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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.
261

ESR observation of optically generated solitons in the quasi-one-dimensional iodo-bridged diplatinum complex Pt_2(n-pentylCS_2)_4I

Tanaka, Hisaaki, Nishiyama, Hideshi, Kuroda, Shin-ichi, Yamashita, Takami, Mitsumi, Minoru, Toriumi, Koshiro 07 1900 (has links)
No description available.
262

韓国の拡大生産者責任政策に関する経済分析 / Economic analysis of EPR policy in South Korea

金, 小瑛 23 March 2015 (has links)
Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(地球環境学) / 甲第19156号 / 地環博第131号 / 新制||地環||27 / 32107 / 京都大学大学院地球環境学舎地球環境学専攻 / (主査)准教授 森 晶寿, 教授 劉 徳強, 准教授 吉野 章 / 学位規則第4条第1項該当
263

Réalisation d'un magnétomètre à centre coloré NV du diamant

Rondin, Loïc 23 November 2012 (has links) (PDF)
L'imagerie de champs magnétiques de faible amplitude avec une résolution spatiale à l'échelle nanométrique est un enjeu important dans de nombreux domaines de la physique et pour de multiples applications, que ce soit par exemple en science des matériaux pour le stockage magnétique de l'information, ou bien en optique quantique afin de pouvoir contrôler un spin individuel utilisé comme bit quantique, ou encore en biophysique pour l'étude structurelle de protéines par résonance magnétique. Dans ce contexte, cette thèse décrit la réalisation d'un magnétomètre à balayage fondé sur la réponse magnétique du spin électronique d'un centre coloré NV du diamant. Un tel magnétomètre présente des propriétés sans équivalent, en combinant une résolution spatiale sub-nanométrique, assurée par la dimension atomique du capteur, et une très haute sensibilité (< 1 µT/Hz^(-1/2)), ceci même à température ambiante. De plus la mesure de champ magnétique est quantitative et non perturbative, offrant ainsi un avantage majeur par rapport à la microscopie à force magnétique couramment utilisée pour l'imagerie magnétique de nanostructures. Nous aborderons, dans un premier temps, les problématiques liées à la fabrication de la sonde magnétique, constituée par un centre coloré NV unique dans un nanocristal de diamant positionné à l'extrémité d'une pointe AFM. Les propriétés de ce magnétomètre seront caractérisées en imageant le champ de fuite d'un disque dur magnétique. Cette étude nous permettra d'introduire différentes méthodes d'imagerie magnétique et de comparer leurs performances. Le magnétomètre à centre NV sera par la suite utilisé pour imager des distributions d'aimantation vortex dans des plots ferromagnétiques, dont le cœur est connu pour être l'un des objets les plus petits du micromagnétisme, le rendant extrêmement difficile à observer. Les propriétés du magnétomètre à centre coloré NV du diamant, démontrées dans cette thèse, ouvrent la voie à de nombreuse études en nanomagnétisme et en spintronique.
264

A model of mind from the perspective of temporal structuralism

Pike, Stephen Mace January 2009 (has links)
Symmetry and symmetry-breaking have, in the last one hundred and fifty years, become incorporated as central explanatory concepts within the natural sciences and mathematics. An abbreviated review of the incorporation of symmetry within the disciplines of mathematics, physics, philosophy and biology, provides a frame within which to develop of a model of mind. This thesis combines the framework provided by symmetry and symmetry-breaking with a structural understanding of self-referential dynamics in examining the implied Kantian model of mind. It considers that Kant’s assumption of a transcendental self unnecessarily isolates consciousness from being understood as a product of complex natural processes. Kant’s structural model of mind is examined and reformulated in terms of a more fundamental form and process. The space required for any non-reductionist model of mind is proposed as being generated through an enfolding of dimensionality in the occurrence of categorical level symmetry breaking during evolutionary development. The temporally extended function is accounted for in terms of self-referential structural dynamics operating within the primary temporal asymmetry. The model of mind proposed is created through application of naturalistic explanations incorporating symmetry and has attributes that may prove of interest to non-reductionists. The phenomenological geometry established provides a framework to understand the experiential phenomenon of qualia while conforming to the requirements of a natural explanation. Information is conceived as being transmitted inwaveforms propagated across spaces of enfolded dimensionalities through structural framesdemarcating nested spaces and condensing in the synthesis of unity in the object of attention,or image, and returning to distribute, the now reformulated, information outward acrosscontextual frames and spaces. This simplified dynamic is considered to operate at all levels of natural phenomena and involves the reintroduction of Bohm’s concepts of implicate and explicate order. The result is a model of mind employing a minimum structural form and self-referential dynamics that has potential for integration across the discipline theoretic frames of the natural sciences while retaining, for the domain of conscious phenomena, an independent causal significance in terms of a temporal structuralism.
265

Dynamic Nuclear Polarisation Surface Enhanced NMR Spectroscopy

Zagdoun, Alexandre 12 June 2014 (has links) (PDF)
Since its discovery in the 1950's, DNP has been a topic of significant interest in magnetic resonance. DNP is the transfer of polarization between single electrons and nuclei, driven by micro-wave irradiation. Since its renaissance at high field in the 90's, due to the introduction of gyrotrons as high-power, high-frequency microwave sources most application of this technique have been samples of biological interest in frozen solution. The long standing interest of our group in the characterization of surface species such as supported catalysts on silica lead us to apply this technique to the study of surfaces. The goal of this thesis is the development of this method, dubbed DNP Surface Enhanced NMR Spectroscopy. To that end, we first introduce new polarizing agents, soluble in organic solvents. The influence of the electron relaxation times on the DNP enhancements is demonstrated and efficient tailored polarizing agents are introduced. The optimization of the sample preparation to obtain optimal sensitivity is also discussed, as well as the interaction between the radical and the surface. These developments made it possible to apply the technique to many functionalized materials, with some examples developed in this manuscript. Finally, the issue of DNP on polarization conductors is discussed, and we show how microcrystals can be efficiently polarized using DNP.
266

The Effect of Stakeholders’ Background on Perceptions of Usability and Usefulness on Personal Health Records

Guarin, Desmond Medina 24 December 2013 (has links)
Despite rapid advances in technology, there is currently a complex, and somewhat disjointed approach to the way health information is collected, stored, and organized for both healthcare consumers and professionals. Incompatible electronic medical records from various healthcare providers add to the complexity of a system tasked with delivering a patient’s relevant medical information in a timely manner to the appropriate point of care. Personal health records (PHR) grew out of the efforts to produce an integrated electronic record to manage the multifaceted aspects of healthcare required by both healthcare consumers and professionals. PHRs are a transformative technology with the potential to alter patient-provider relationships in a way that produces a more efficient and cost effective healthcare system as a result of better patient outcomes. PHRs can potentially include a wide variety of users ranging from the lay public to clinical professionals. As such, it is important to identify potential user groups and their corresponding health information needs in order to design PHRs that maximize accessibility, usability, and clinical relevance. This study focused on laypeople who represented a wide age-range of individuals, evenly split in gender, with an above average level of computer literacy. Most of the participants had not used an electronic PHR prior to this study. However, after a hands-on session with PHR software, most participants found it to be easy to use, accompanied with the functionality they expected from such a system. Most participants were satisfied that an electronic PHR would meet their health information needs and would recommend the use of PHRs to family and friends. Anyone in the general public is a potential PHR user. However, this study found that individuals with chronic conditions and those with complex health needs had the most to gain from using a PHR as an integral part of their healthcare routine. This study also demonstrated that an individual’s health condition has a stronger influence on their perceptions about the usefulness of PHRs than does their demographic background (age, education, computer literacy). Finally, this study established that PHRs are considered by participants of the study to be useful tools in meeting their health information needs. / Graduate / 0723 / 0769 / 0984 / dguarin@uvic.ca
267

Estudos espectroscópicos de complexos de glicil-tirosina e tirosil-glicina com o íon Cu(II) / Spectroscopic studies of complexes of glycil-tyrosine and tyrosyl-glicine with Cu(II) íons

Tania Toyomi Tominaga 01 October 1993 (has links)
Neste trabalho estudou-se a formação de complexos da tirosina e de seus dipeptídeos tirosil-glicina e glicil-tirosina com o íon Cu2+. Para a caracterização destes complexos foram utilizadas as técnicas espectroscópicas de Absorção ótica na região do visível (400 a 800 nm), Ressonância paramagnética eletrônica em duas temperaturas (ambiente e &#8764-150&#176C) e a técnica de fluorescência. No caso da tyr os dados experimentais obtidos pela espectroscopia de RPE sugerem a formação de pelo menos duas espécies distintas de complexos além do cobre hidratado. Os complexos propostos foram: o CuL4 (ao redor de pH 3,5) e o CuL2 (na faixa de pH 4,0 e 12,0). Já para os dipeptídeos são evidenciados três tipos diferentes de complexos. São propostos os seguintes complexos: CuL2 (ao redor de pH 4,5), CuL (H2O) (na faixa de pH 7,0 e 12,0) e CuL(OH)22- (acima de pH 12,0). Os espectros de RPE mostram claramente que com o aumento de pH, ocorre a complexação do Cu2+ com os dipeptídeos. Em pHs altos (acima de pH 10,0) surgem nestes espectros uma estrutura superhiperfina de 5 linhas típicas para a coordenação de Cu2+ com dois nitrogênios. Quanto a tirosina, o espectro de seu complexo com Cu2+, não apresenta estrutura superhiperfina, sendo o sinal obtido, típico do complexo com Cu2+. Da mesma forma que foi observado por RPE, pode-se observar pelos espectros óticos, que em pHs baixos (2,0 a 3,5) para os dipeptídeos, os espectros apresentam uma banda larga e mal-resolvida, característica do íon de Cu2+ livre em solução. Observou-se também um deslocamento do máximo das bandas para o azul, apresentando características típicas das transições d-d correspondentes às várias espécies de complexos do metal em equilíbrio. Os dados de fluorescência foram muito informativos. As titulações da tyr e dos dipeptídeos puros em função do pH permitiram a determinação dos valores de pKs dos grupos ionizáveis. O efeito de supressão de fluorescência devido ao paramagnetismo do cobre foi usado tanto para a determinação da estequiometria quanto para a determinação das constantes de associação dos complexos dos dipeptídeos com Cu2+ em dois pHs fixos (pH 7,0 e 9,0). Encontrou-se complexos com a seguinte estequiometria (ligante/metal) : 2:1 e 1:1 respectivamente para a tyr e para os dipeptídeos nestes pHs. Um modelo simples de equilíbrio foi desenvolvido e estimou-se as constantes de associação da ordem de 107M-1 para os complexos de dipeptídeos- Cu2+. / The main goal of this work was to study the formation of the complexes of tyrosine and its dipeptides tyrosil-glycil and glycil-tyrosine with the transition metal íon Cu2+. The characterization of these complexes was performed through the use of spectroscopic techniques: optical absorption, electron paramagnetic resonance at both room temperature and -150&#176C and fluorescence emission. The EPR spectroscopy suggested for tyrosine two distints species. The following complexes were proposed: CuL4 (pH 3,5) and CuL2 (in the range of pH between 4,0-12,0). Three different complexes were evidentiated for dipeptides- Cu2+: CuL2 (pH 4,5); CuL(H2O) (in the range of pH between 7,0-12,0) and CuL(OH)22- (above pH 12,0). EPR spectra shows clearly the complexation of Cu2+ to the dipeptides. Both at intermediate and high pHs and specially above pH 10,0 a superhyoerfine structure of five lines typical for coordination of copper to two nitrogens was observed. In the case of the aminoacid no superhyperfine structure is observed. EPR data suggest that in a wide pH range between 7,0 and 11,0 the complex formed by the dipeptides was CuL(H2O). Electronic optical absorption was measured at room temperature as a function of pH in the range 2,0-13,0. It was observed that at low pHs (2,0 3,5) the spectra for the dipeptides was characterized by a broad not well resolved band around 800 nm characteristic of hidrated free Cu2+ in water solution. EPR spectra are in agreement with this observation. Increase of pH leads to a blue shift in the absorption band maximum and as a consequence to typical spectra for d-d transitions of the various species of complexes of cooper in equilibrium in solution. Fluorescence data were also very informative. The pure tyr and dipeptides tritation allowed to determine pKs values of ionizable groups. The effect of fluorescence suppression due to paramagnetic copper was used both to establish the stoichiometry of the complexes and the association constants. The stoichiometry of the complexes was determined as 2:1 and 1:1 ligand:metal for tyrosine and the dipeptides respectively at pH 7,0 and pH 9,0. A simple equilibrium model was developed and the association constants for the Cu2+ dipeptides complexes at pH 7,0 and pH 9,0 were estimated to be around 107M-1.
268

Ressonância paramagnética eletrônica em sistemas antiferromagnéticos / Electron paramagnetic resonance in antiferromagnetic systems

Vinicius Tadeu Santana 26 September 2016 (has links)
Neste trabalho, dois óxidos de metal de transição com ordem magnética de longo alcance e uma polianilina dopada com plastificante foram estudados através da técnica de ressonância paramagnética eletrônica. O sistema multiferróico óxido de bismuto-manganês, BiMn2O5, foi estudado em sua forma policristalina. Este material apresenta modos de ressonância antiferromagnética que foram identificados a partir de medidas multifrequência em altos campos magnéticos. Estes dados foram ajustados segundo a teoria de Yosida e Nagamiya da ressonância antiferromagnética para obtenção das constantes macroscópicas de anisotropia magnética K1=7.0 x 108 emu Oe mol1 e K2=3.9 x 108 emu Oe mol1, a partir das quais uma estimativa da constate de anisotropia microscópica foi determinada. A caracterização destas grandezas pode ser importante para trabalhos futuros, uma vez que a anisotropia magnética é considerada uma das causas da magnetoelasticidade que dá origem a ferroeletricidade neste material. A ludwigita homometálica de ferro, Fe3O2BO3, foi estudada em sua forma monocristalina. Este óxido de ferro possui uma estrutura com duas sub-redes de ferro praticamente independentes, que se ordenam magneticamente em temperaturas distintas, além de apresentar correlações eletrônicas desde temperatura ambiente. A existência dessas correlações numa dessas estruturas, conhecida como \"escada de três pernas\", foi demonstrada através do espectro de RPE associado com a existência de dímeros Fe3+-Fe2+ nessa estrutura, desde temperatura ambiente até baixas temperaturas. Mostrou-se que os dímeros formam um estado antiferromagneticamente acoplado sujeito a interação de troca dupla, estimando valores da integral de transferência de carga b. Medidas de RPE em filmes automontados de polianilinas dopadas com plastificantes sugerem a população e despopulação de um estado tripleto a partir dos parâmetros dos espectros em função da temperatura, típica de dímeros de spin 1. Diferenças nos parâmetros com ciclagens térmicas sugere o congelamento da estrutura em diferentes estados condizente com a existência de termocromismo nesses polímeros. Enfim, demonstrou-se a relevância da técnica de espectroscopia de ressonância paramagnética eletrônica na caracterização de sistemas sujeitos a interação de troca antiferromagnética. / In this work, two transition metal oxides presenting long range magnetic order and a plastdoped polyaniline were investigated via electron paramagnetic resonance. Polycrystalline samples of the multiferroic manganese oxide, BiMn2O5, showed antiferromagnetic resonance modes which were identified from high magnetic fields multi frequency electron paramagnetic resonance. These data were fitted according to Yosida and Nagamiya theory of antiferromagnetic resonance. The macroscopic constants of magnetic anisotropy K1=7.0 x 108 emu Oe mol1 and K2=3.9 x 108 emu Oe mol1 were obtained from this fitting and allowed for estimating the microscopic constant of anisotropy. Magnetic anisotropy may lead to magnetoelasticity, which is related to the ferroelectricity in this material. Thus, the characterization of this physical quantities may be useful to future research. Single crystals of a homometallic iron ludwigite, Fe3O2BO3, were investigated in its distinct magnetic phases. This system has two independent iron sub-lattices which order magnetically in two distinct temperatures, presenting electronic correlations from room temperature. Despite the broad and superposed lines in the EPR spectra, the presence of such correlations was demonstrated in one of these structures, which is known as three leg ladders (3LL). A dimer Fe3+-Fe2+ was identified at room temperature, showing an antiferromagnetically coupled state subjected to double exchange interactions. The charge transfer integral b was estimated. Temperature sweep EPR measurements in films of plastdoped polyanilines suggested the population and depopulation if a triplet state typical of spin 1 dimers. Differences in the parameters after thermal cycling suggested the freezing of the structure at different states in accordance to observed thermocromism in these polymers. In conclusion, the relevance of the EPR technique was demonstrated to the characterization of exchange coupled systems.
269

Estudo através da técnica de ressonância paramagnética eletrônica, em bandas X e Q, dos compostos dinucleares Cu2(TzTs)4 e [Cu(flu)2DMF]2 / Electron paramagnetic resonance studies at X- and Q- bands of the dinuclear compounds Cu2(TzTs)4 and [Cu(flu)2DMF]2

Lia Munhoz Benati Napolitano 29 May 2009 (has links)
Esta tese relata um estudo pormenorizado, efetuado através da técnica de Ressonância Paramagnética Eletrônica (RPE) em bandas X (~ 9.5 GHz) e Q (~ 34.5 GHz), de amostras nas formas cristalina e pulverizada dos compostos dinucleares Cu2(TzTs)4, C40H36Cu2N8O8S8, e [Cu(flu)2DMF]2, C62H50Cu2F12N6O10. Tratamentos meticulosos dos espectros de RPE pertinentes a tais compostos propiciaram determinar tanto o parâmetro de interação antiferromagnética, J0, entre pares de íons Cu(II) existentes em uma unidade dinuclear (Hex = J0 S1·S2) como também os valores principais alusivos às matrizes g e D; onde a primeira refere-se à interação Zeeman [Hz = BB0(g1·S1 + g2·S2)] e a última reporta as interações spin-spin anisotrópicas (Hani = S1·D·S2) entre pares de íons Cu(II) presentes em uma unidade dinuclear. Ademais, medidas de RPE realizadas com um monocristal do composto Cu2(TzTs)4 permitiram detectar e estimar, no contexto interdinuclear, o fraco acoplamento de exchange, |J\'| = (0.060 ± 0.015) cm-1, existente entre unidades dinucleares vizinhas: este acoplamento existente entre uma unidade dinuclear e o meio randômico constituído pelas unidades dinucleares vizinhas conduz à decoerência (i.e. uma transição de fase quântica que colapsa a interação dipolar quando a magnitude do acoplamento de exchange isotrópico entre as unidades dinucleares vizinhas iguala-se à magnitude do acoplamento dipolar intradinuclear). No âmbito concernente ao composto [Cu(flu)2DMF]2, foi possível simular acuradamente as sete linhas de ressonância características do desdobramento hiperfino advindo de n = 2 núcleos equivalentes de centros paramagnéticos Cu2+ (I = 3/2) e, por conseguinte, os valores principais pertinentes à matriz de interação hiperfina A (Hhyper = S1·A·I1 + S2·A·I2) puderam ser precisamente determinados. / We report detailed Electron Paramagnetic Resonance (EPR) studies at X-band (~ 9.5 GHz) and Q-band (~ 34.5 GHz) of powder and single-crystal samples of the dinuclear compounds Cu2(TzTs)4, C40H36Cu2N8O8S8, and [Cu(flu)2DMF]2, C62H50Cu2F12N6O10. Meticulous investigations of their EPR data allow determining the antiferromagnetic interaction parameter, J0, between Cu(II) ions in the dinuclear unit (Hex = J0 S1·S2) as well as the principal values of both matrices g and D, where the first one is related to the Zeeman interaction [Hz = BB0(g1·S1 + g2·S2)] and the latter is associated with the anisotropic spin-spin interactions (Hani = S1·D·S2) between Cu(II) ion pairs in a dinuclear unit. In addition, EPR measurements of single-crystal samples of the compound Cu2(TzTs)4 allow detecting and estimating very weak exchange couplings between neighbour dinuclear units with an estimated magnitude |J\'| = (0.060 ± 0.015) cm-1: this coupling with the environment leads to decoherence (i.e. a quantum phase transition that collapses the dipolar interaction when the isotropic exchange coupling with neighbor dinuclear units equals the magnitude of the intradinuclear dipolar coupling). With reference to [Cu(flu)2DMF]2 compound, it was possible to simulate precisely the seven-line copper hyperfine splitting arising from n = 2 nonequivalent nuclei related to paramagnetic Cu2+ (I = 3/2) centers and, as a consequence of these accurate simulations, the principal values of the hyperfine interaction matrix A (Hhyper = S1·A·I1 + S2·A·I2) could be reliably obtained.
270

Interações da albumina de soro bovino com surfactantes e efeitos de antioxidantes sobre a oxidação de lipoproteínas de baixa densidade induzida por íons de cobre / Interactions of bovine serum albumin with surfactants and effects of antioxidants on the oxidation of low density lipoproteins induced by cooper ions

ANJOS, Jorge Luiz Vieira dos 02 August 2012 (has links)
Made available in DSpace on 2014-07-29T15:15:47Z (GMT). No. of bitstreams: 1 Jorge Luiz Vieira dos Anjos.pdf: 4028971 bytes, checksum: 465f3f841d85c1929df7648b16aeb163 (MD5) Previous issue date: 2012-08-02 / Human plasma contains primarily large proteins, ranging in composition and concentration as the individual's physiological state. Among these proteins, albumin and low density lipoprotein (LDL) have been widely studied. The albumin (the most abundant protein in blood plasma) is responsible for important functions in the human body due to its excellent ability to bind and transport small molecules. In turn, the LDL (responsible for transporting cholesterol to the cells) in its oxidized form is directly associated with atherosclerosis, the main cause of cardiovascular disease. In the first part of this work, the interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS), cetyltrimethylammonium chloride (CTAC) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. In the second part was studied the oxidation of human LDL by copper ions and also the antioxidant potential of polyphenols resveratrol, (+)-catechin and quercetin, using the EPR of a spin label, derived from stearic acid (5-DSA), and the method malondialdehyde content (MDA). Part I: The dynamics of the BSA and the thermodynamic parameters for transferring the nitroxide side chain from the more motionally restricted to the less restricted component were monitored through EPR spectra simulation. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all concentrations used, HPS presented a smaller effect at concentrations above 1.5mM. At 10mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the Mal-5 induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS (Dynamic Light Scattering) data suggests that the temperature induced changes monitored by the Mal-5 reflects local changes in the vicinity of Cys-34 BSA residue. Part II: The oxidative process induced by copper ions results in lipid peroxidation of LDL (evidenced by high concentration of MDA) could also be monitored by the decrease in the dynamics of 5-DSA, reflected in increased spectral parameter 2A//. The oxidation of LDL resulted in increased energy barrier that the spin labels must overcome to achieve higher degrees of motion. All polyphenols studied were able to protect LDL completely against oxidation for concentrations from 30 &#61549;M, whereas the protection provided by the Butylated hydroxytoluene (BHT) occurred only partially. This result, based on data from the literature, was attributed to the ability of polyphenols act as scavenger and chelating agents, while the BHT acts just like scavenger due the presence of only a single hydroxyl group in its molecule. / O plasma humano contém principalmente grandes proteínas, com variação na composição e concentração conforme o estado fisiológico do individuo. Entre essas proteínas, a albumina e a lipoproteína de baixa densidade (LDL) têm sido amplamente estudadas. A albumina (proteína mais abundante do plasma sanguíneo) é a responsável por importantes funções no organismo humano devido a sua excelente capacidade de se ligar e transportar pequenas moléculas. Por sua vez, a LDL (responsável pelo transporte de colesterol para as células) em sua forma oxidada está diretamente associada à aterosclerose, principal causa de doenças cardiovasculares. Na primeira parte deste trabalho, a interação da albumina de soro bovino (BSA) com os surfactantes iônicos dodecil sulfato de sódio (SDS), cloreto de cetiltrimetilamônio (CTAC) e N-hexadecil-N,N, dimetil-3-3amônio-1-propano sulfonato (HPS) foi estudada através da espectroscopia de ressonância paramagnética eletrônica (RPE) do marcador de spin Mal-5 ligado covalentemente na cadeia lateral do resíduo Cys-34 da BSA. Na segunda parte foi estudada a oxidação da LDL humana por íons de cobre e também o potencial antioxidante dos polifenóis resveratrol, (+)-catequina e quercetina, usando a RPE de um marcador de spin derivado do ácido esteárico (5-DSA) e o método de formação de malondialdeído (MDA). Parte I: A dinâmica da BSA e os parâmetros termodinâmicos para transferir a cadeia lateral do nitróxido da componente de movimento mais restrito para a componente menos restrita foram monitorados através da simulação dos espectros de RPE. Enquanto o SDS e o CTAC mostraram efeitos similares na dinâmica da proteína para todas as concentrações usadas, o HPS apresentou menor efeito em concentrações acima de 1,5 mM. Em 10 mM de surfactantes e 0,15 mM de BSA, a variação da energia livre padrão de Gibbs foi consistente com a conformação da cadeia proteica mais expandida e mais exposta ao solvente, mas com um efeito menos pronunciado para o HPS. Na presença dos surfactantes, a variação de entalpia, relacionada a energia necessária para dissociar a cadeia lateral do nitróxido da proteína, foi grande, sugerindo uma menor atividade da água. A cadeia lateral do nitróxido também detectou um ambiente com maior viscosidade nas vizinhanças do Mal-5 induzida pela adição dos surfactantes. Os resultados sugerem que a interação surfactante-BSA, em altas concentrações, é afetada pela afinidade do surfactante por suas próprias micelas e agregados micelares incorporados na proteína. Complementarmente, dados obtidos com DLS (Dynamic Light Scattering) sugerem que as mudanças induzidas pela temperatura que são monitoradas pelo Mal-5 são mudanças locais na vizinhança do único resíduo Cys-34 da BSA. Parte II: O processo oxidativo induzido pelos íons de cobre resulta na peroxidação dos lipídios da LDL (evidenciado pela elevação da concentração de MDA) também pôde ser monitorado pela diminuição na dinâmica do marcador de spin 5-DSA refletida no aumento do parâmetro espectral 2A//. A oxidação da LDL acarretou no aumento da barreira da energia que os marcadores de spin precisam superar para alcançar graus superiores de movimento. Todos os polifenóis estudados foram capazes de proteger completamente a LDL contra a oxidação em concentrações a partir de 30 &#61549;M, enquanto que a proteção fornecida pelo butil-hidroxi-tolueno (BHT) se deu apenas parcialmente. Este resultado, baseado em dados da literatura, foi atribuído à capacidade dos polifenóis atuarem tanto como scavenger quanto como quelantes, ao passo que o BHT é capaz de atuar apenas como scavenger devido à presença de apenas uma única hidroxila em sua molécula.

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