeptídica podem influenciar fortemente na velocidade de auto-oxidação das hemoproteínas, assim como os diferentes nucleófilos que atuam neste processo em função do pH. No presente trabalho, a velocidade de auto-oxidação da hemoglobina extracelular gigante de Glossoscolex paulistus (HbGp) em seu estado íntegro e do monômero d isolado é estudada em função do pH e na presença do ligante cianeto. O comportamento da curva cinética é dependente do pH, apresentando-se monofásico ou bifásico dependendo do estado de oligomerização da proteína. Assim, nos valores de pH que geram a dissociação oligomérica, a curva cinética foi bifásica. Na faixa de pH 5,9-7,3, que apresenta a proteína íntegra, foi verificado um comportamento cinético mono-exponencial. Em meio alcalino, a auto-oxidação da hemoglobina íntegra na presença dos ligantes hidroxila e/ou cianeto apresenta comportamento complexo, descrito pela combinação de duas cinéticas de primeira-ordem. O processo lento ocorre devido à auto-oxidação do monômero d e o processo rápido é atribuído ao trímero abc. Em pH 7,0, a cinética é mono-exponencial, indicando uma estrutura oligomérica altamente preservada. Em meio ácido, tanto a hemoglobina íntegra como o monômero d apresentam a auto-oxidação catalisada por próton. É observada, através das constantes de velocidade de auto-oxidação da hemoglobina íntegra na presença de cianeto, uma cooperatividade no processo rápido devido ao trímero da HbGp. Além disso, a influência do surfactante dodecil sulfato de sódio na auto-oxidação da HbGp é avaliada. Uma influência mais efetiva do SDS é constatada em pH 7,0, enquanto que, em pH 9,0, a dissociação oligomérica é a influência predominante. Provavelmente, esta diferença está relacionada ao ponto isoelétrico ácido da HbGp, que favorece a interação entre SDS e HbGp em pH 7,0, quando comparado ao pH 9,0. O mecanismo de auto-oxidação e as correlações entre a cinética e o arranjo oligomérico são discutidos em detalhes no presente trabalho. / The oligomeric assembly and the changes in the polypeptidic structure can to influence in the autoxidation rate of the heme proteins, as well as the different nucleophiles, which act in this process as a function of pH. In the present work, the autoxidation rate of the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp) in integral state and of the isolated d monomer is studied as a function of pH and in the presence of the cyanide ligand. The kinetic decay behavior is dependent of pH, presenting mono-exponential or biexponential character, depending of the oligomeric state of the protein. Thus, in the pH values that originated the oligomeric dissociation, the kinetic decay was i-exponential. In the pH range 5.9 - 7.3, which show the whole protein, a monoexponential kinetic behavior was verified. In alkaline medium, the whole hemoglobin autoxidation in the presence of the hydroxyl and/or cyanide presents complex behavior described by the combination of two first order kinetics. The slow process occurs due to the d monomer autoxidation and the fast process is attributed to abc trimer. At pH 7.0, the kinetic is monoexponential,indicating a highly conserved oligomeric structure. In acid medium, both, the whole hemoglobin and the d monomer presented the proton-catalyzed autoxidation. A cooperativity in the fast process due to trimer of the HbGp can be observed, through the autoxidation rate constants of the whole hemoglobin in the presence of cyanide. Furthermore, the influence of the anionic surfactant sodium dodecyl sulfate (SDS) in the HbGp autoxidation was evaluated. At pH 7.0, it was verified a more effective influence for SDS, while at pH 9.0, the oligomeric dissociation was the main influence. Probably, this difference is related to the acid isoelectric point of the HbGp, which favors the interaction between SDS and HbGp at pH 7.0, as compared with the pH 9.0. The autoxidation mechanism and the correlation between the kinetic and the oligomeric arrangement are discussed in details in the present work.
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The Health Consequences of Fructose, its Metabolite, Dihydroxyacetone and the Hepatoprotective Effects of Selected Natural Polyphenols in Rat HhepatocytesLip, Ho Yin 26 June 2014 (has links)
The introduction of high fructose corn syrup into the diet has been proposed to be the cause of many illnesses related to the metabolic syndrome. Fructose and its metabolites can be metabolized into cytotoxic reactive dicarbonyls that can cause damage to macromolecules leading to deleterious consequences. Dihydroxyacetone, a fructose metabolite, was studied in this thesis. Its ability to autoxidize and cause protein carbonylation under standard (pH 7.4, 37°C) and oxidative stress conditions (Fentons reagent) was investigated. Dihydroxyacetone was able to form significant amounts of dicarbonyls and protein carbonylation. Several selected natural polyphenols were chosen for an in vitro toxicological study involving rat hepatocytes. The chosen dietary polyphenols were rutin, gallic acid, methylgallate, ethylgallate, propylgallate and curcumin. In this thesis, the polyphenols were found to be able to significantly protect against the deleterious effects of glyoxal and methylglyoxal. In summary, these polyphenols could be candidates for future in vivo studies.
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The Health Consequences of Fructose, its Metabolite, Dihydroxyacetone and the Hepatoprotective Effects of Selected Natural Polyphenols in Rat HhepatocytesLip, Ho Yin 26 June 2014 (has links)
The introduction of high fructose corn syrup into the diet has been proposed to be the cause of many illnesses related to the metabolic syndrome. Fructose and its metabolites can be metabolized into cytotoxic reactive dicarbonyls that can cause damage to macromolecules leading to deleterious consequences. Dihydroxyacetone, a fructose metabolite, was studied in this thesis. Its ability to autoxidize and cause protein carbonylation under standard (pH 7.4, 37°C) and oxidative stress conditions (Fentons reagent) was investigated. Dihydroxyacetone was able to form significant amounts of dicarbonyls and protein carbonylation. Several selected natural polyphenols were chosen for an in vitro toxicological study involving rat hepatocytes. The chosen dietary polyphenols were rutin, gallic acid, methylgallate, ethylgallate, propylgallate and curcumin. In this thesis, the polyphenols were found to be able to significantly protect against the deleterious effects of glyoxal and methylglyoxal. In summary, these polyphenols could be candidates for future in vivo studies.
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Avaliação de metodologias teóricas no estudo de propiedades termoquímicas e mecanismos reacionais envolvidos na oxidação do colesterol / Evaluation of theorical methodologies in the study of thermochemical properties and reaction mechanisms involved in the cholesterol oxidationHeerdt, Gabriel, 1987- 17 August 2018 (has links)
Orientador: Nelson Henrique Morgon / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-17T17:43:18Z (GMT). No. of bitstreams: 1
Heerdt_Gabriel_M.pdf: 1500564 bytes, checksum: dd39ed6bdcbfe660248d76bcaee6963f (MD5)
Previous issue date: 2011 / Resumo: O objetivo principal deste trabalho foi analisar alguns dos mecanismos reacionais de oxidação da molécula de colesterol. Para que isso fosse possível, desenvolveu-se uma metodologia de cálculos à partir da análise de diferentes funcionais de densidade, conjuntos de funções de base e método ONIOM. A metodologia que realiza cálculos no nível ONIOM2(QCISD(T)/6-311++G(2df,p): HF/6-31G(d)//B3LYP/6-31G(d):HF/6-31G(d)) resultou nos menores desvios médios absolutos para afinidades por próton e eletrônica, 5,38 kJ/mol e 0,107 eV, respectivamente, para as 65 moléculas utilizadas no processo de validação. Essa metodologia comparada aos métodos propostos na literatura, G3(MP2) e G3(B3), possui desvios absolutos estatisticamente inferiores e vantagem em tempo computacional. Ao aplicar-se esse nível de teoria no estudo dos mecanismos de autoxidação do colesterol, observa-se uma concordância com dados experimentais que indicam a preferência pela reação através da posição equatorial. As reações de epoxidação seguida pela hidratação, foram realizadas pela transferência de um átomo de oxigênio da molécula de peróxido de hidrogênio para o colesterol, havendo a quebra da insaturação e consequente formação de um triol da molécula de colesterol / Abstract: The main objective of this study was to analyze some oxidation reaction mechanisms involving cholesterol molecule. A calculation methodology considering the analysis of different density functionals, basis sets and ONIOM method. The methodology that performs calculations at the level ONIOM2(QCISD(T)/6-311++G(2df,p):HF/6-31G(d)//B3LYP/6-31G(d):HF/6-31G(d)) resulted in smaller absolute mean deviations for proton and electron affinities, 5.38 kJ/mol and 0.107 eV, respectively, for the 65 molecules used in the validation process. This methodology in comparison with composite methods G3(MP2) and G3(B3), has a lower absolute deviation. Another advantage is the lower computational cost. This methodology when applied to the cholesterol autoxidation mechanisms gives a good agreement with experimental data. The results indicate that the reaction proceeds through the attach at the equatorial position. The next steps involve epoxidation and hidratation reactions. The oxigen is transfered from hydrogen peroxide to cholesterol molecule. The insaturation is broken and the cholesterol triol molecule is formed / Mestrado / Físico-Química / Mestre em Química
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\"Auto-oxidação da hemoglobina de Glossoscolex paulistus: efeito do pH, do cianeto e do surfactante aniônico SDS\" / \"Autoxidation of Glossoscolex paulistus hemoglobin: effect of pH, cianide and anionic surfactant SDS\"Alessandra Lima Poli Leves 25 May 2006 (has links)
O arranjo oligomérico e as mudanças na estrutura polipeptídica podem influenciar fortemente na velocidade de auto-oxidação das hemoproteínas, assim como os diferentes nucleófilos que atuam neste processo em função do pH. No presente trabalho, a velocidade de auto-oxidação da hemoglobina extracelular gigante de Glossoscolex paulistus (HbGp) em seu estado íntegro e do monômero d isolado é estudada em função do pH e na presença do ligante cianeto. O comportamento da curva cinética é dependente do pH, apresentando-se monofásico ou bifásico dependendo do estado de oligomerização da proteína. Assim, nos valores de pH que geram a dissociação oligomérica, a curva cinética foi bifásica. Na faixa de pH 5,9-7,3, que apresenta a proteína íntegra, foi verificado um comportamento cinético mono-exponencial. Em meio alcalino, a auto-oxidação da hemoglobina íntegra na presença dos ligantes hidroxila e/ou cianeto apresenta comportamento complexo, descrito pela combinação de duas cinéticas de primeira-ordem. O processo lento ocorre devido à auto-oxidação do monômero d e o processo rápido é atribuído ao trímero abc. Em pH 7,0, a cinética é mono-exponencial, indicando uma estrutura oligomérica altamente preservada. Em meio ácido, tanto a hemoglobina íntegra como o monômero d apresentam a auto-oxidação catalisada por próton. É observada, através das constantes de velocidade de auto-oxidação da hemoglobina íntegra na presença de cianeto, uma cooperatividade no processo rápido devido ao trímero da HbGp. Além disso, a influência do surfactante dodecil sulfato de sódio na auto-oxidação da HbGp é avaliada. Uma influência mais efetiva do SDS é constatada em pH 7,0, enquanto que, em pH 9,0, a dissociação oligomérica é a influência predominante. Provavelmente, esta diferença está relacionada ao ponto isoelétrico ácido da HbGp, que favorece a interação entre SDS e HbGp em pH 7,0, quando comparado ao pH 9,0. O mecanismo de auto-oxidação e as correlações entre a cinética e o arranjo oligomérico são discutidos em detalhes no presente trabalho. / The oligomeric assembly and the changes in the polypeptidic structure can to influence in the autoxidation rate of the heme proteins, as well as the different nucleophiles, which act in this process as a function of pH. In the present work, the autoxidation rate of the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp) in integral state and of the isolated d monomer is studied as a function of pH and in the presence of the cyanide ligand. The kinetic decay behavior is dependent of pH, presenting mono-exponential or biexponential character, depending of the oligomeric state of the protein. Thus, in the pH values that originated the oligomeric dissociation, the kinetic decay was i-exponential. In the pH range 5.9 - 7.3, which show the whole protein, a monoexponential kinetic behavior was verified. In alkaline medium, the whole hemoglobin autoxidation in the presence of the hydroxyl and/or cyanide presents complex behavior described by the combination of two first order kinetics. The slow process occurs due to the d monomer autoxidation and the fast process is attributed to abc trimer. At pH 7.0, the kinetic is monoexponential,indicating a highly conserved oligomeric structure. In acid medium, both, the whole hemoglobin and the d monomer presented the proton-catalyzed autoxidation. A cooperativity in the fast process due to trimer of the HbGp can be observed, through the autoxidation rate constants of the whole hemoglobin in the presence of cyanide. Furthermore, the influence of the anionic surfactant sodium dodecyl sulfate (SDS) in the HbGp autoxidation was evaluated. At pH 7.0, it was verified a more effective influence for SDS, while at pH 9.0, the oligomeric dissociation was the main influence. Probably, this difference is related to the acid isoelectric point of the HbGp, which favors the interaction between SDS and HbGp at pH 7.0, as compared with the pH 9.0. The autoxidation mechanism and the correlation between the kinetic and the oligomeric arrangement are discussed in details in the present work.
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Inhibitory Mechanism for Amyloid β42 Aggregation by Catechol-type Flavonoids / カテコール型フラボノイドによるアミロイドβ42 凝集抑制機構Sato, Mizuho 24 March 2014 (has links)
Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(農学) / 甲第18328号 / 農博第2053号 / 新制||農||1022(附属図書館) / 学位論文||H26||N4835(農学部図書室) / 31186 / 京都大学大学院農学研究科食品生物科学専攻 / (主査)教授 入江 一浩, 教授 河田 照雄, 教授 保川 清 / 学位規則第4条第1項該当
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On the Mechanism of Cytoprotection by Ferrostatin-1 and Liproxstatin-1 and the Role of Lipid Peroxidation in Ferroptotic Cell Death & Targeting Tetrahydronaphthyridinols to the MitochondriaZilka, Omkar 28 March 2018 (has links)
Lipid peroxidation is well established to contribute to the etiology of many deteriorative conditions including neurodegeneration, cardiovascular disease, cancer, aging, and recently in ferroptosis—a regulated, necrotic modality of cell death that results from the accumulation of lipid hydroperoxides. Recent high-throughput screening efforts have uncovered ferrostatin-1 (Fer-1) and liproxstatin-1 (Lip-1) as two premiere inhibitors of ferroptosis. We propose that these compounds function as radical trapping antioxidants. We employ a systematic methodology of evaluating inherent radical trapping antioxidant (RTA) activity of Lip-1, Fer-1, and various aryl amine and aryl nitroxide analogues to put forward a biologically relevant mechanism of action based on our previous work in the field. Joining these observations with the efficacy of tetrahydronaphthyridinols (THNs), the results support a clear role of autoxidation in the execution of ferroptosis.
Next, we expand the THN repertoire by targeting the payload towards the engine of our cells, the mitochondria. Decades of research have implicated mitochondrial dysfunction brought about by the peroxidation of mitochondrial membranes and the leaking of downstream oxidants, in the death of their symbiotic host cells. Isolated successes in the field have been demonstrated academically, though viable drugs remain to be developed, partially due to the lack of effective diagnostic tools. We endeavor to address some of these issues by investigating mitochondrially-targeted THNs (MitoTHNs) as a targeted chain-breaking antioxidant of unparalleled potency. Furthermore, we advance development of the THNs towards therapeutic applications by demonstrating their biodistribution in mice.
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Deposit Formation of Deoxygenated JP-8 Fuel with Added HydroperoxidesKerr, Kristen Rita January 2013 (has links)
No description available.
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