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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
51

Bilirubin: an Animal Pigment in the Zingiberales and Diverse Angiosperm Orders

Pirone, Cary L 05 November 2010 (has links)
Strelitziaceae is a tropical monocot family comprising three genera and seven species: Ravenala Adans and Phenkospermum Endl., which are monotypic, and five species of Strelitzia Aiton. All species produce woody capsular fruits that contain vibrantly colored arillate seeds. Arils of the Strelitzia species are orange, those of Phenakospermum are red, and those of Ravenala are blue. Unlike most plant pigments, which degrade after cell death, aril pigments in the family persist for decades. Chemical properties of the compounds are unusual, and do not match those of known pigment classes (carotenoids, flavonoids, betalains, and the chlorophylls). I isolated the orange pigment from the arils of Strelitzia nicolai, and performed HPLC-ESMS, UV-visible, 1H NMR and 13C NMR analyses to determine its chemical structure. These data indicated the pigment was bilirubin-IX, an orange-yellow tetrapyrrole previously known only in mammals and some other vertebrates as the breakdown product of heme. Although related tetrapyrroles are ubiquitous throughout the plant kingdom and include vital biosynthetic products such as chlorophyll and phytochromobilin, this is the first report of bilirubin in a plant, and evidence of an additional biosynthetic pathway producing orange coloration in flowers and fruits.
52

EN KLINISK STUDIE AV ANALYSEN CSV-SPEKTROFOTOMETRI - EN JÄMFÖRELSE AV GLAS- OCH PLASTKYETTER FÖR SPEKTROFOTOMETRISK MÄTNING AV BILIRUBIN OCH DEOXIHEMOGLOBIN I CEREBROSPINALVÄTSKA

Carlander, Jonatan January 2016 (has links)
En subaraknoidalblödning (SAB) orsakas av ruptuerade aneurysmer mellan den mjuka hjärnhinnan och spindelvävshinnan (arachnoidea). Symptomen för SAB är allvarlig spontan huvudvärk, stelhet i nacken, kräkningar, förvirring och svimning. Vid erhållna symptom görs en datortomografi (CT) av hjärnan för påvisning av blod i subaraknoidalrummet. I 98 % av fallen påvisar CT blod om undersökning görs inom 12 timmar från uppvisat symtom. Sannolikheten att påvisa blod med CT minskar dock med tiden. Efter en vecka kan blod påvisas i drygt 50 % av fallen. Vid symptom för en SAB men där CT inte påvisar blod görs en lumbalpunktion för analys av cerebrospinalvätska (CSV). Provtagning bör ske minst 12 timmar efter uppvisat symptom för bilirubin ska ha hunnit bildats från oxihemoglobin via enzymatiska reaktioner. Spektrofotometri används vid 415 nm för detektion av oxihemoglobin och vid 476 nm för detektion av bilirubin. Denna studie kommer undersöka huruvida det finns någon skillnad i uppmätt absorbans vid 415 nm respektive 476 nm mellan glas- och plastkyvetter samt undersöka hur ett dygns extra förvaring av CSV-prover påverkar absorbansen vid 476 nm. Resultatet för 20 CSV-prover visade på att det inte fanns någon statistiskt signifikant skillnad mellan glas- och plastkyvetter (p=0,825 för 476 nm, p=0,632 för 415 nm) samt att absorbansen för 9 CSV-prover signifikant förändrades vid 476 nm efter ett dygns extra förvaring (p=0,01). / A subarachnoid haemorrhage (SAH) is caused by ruptured aneurysms between the soft meninges and arachnoid (arachnoid). Symptoms of an SAH is severe spontaneous headaches, stiff neck, vomiting, confusion and fainting. A computed tomography (CT) of the brain is used, on patients sustaining symptoms, to detect blood in the subarachnoid space. CT detects blood in 98% of the cases if examination is made within 12 hours from the shown symptoms. However, the probability of detecting blood with CT decreases with time. After a week, only 50 % of the CT-scans identifies blood. If patients suffers from typical symptoms but no detection of blood using CT-scan, a lumbar puncture is performed to analyse the cerebrospinal fluid (CSF). Sampling should be made at least 12 hours after presented symptoms because of the time-dependent creation of bilirubin from oxyhemoglobin via enzymatic reactions. Spectrophotometry is used in the wavelengths 415 nm for the detection of oxyhemoglobin and at 476 nm for detection of bilirubin. This study will examine whether there is any difference in the absorbance measured at 415 nm and 476 nm between glass-and plastic cuvettes as well as examine how 24 hours of extra storage of samples affect the absorbance at 476 nm. The result for 20 CSF-samples showed that there was no statistically significant difference between the glass and plastic cuvettes (p = 0,825 of 476 nm, p = 0,632 for 415 nm), and absorbance for 9 CSF-samples significantly changed at 476 nm after 24 hours of extra storage (p = 0.01).
53

Bilirubin modulates leukocyte recruitment to sites of inflammation

Vogel, Megan E. 07 September 2017 (has links)
No description available.
54

Stanovení oxidačních produktů bilirubinu / Determination of bilirubine oxidation products

Čepa, Adam January 2013 (has links)
This thesis is focused on protective and antioxidant properties of bile pigment bilirubin. Bilirubin is a potent scavenger of free radicals and reactive oxygen species generated by increased oxidative stress. Mildly elevated systemic levels of bilirubin are actually associated with lower incidence of oxidative stress-mediated diseases, such as cardiovascular disease, atherosclerosis, diabetes and certain types of cancer. The main aim of this thesis was to prepare bilirubin oxidation products in vitro, characterize their physical-chemical properties and thein determine biological impact.
55

Nanostructuration des électrodes pour l'électrocatalyse enzymatique : vers une biopile H2/O2 "verte" / Electrode nanostructuration for enzyme electrocatalyst : towards a "green" H2/O2 fuel cell

Monsalve Grijalba, Karen 06 December 2016 (has links)
Parmi les technologies basées sur H2 comme vecteur d’énergie, les biopiles à combustibles utilisant des enzymes comme biocatalyseurs spécifiques et efficaces au lieu des catalyseurs au platine apparaissent comme des alternatives émergentes. L’objectif de cette thèse est de comprendre les paramètres gouvernant l’immobilisation fonctionnelle sur des interfaces nanostructurées d'enzymes spécifiques de l’oxydation de H2 et de la réduction d’O2 en vue de désigner une biopile H2/O2 performante.Divers nanomatériaux sont caractérisés, nanoparticules d’or (AuNP) et nanotubes de carbone (CNT), présentant différentes tailles et chimie de surface, aptes à développer des ratios importants surface/volume, autorisant une augmentation du nombre de molécules enzymatiques incorporées et donc une augmentation des courants catalytiques. L’immobilisation des enzymes sur AuNP a permis de discriminer entre l’augmentation de surface ou un effet nano sur l’efficacité catalytique. L’étude intégrée sur CNT, avec les charges de l’interface électrochimique, les charges et moments dipolaires des enzymes considérées, a permis de démontrer que les interactions électrostatiques contrôlent le processus de transfert d’électrons. Cette étude montre que les bases moléculaires pour une immobilisation efficace des enzymes, obtenues sur monocouches est applicables aux réseaux 3D.La détermination des nanostructures optimales pour les réactions enzymatiques est étudiée pour un changement d’échelle. Ainsi des feutres de carbone sont fonctionnalisés avec les nanostructures adaptées, pour au final développer la première biopile H2/O2 capable d’alimenter un multicapteur et un système de communication sans fil. / Among the technologies based on H2 as an energy carrier, biofuel cells that use specific and effective enzymes as biocatalysts instead of platinum catalysts appear as emerging alternative. The objective of this thesis is to understand the parameters governing the functional immobilization of specific enzymes for H2 oxidation and O2 reduction reactions on nanostructured interfaces, aimed to design a performant H2 / O2 biofuel cell.Gold nanoparticles (AuNP) and carbon nanotubes (CNT) having different sizes and surface chemistry are characterized. These nanomaterials develop important ratios surface / volume ratio, allow an increment in the number of enzyme molecules immobilized and therefore an increase catalytic currents. The immobilization of enzymes on AuNP allowed the discrimination between the increase in surface area and a nanomaterial effect on catalytic efficiency. The study on CNT integrates the charge of the electrochemical interface, dipole moments and the surface charge of enzymes. It demonstrated that electrostatic interactions control the electron transfer process. This study shows that the molecular basis for effective immobilization of enzymes, obtained on monolayers is applicable to 3D networks.The determination of the best parameters for enzymatic reactions, allows the development of an optimized 3-D volumetric interface based on carbon felt. We finally design for the first time a H2/O2 biofuel cell able to generate enough electric power to feed a complete wireless communication device.
56

Clinical and clinicopathological studies in healthy horses and horses with colic / Klinische und klinisch-pathologische Studien von gesunden Pferden und Pferden mit Kolik

Gomaa, Naglaa Abdel Megid 20 June 2011 (has links) (PDF)
In order to investigate the effect of food restriction on fat mobilization in horses with impaction in left ventral colon during treatment, serum triglycerides, NEFA and total bilirubine (TB) were measured before and after treatment. On another side, the determination of alcohol dehydrogenase (ADH) activity in serum could facilitate the distinguishing of the non-strangulating intestinal obstruction from the potential fatal strangulation obstruction and could submit a new prognostic biochemical parameter for intestinal strangulation. With the intention of giving a highlight over the analgesic effect of Buscopan® compositum in horses with colic, it was attempted to investigate the effect of Buscopan® compositum on the intestinal motility of healthy conscious horses in different regions of intestine. A significant elevation of NEFA and TB was observed in horses with impaction in left ventral colon at admission. By relieving the impaction, there was a significant elevation of triglycerides in comparison to its level at admission. There was a significant increase in ADH activity in all horses with acute intestinal obstruction. ADH activity was significantly higher in horses with strangulation in comparison to non-strangulation obstruction. There was only a significant correlation between ADH and lactate in horses with non-strangulation obstruction and colon torsion. Only AST and GLDH were significantly increased in horses with colon torsion. ADH activity > 20 U/l had 80.56% specificity and 80.49% sensitivity for discriminating horses with intestinal strangulation from non-strangulation obstruction. ADH activity < 80 U/l had 94.44% specificity and 66.67% sensitivity for survival. Buscopan® compositum had an immediate, rapid and significant (p< 0.05) reduction of duodenal, cecal and left ventral colon contractions after application. Cecal and left ventral colon contractions restored rapidly their normal contractions after 30 min, while duodenal contractions returned to the normal rate after 120 min of Buscopan® compositum administration. The horses with impaction in left ventral colon are susceptible to fat mobilization during the period of treatment as a result of food restriction. It was characterized by a revisable hypertri-glyceridemia and hyperbililrubinemia. Serum ADH activity could have a useful clinical value in detecting the intestinal strangulation and predicting the prognosis in horses with intestinal strangulation. Buscopan® compositum at its therapeutic dosage has an immediate, potent, short-lived reductive effect on cecum and left ventral colon contractions but a minor, longer effect on the duodenal contractions. Therefore, it is thought to be more effective in treatment of spasmodic colic than in large colon impaction. / Um den Effekt der Nahrungskarenz auf die Fettmobilisation bei Pferden mit Verstopfung der linken ventralen Längslagen des Kolons während der Behandlung zu untersuchen, wurden Triglyceride (TG), freie Fettsäuren (FFS) und Gesamtbilirubin (GB) bestimmt. Andererseits ermöglicht die Bestimmung der Aktivität der Alkoholdehydrogenase (ADH) im Serum die Unterscheidung zwischen einer nichtstrangulierenden intestinalen Obstruktion und einer potentiell tödlichen Strangulation. ADH kann somit als ein neuer prognostischer biochemischer Parameter für die intestinale Strangulation eingesetzt werden. Um den spasmolytischen Effekt von Buscopan compositum bei Pferden mit Kolik zu untersuchen, wurde der Effekt von Buscopan compositum auf die intestinale Kontraktion von gesunden Pferden in verschiedenen Regionen des Darmes getestet. Eine signifikante Erhöhung der FFS und des GB wurde bei Aufnahme von Pferden mit einer Verstopfung in der linken ventralen Längslagen festgestellt. Nach der Behandlung der Verstopfung konnte eine signifikante Erhöhung der Konzentration von TG, bezogen auf die TG Konzentration bei Aufnahme in die Klinik, festgestellt werden. Bei Pferden mit akuter intestinaler Obstruktion wurde eine signifikante Erhöhung der Aktivität der ADH beobachtet. Die Aktivität der ADH war bei Pferden mit einer Strangulation signifikant höher als bei Pferden, die eine nichtstrangulierende Obstruktion des Darmes hatten. Bei Pferden mit einer nichtstrangulierenden Obstruktion oder einer Kolontorsion wurde eine positive Korrelation zwischen der ADH-Aktivität und der Laktatkonzentration im Serum festgestellt. Nur bei Pferden mit Kolontorsion waren die Aktivitäten von AST und GLDH signifikant erhöht. Für die Unterscheidung zwischen Pferden mit einer intestinalen Strangulation oder einer nichtstrangulierenden Obstruktion wurde für die ADH- Aktivität größer als 20 U/l eine Spezifität von 80,56% und eine Sensitivität von 80,49% ermittelt. Eine ADH-Aktivität kleiner 80 U/l zeigt, mit einer Spezifität von 94,44% und einer Sensitivität von 66,67%, eine günstige Prognose für das Überleben des Pferdes an. Nach Gabe von Buscopan® compositum trat eine sofortige schnelle und signifikante (p<0,05) Reduktion der Kontraktionen im Duodenum, Zäkum und den linken ventralen Längslagen ein. Die Kontraktionen des Zäkums und der linken ventralen Längslagen normalisierten sich schnell innerhalb von 30 min, wogegen die Kontraktionen des Duodenums erst 120 min nach der Applikation von Buscopan® compositum den Normalzustand erreichten. Pferde mit einer Verstopfung in der linken ventralen Längslagen des Kolons sind während der medizinischen Behandlung anfällig für Fettmobilisation aufgrund der reduzierten Futter-aufnahme. Dies ist gekennzeichnet durch eine reversible Hypertriglyceridämie und eine Hyperbilirubinämie. Die Aktivität von ADH im Serum kann ein nützlicher klinischer Parameter sein, um eine intestinale Strangulation zu identifizieren und bietet sich auch als prognostischer Marker bei intestinaler Strangulation an. Die Applikation von Buscopan® compositum in der therapeutischen Dosierung hat eine sofortige, potente und kurzzeitige Reduktion der Kontraktionen des Zäkums und der linken ventralen Längslage aber einen geringen und länger anhaltenden Effekt auf die duodenalen Kontraktionen zur Folge. Daraus folgt, dass Buscopan® compositum bei der Behandlung von Krampfkoliken effektiver ist als bei Verstopfungen des großen Kolons.
57

Bilirubin Exerts Hormonal Regulation on Transcription of Genes Through Modulation of Key Coregulator Protein Recruitment

Miruzzi, Scott A. January 2021 (has links)
No description available.
58

Effets d’une hyperbilirubinémie modérée sur la physiologie de la déglutition nutritive et de la coordination déglutition-respiration chez l’agneau prématuré / Effect of moderate hyperbilirubinemia on nutritive swallowing and swallowing-breathing coordination in the preterm lamb

Bourgoin-Heck, Mélisande January 2016 (has links)
Résumé : L’ictère néonatal, lié à l’hyperbilirubinémie, touche 90% des nouveau-nés prématurés. L’hyperbilirubinémie provoque des troubles neurologiques aigus (somnolence, dystonie, difficultés alimentaires, atteinte de l’audition) et a été reliée à des anomalies du contrôle respiratoire. Ces résultats suggèrent une neurotoxicité de la bilirubine sur le tronc cérébral, qui pourrait aussi affecter les centres déglutiteurs. Le but de cette étude est de tester notre hypothèse selon laquelle l’hyperbilirubinémie altère la déglutition nutritive et la coordination déglutition-respiration chez l’agneau prématuré. 11 agneaux prématurés (nés 14 jours avant terme) ont été randomisés dans un groupe contrôle (n = 6) et un groupe bilirubine (n = 5). À 5 jours de vie, une hyperbilirubinémie modérée (150-250 μmol/L) était induite pendant 17h chez les agneaux du groupe bilirubine. La déglutition était étudiée par l’enregistrement de la pression pharyngée, et la respiration était évaluée par pléthysmographie d’inductance respiratoire et oxymétrie de pouls. L’effet de l’hyperbilirubinémie sur la déglutition nutritive (DN) était évalué pendant une alimentation au biberon standardisée, avec du lait de brebis. Un second enregistrement était réalisé 48h plus tard, après normalisation de la bilirubine. L’alimentation était moins performante (mL/min) dans le groupe bilirubine (p = 0,002) avec des DN moins fréquentes (p = 0,003) et de plus petit volume (p = 0,01). Ces différences n’étaient pas retrouvées à distance de l’hyperbilirubinémie. La coordination déglutition-respiration était également altérée chez les agneaux du groupe bilirubine, indiquée par une tendance à la diminution de la durée de l’inhibition respiratoire pendant les bouffées de DN (p < 0,1), ceci pendant et après l’hyperbilirubinémie. Simultanément, pendant l’alimentation, les agneaux du groupe bilirubine passaient plus de temps en désaturations sévère (< 80%) que ceux du groupe contrôle. Enfin, une diminution de la fréquence respiratoire associée à une augmentation des apnées étaient observées dans les minutes suivant l’alimentation dans le groupe bilirubine (p < 0,05). La déglutition et la coordination déglutition-respiration sont altérées par l’hyperbilirubinémie modérée, chez l’agneau prématuré. La diminution globale d’efficacité de l’alimentation au biberon est associée à une poursuite de la respiration durant les bouffées de DN, ce qui pourrait favoriser les aspirations pulmonaires de lait. / Abstract : Rationale: Jaundice, secondary to hyperbilirubinemia (HB), develops in 90% of preterm newborns. HB induces acute neurological disorders (somnolence, abnormal tone, feeding difficulties, auditory dysfunction) and has been linked to alterations in respiratory control. These findings suggest neurotoxicity in the brainstem that could also affect swallowing centers. This study aims to test our hypothesis that HB impairs nutritive swallowing and swallowing‐breathing coordination in the preterm lamb. Methods: Two groups of preterm lambs (born 14 days prior to term), control (C, n = 6) and hyperbilirubinemia (HB, n = 5) were studied. At day 5 of life, moderate HB (150‐250 μmol/L) was induced during 17 h in HB lambs. Swallowing was assessed via recording of pharyngeal pressure, and respiration was studied by respiratory inductance plethysmography and pulsed oximetry. HB effect on nutritive swallowing was assessed during standardized bottle‐feeding with ewe milk. A second recording was performed 48 hours later, after recovery from hyperbilirubinemia. Results: Swallows were less frequent (p = 0.003) and of smaller volume (p = 0.01) in HB lambs, with a consequent decrease in minute swallowing in HB lambs (p = 0,004). These differences were not found after bilirubinemia was returned to normal. Swallowing‐breathing coordination was also impaired in HB lambs, as indicated by a tendency towards a decrease in % time with respiratory inhibition during bursts of swallows, during and after hyperbilirubinemia. Simultaneously, severe desaturations (< 80%) were longer in HB lambs than in C lambs. Finally, a decreased respiratory rate was observed immediately after feeding (p < 0,05), along with increased apneas duration. Conclusions: Both swallowing and swallowing‐breathing coordination are altered by acute, moderate HB in preterm lambs. The overall decreased efficiency at bottle‐feeding is accompanied by continuation of breathing during bursts of swallows, which may promote lung aspiration.
59

Investigação da enzima Bilirrubina oxidase como catalisador da reação de redução eletroquímica de oxigênio / Investigation of the enzyme Bilirubin Oxidase as a catalyst for the oxygen electrochemical reduction reaction

Santos, Luciano dos 12 August 2010 (has links)
Bilirrubina oxidase de Myrothecium verrucaria é uma multicobre oxidase capaz de reduzir O2 pela oxidação de fenóis, aminas aromáticas e polipirróis. Eletroquimicamente, essa reação de redução ocorre pela transferência de elétrons entre a enzima e um eletrodo. Nesta tese, foi investigada a eficiência da enzima como agente redutor de O2 na superfície de eletrodos modificados pela função orgânica naftil-2-carboxilato por acoplamento de diazônio. Essa modificação na superfície do eletrodo aumenta em até quatro vezes a atividade do filme catalítico em relação à obtida por eletrodos em que a adsorção da enzima foi feita de forma convencional, sem a modificação. Foram estudados os efeitos da temperatura sobre a atividade da enzima para a redução de O2, sendo observado um aumento linear da atividade do eletrodo com o aumento da temperatura até 30 &deg;C, de tal forma que temperaturas mais altas proporcionaram o aumento da inativação natural das moléculas de enzima. Esse efeito de inativação foi confirmado pela diminuição da atividade com o tempo na presença de O2, por cronoamperometria, sendo a atividade interrompida pela inserção de argônio e retomada do mesmo ponto pela reinserção de O2, descartando a idéia da queda de corrente proveniente da dessorção de enzima. Foi estudado também o efeito do pH na máxima atividade da bilirrubina oxidase, conduzidos entre pH 5,0 e 8,0, e verificando-se que a máxima atividade da enzima foi obtida entre pH 5,5 e 6,0 e, além disso, verificou-se que a corrente catalítica em baixos valores de pH aumenta diretamente com o aumento do sobrepotencial aplicado. Porém, em altos valores de pH, a curva de redução toma a forma sigmoidal e passa a ser independente do sobrepotencial aplicado, sendo a reação governada por etapas químicas de transferência de prótons. O uso de eletrodos de disco rotatório possibilitou resolver parâmetros de Michaelis-Menten para a cinética do filme catalítico de forma mais precisa (a resposta de corrente é menos dependente do transporte de massa de reagentes) e esses dados foram obtidos dentro de um intervalo de pH importante para aplicações práticas. O sobrepotencial da reação de redução de O2 catalisada por bilirrubina oxidase foi comparado com o sobrepotencial obtido para a mesma reação catalisada por Platina eletrodepositada sobre a superfície de grafite pirolítico, onde foi observado um sobrepotencial de 140 mV para a catálise enzimática, demasiado menor que o valor de 415 mV obtidos para a Platina, sob as mesmas condições experimentais, em pH neutro. A metodologia proposta para a construção de um cátodo para aplicação em células a combustível enzimáticas e os subsequentes estudos possibilitaram uma investigação minuciosa para caracterizar a enzima bilirrubina oxidase como talvez o catalisador mais eficiente na redução eletroquímica de oxigênio molecular em células a combustível até o momento. / Bilirubin oxidase from Myrothecium verrucaria is a multicopper oxidase reducing O2 at the expenses of phenols, aromatic amines and polypyrrols oxidation. Electrochemically, this reduction reaction undergoes through the electron transfer between enzyme and electrode. In this thesis, the enzyme was investigated as an efficient O2 reducing agent on electrode surfaces modified by naphthil-2-carboxylate functionalities through diazonium coupling. This modification of the electrode surface increases the activity of the catalytic film up to four times comparing to that obtained by electrodes in which the enzyme molecules were adsorbed conventionally, without modification. It was studied the effect of temperature on O2 reduction, in which catalysis increased linearly with temperature up to 30 &deg;C, and higher temperatures increased the natural enzyme inactivation. This inactivation was confirmed by the activity drop off with time in the presence of O2, by chronoamperometry, ceased out when argon was inserted into the cell and re-established from the same point when argon was purged out by insertion of O2. These results cast aside the idea of activity drop off caused by enzyme desorption. It was also investigated the pH effect on the maximum activity of bilirubin oxidase, carried out between pH 5.0 and 8.0, being the highest activity obtained at pH 5.5-6.0. Furthermore, it was observed that the catalytic current directly increases with applied overpotential, at low pH values, and the reduction wave shape becomes sigmoidal and independent on applied overpotential at high pH values. The reaction is then governed by chemical steps, as the proton transfer. The use of rotating-disc electrodes favored solving the Michaelis-Menten kinetics for the catalytic film in a much greater accuracy (the current response is much less dependent on reagent mass transport) and these data were obtained for pH interval important for practical applications. The overpotential for the O2 reduction reaction catalyzed by bilirubin oxidase was compared to the overpotential obtained by the same reaction catalyzed by Platinum electrodeposited onto a pyrolytic graphite electrode. An overpotential of only 140 mV was observed for the enzymatic catalysis, much lower compared to the 415 mV obtained for the Platinum electrode, under the same experimental conditions, at neutral pH. The proposed method for constructing a cathode for enzymatic fuel cell application and subsequent investigation described allowed an in-depth study of bilirubin oxidase characterization as perhaps the most efficient catalysts for the electrochemical reduction of molecular oxygen in fuel cells to date.
60

Desenvolvimento de bioeletrodos miniaturizados para a aplicação em biocélulas a combustível implantáveis / Development of Implantable Glucose and Oxygen Biofuel Cell in Insects

Sales, Fernanda Cristina Pena Ferreira 07 November 2017 (has links)
As biocélulas a combustível enzimáticas (BFCs) são dispositivos eletroquímicos que convertem energia química em energia elétrica, utilizando enzimas como biocatalisadores. Quando miniaturizada, uma BFC pode ser implantada em animais vertebrados e invertebrados, vislumbrando-se sua utilização na produção de energia elétrica para alimentar microdispositivos biomédicos e microssensores em pequenos insetos. No entanto, ainda é um desafio obter BFCs implantáveis e miniaturizadas, com uma potência suficiente (dezenas de microwatts) para alimentar microcircuitos eletrônicos de maneira estável e em longo prazo. Diante do exposto, esta tese de doutorado apresenta um estudo das propriedades eletroquímicas de eletrodos enzimáticos, visando a aplicação em BFCs de glicose/O2 miniaturizadas e implantáveis. Para isso, utilizaram-se fibras flexíveis de carbono (FCFs) modificadas com as enzimas bilirrubina oxidase (BOx) no cátodo e glicose desidrogenase (GDh) NAD-dependente no ânodo, a fim de se obter a redução de O2 e a oxidação de glicose, respectivamente. Os resultados obtidos mostram que FCFs previamente submetidas a um tratamento químico de oxidação com permanganato de potássio e com posterior eletrodepolimerização do mediador vermelho neutro produzem bioânodos estáveis e robustos. Estes eletrodos, combinados com biocátodos compostos por FCFs na ausência de mediadores redox, foram utilizados em BFCs miniaturizadas, que foram implantadas em formigas da espécie Atta sexdens rubrupilosa. A potência máxima da BFC operando in vivo foi 13,5 &plusmn; 3,8 &micro;W cm-2 em 190 &plusmn; 58,9 mV, com corrente máxima de 143 &plusmn; 40,2 &micro;A cm-2 e a voltagem de circuito aberto de 260 &plusmn; 99,6 mV. Acredita-se que estes valores ainda possam ser otimizados e este trabalho contribui para mostrar que a flexibilidade das FFC, a presença de um mediador de elétrons polimérico no ânodo, o uso do tratamento químico de oxidação com permanganato de potássio das fibras e a miniaturização dos eletrodos são elementos importantes, e que podem ser considerados no desenvolvimento de biocélulas a combustível implantáveis. / Enzymatic biofuel cells (BFCs) are electrochemical devices that convert chemical energy into electrical energy using enzymes as biocatalysts. When miniaturized, BFCs can be implanted in vertebrate and invertebrate animals and, their use to produce electrical energy to feed biomedical microdevices and micro-sensors in small insects can be observed. However, it is still challenging to obtain implantable and miniaturized BFCs, with sufficient power (tens of microwatts) to power electronic microcircuits in a stable and long-term manner. In view of the above, this PhD thesis presents a study of the electrochemical properties of enzymatic electrodes, aiming to use them in miniaturized and implantable glucose/O2 BFCs. In order to obtain a reduction in O2 and oxidation of glucose, flexible carbon fibers (FCFs) modified with bilirubin oxidase (BOx) enzymes in the cathode and glucose dehydrogenase (GDh) at the anode, respectively, were used. The results show that FCFs previously submitted to a chemical treatment of oxidation with potassium permanganate and, subsequently, electropolymerization of the neutral red mediator produce stable and robust bioanodes. These electrodes, combined with biocathodes consisting of FCFs in the absence of redox mediators, were used in miniaturized BFCs, which were implanted in Atta sexdens rubrupilosa ant species. The BFC maximum power source, operating in vivo, was 13.5 &plusmn; 3.8 &mu;W cm-2 at 190 ± 58.9 mV, with a maximum current of 143 &plusmn; 40.2 &mu;A cm-2 and the open circuit voltage was 260 &plusmn; 99.6 mV. Although these values can be optimized, this research shows that the flexibility of the FCF, the presence of a polymer electron mediator on the anode, using the chemical treatment of oxidation with potassium permanganate of the fibers and electrode miniaturization are important elements, which can be considered in the development of implantable biofuels.

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