Research is presented which encompasses a study of epoxies based on diglycidyl ether of bisphenol A (DGEBA) cured with 2-ethyl-4-methylimidazole (EMI-24) in the presence of the nonionic surfactant Triton X-100. Interest in this epoxy system is due partially to the potential application as a waterborne replacement for solvent cast epoxies in E-glass laminated printed circuit boards. This research has revealed that the viscoelastic behavior of the cured epoxy is altered when serving as the matrix in a glass composite. The additional constraining and coupling of the E-glass fibers to the segmental motion of the epoxy matrix results in an increased level of viscoelastic cooperativity. Current research has determined that the cooperativity of an epoxy/E-glass composite is also sensitive to the surface chemistry of the glass fibers. Model single-ply epoxy/E-glass laminates were constructed in which the glass was pretreated with either 3-aminopropyltriethoxysilane (APS) or 3-glycidoxypropyltrimethoxysilane (GPS) coupling agents. Dynamic mechanical analysis (DMA) was then used to create master curves of the storage modulus (E') in the frequency domain. The frequency range of the master curves and resulting cooperativity plots clearly varied depending on the surface treatment of the glass fibers. It was determined that the surfactant has surprisingly little effect in the observed trends in cooperativity of the composites. However, the changes in cooperativity due to the surface pretreatment of the glass were lessened by the aqueous phase of the waterborne resin. Moisture uptake experiments were also performed on epoxy samples that were filled with spherical glass beads as well as multi-ply laminated composites. No increases in the diffusion constant could be attributed to the surfactant. However, the surfactant did enhance the final equilibrium moisture uptake levels. These equilibrium moisture uptake levels were also sensitive to the surface pretreatment of the E-glass. / Ph. D.

Nonheme iron(II) oxygenases within a common 2-His-1-carboxylate binding motif catalyze a wide range of oxidation reactions involved in biological functions like DNA repair and secondary metabolic processes. The mechanism of O2 activation catalyzed by this enzyme family has been examined by spectroscopic, crystallographic, and computational studies, where it is clear the iron(II) center works with substrate, and cosubstrate to activate O2 by forming a highly oxidizing iron species (iron(IV)-oxo). From a thermodynamic perspective, substrate and/or co-substrate binding organizes the active site for O2 activation, and understanding the interactions among metal, substrate, cosubstrate, and enzyme provides insight into the intramolecular contacts that guide the reaction catalyzed by the enzymes. This dissertation is focused on elucidating the interactions between metal, substrate, and co-substrate in a representative enzyme subfamily of nonheme iron(II) oxygenases, namely the 2-oxoglutarate dependent dioxygenases. Specifically, we investigated the thermodynamic properties of divalent metal ions binding to taurine-dependent dioxygenase (TauD), using Mn2+, Fe2+, and Co2+ ions. Additionally, the thermodynamics associated with substrate and co-substrate binding to Fe·TauD and iron(II)-ethylene forming enzyme (Fe·EFE) were explored using calorimetry and other biophysical techniques.

No description available.

No description available.

No / Beta 2-microglobulin (ß2m) is known to form amyloid fibrils de novo in vitro under acidic conditions (below pH 4.8). Fibril formation at neutral pH, however, has only been observed by deletion of the N-terminal six residues; by the addition of pre-assembled seeds; or in the presence of Cu2+. Based on these observations, and other structural data, models for fibril formation of ß2m have been proposed that involve the fraying of the N and C-terminal ß-strands and the consequent loss of edge strand protective features. Here, we examine the role of the N and C-terminal strands in the initiation of fibrillogenesis of ß2m by creating point mutations in strands A and G and comparing the properties of the resulting proteins with variants containing similar mutations elsewhere in the protein. We show that truncation of buried hydrophobic side-chains in strands A and G promotes rapid fibril formation at neutral pH, even in unseeded reactions, and increases the rate of fibril formation under acidic conditions. By contrast, similar mutations created in the remaining seven ß-strands of the native protein have little effect on the rate or pH dependence of fibril formation. The data are consistent with the view that perturbation of the N and C-terminal edge strands is an important feature in the generation of assembly-competent states of ß2m.

As fiber reinforced polymer matrix composites find greater use in markets such as civil infrastructure and ground transportation, the expectations placed on these materials are ever increasing. The overall cost and reliability have become the drivers of these high performance materials and have led to the disappearance of resins such as bismaleimides (BMI), cyanate esters and other high performance polyimides and epoxys. In their place polymers, such polyester and vinylester have arisen. The reinforcing fiber scenario has also undergone changes from the high quality and performance assured IM7 and AS4 to cheaper and hybrid systems consisting of both glass and low cost carbon. Manufacturing processes have had their share of changes too with processes such as pultrusion and other mass production techniques replacing hand lay-up and resin transfer molding. All of this has however come with little or no concession on material performance. The motivation of the present research has therefore been to try to improve the properties of these low cost composites by better understanding the constituent materials (fiber and matrix) and the region that lies in-between them namely the interphase. In order to achieve this, working with controls is necessary and the present discourse therefore deals with the AS4 fiber system from Hexcel Corporation and the vinyl ester resin, Derakane 441-400 from The Dow Chemical Company. The following eight chapters sum up the work done thus far on composites made with sized fibers and the above mentioned resin and fiber systems. They are in the form of publications that have either been accepted, submitted or going to be submitted to various peer reviewed journals. The sizings used have been poly(vinylpyrrolidone) PVP and Polyhydroxyether (Phenoxy) thermoplastic polymers and G' an industrial sizing material supplied by Hexcel. A number of issues have been addressed ranging from viscoelastic relaxation to enviro-mechanical durability. Chapter 1 deals with the influence of the sizing material on the fatigue response of cross ply composites made with the help of resin infusion molding. Chapter 2 describes the effects of a controlled set of interphase polymers that have the same chemical structure but differ from each other in polarity. The importance of the atomic force microscope (AFM) to view and perform nano-indentations on the interphase regions has been demonstrated. Finally, it attempts to tie everything together with the help of the fatigue response of the different composites. Chapter 3 deals only with the vinyl ester resin and examines the influence of network structure on the molecular relaxation behavior (cooperativity) of the glassy polymer. It also tries to make connections between structural features of the glass and fracture toughness as measured in its glassy state. Chapter 4 extends the results obtained in chapter 3 to examine the cooperativity of pultruded composites made with the different sizings. A correlation between strength and cooperativity is found to exist, with systems having greater cooperativity being stronger. Chapter 5 moves into the area of hygrothermal aging of Derakane 441-400 resin. It looks specifically at identifying a mechanism for the unusual moisture uptake behavior of the polymer subjected to a thermal-spiking environment. This it does by identifying the presence of hydrogen bonding in the resin. Finally, chapters 6 to 8 present experimental and analytical results obtained on PVP K90, Phenoxy and G' sized, AS4/Derakane 411-350 LI vinyl ester composites that were pultruded at Strongwell Inc., on their lab-scale pultruder in Bristol, Virginia. / Ph. D.

BACKGROUND:A hub protein is one that interacts with many functional partners. The annotation of hub proteins, or more generally the protein-protein interaction "degree" of each gene, requires quality genome-wide data. Data obtained using yeast two-hybrid methods contain many false positive interactions between proteins that rarely encounter each other in living cells, and such data have fallen out of favor.RESULTS:We find that protein "stickiness", measured as network degree in ostensibly low quality yeast two-hybrid data, is a more predictive genomic metric than the number of functional protein-protein interactions, as assessed by supposedly higher quality high throughput affinity capture mass spectrometry data. In the yeast Saccharomyces cerevisiae, a protein's high stickiness, but not its high number of functional interactions, predicts low stochastic noise in gene expression, low plasticity of gene expression across different environments, and high probability of forming a homo-oligomer. Our results are robust to a multiple regression analysis correcting for other known predictors including protein abundance, presence of a TATA box and whether a gene is essential. Once the higher stickiness of homo-oligomers is controlled for, we find that homo-oligomers have noisier and more plastic gene expression than other proteins, consistent with a role for homo-oligomerization in mediating robustness.CONCLUSIONS:Our work validates use of the number of yeast two-hybrid interactions as a metric for protein stickiness. Sticky proteins exhibit low stochastic noise in gene expression, and low plasticity in expression across different environments.

L’objet majeur de cette étude est de contrôler la taille de nanoparticules de matériaux à transition de spin (TS), et d’étudier l’influence d’une réduction de taille sur les propriétés de commutation thermique. Plusieurs voies ont été explorées : La première stratégie basée sur la synthèse d’oligomères puis l’assemblage en unités supérieures s’est révélée difficile due à un manque de réactivité. La deuxième approche a consisté à utiliser le confinement moléculaire au sein d’une nanogouttelette pour synthétiser des oligomères de coordination de quelques nanomètres, et mettre en place une véritable “ingénierie moléculaire” en microémulsion. La dernière partie de ce travail est consacrée à la synthèse de particules à TS d’une centaine de nanomètre en milieu micellaire inverse permettant la discussion de l’influence de la taille des particules sur le comportement coopératif. / The main aim of this following study is to control the size of spin crossover nanoparticles, and investigate the influence of size reduction on thermal switch properties. The research has been undertaken along several approaches : Firstly a strategy was developed to build higher dimensionality from synthesized oligomers which revealed difficulties relevant to reactivity. The second approach consisted of using the molecular containment in a nanodrop to synthesize nanometric coordination oligomers and establish a real “molecular engineering” in microemulsion. The last part of this work is devoted to the synthesis of particles with spin crossover property as big as 100 nm in reverse micellar medium allowing the discussion of the interplay of their size with respect to the cooperative behaviour.

Uma das várias formas da hemoglobina do peixe Leporinus Frederici (piava) não apresenta efeito Borh (variação da afinidade ao O2 com o pH). Purificação, caracterização e experimentos de cristalização foram conduzidos visando a determinação da estrutura através de difração de raios X, embora sem resultados positivos. O espectro óptico desta forma particular de hemoglobina foi medido no intervalo de 300-700 nm e subseqüentemente simulado, interpretado e comparado com o espectro da humana. Em outra área do trabalho experimental, três pequenas estruturas moleculares foram determinadas: uma é um intermediário na síntese de alcalóides, com um esqueleto sarpagina; outra é um dipeptídeo complexado com Cu2+; e a terceira é um complexo de picrato com Ce3+. As intensidades das reflexões foram medidas com um difratômetro automático de quatro ciclos CAD-4. As estruturas foram resolvidas por Patterson ou Métodos Diretos e foram refinadas por método de mínimo quadrado. Cetona, C19H21N3O, é um intermediário chave no caminho de reação para síntese de indoloquinolisidinas, pertence ao sistema, P21/C, a=12.200(7), b=16,795(2), c=16,655(l)&#197, &#946=104,18(3)&#176, Z=8, Dc= 1,234 gcm-3, V=3308(3)&#1973. As duas moléculas independentes são aproximadamente relacionadas por um centro de inversão, a principal diferença sendo relativa às configurações dos grupos nitril e metil. As moléculas enantioméricas estão mantidas por ligação de hidrogênio através do N(3)-O(1\') e N(3\')-O(1). A junção N(1)-C(6) é trans e o grupo CH2CN é axial. L-(triptofil)-L-glicinato-cobre(II). C13H13CuN3O3, um composto modelo para conseguir informações para interpretar os dados disponíveis para proteínas azuis, é ortorrômbico, P212121, a=8,284(6), b=9,345(2). c=16.503(2)&#197, Z=4, Dc=1.678 gcm-3, V=1277(2)&#1973. O íon Cu2+ é coordenado por um oxigênio e dois nitrogênios de um dipeptídeo e com um oxigênio de um ligante simetricamente relacionado. A estrutura polimérica resultante está alinhada com o eixo b e tem uma estabilidade maior devido a uma ligação de hidrogênio entre o oxigênio carbonil de um dipeptídeo e o nitrogênio do triptofano do ligante vizinho. A coordenação é essencialmente quadrado planar. O complexo de picrato com Ce3+, CeO33N9C18H30, foi analisado dentro de um grande programa de pesquisa para estudar a química de coordenação dos lantanóides. Duas formas cristalinas são estudadas: uma é monoclínica, P21/n, a=7,799(2), b=26,925(2), c=17,465(2)&#197, &#946=98,93(3)&#176 , Z=4, Dc= 1,908 gcm-3, V=3623(2)޵ e a outra é monoc1ínica, C2/c, a=40,225(5), b=8,08(4), c=24,35l(9), &#946=111,46(2), Z=8, Dc= 1,893 gcm-3, V=7300(8)&#1973. A primeira é relativamente instável sobre a incidência de raios-X e embora a medida das intensidades apresentasse erros sistemáticos significantes, a estrutura pode ser resolvida. O número de coordenação dos dois complexos é 9 e os poliedros de coordenação são intermediários entre antiprisma quadrado monoencapuzado e prisma trigonal triencapuzado / One of the various forms of hemoglobin of the fish Leporinus Frederici (piava) does not present any Bohr effect (variation of the affinity to O2 with pH). Purification, characterization and crystallization experiments were conducted, aimed at the structure determination through X-ray diffraction, although with no positive results. The optical spectrum of this particular hemoglobin form was measured in the range 300-700 nm and subsequently simulated, interpreted and compared with the human hemoglobin spectra. In another area of experimental work, three small molecules structures were determinate: one is an intermediate in the synthesis of alkaloids, with a sarpagine backbone; another is a dipeptide complexes with Cu2+; and a third one is a complex of picrate with Ce3+. The intensities of the reflections were measured with an automatic four-circle difractometer CAD-4. The structures were solved by Patterson or Directs Methods, and were refined by the least squares methods. Ketone, C19H21N3O, is a key intermediate in the reaction pathway for synthesis of indoloquisidines, belongs to the monoclinic system, P21/c, a=12.200(7), b=16,795(2), c=16,655(l)&#197, &#946=104,18(3)&#176, Z=8, Dc= 1,234 gcm-3, V=3308(3)&#1973. The two independent molecule are approximately related by an inversion center, the main difference being the relative configurations of the nitril and methyl groups. The enantiomeric molecules are hydrogen bonded through N(3)-O(1\') and N(3\')-O(1). The junction N(l)-C(6) is trans and the group CH2CN is axial. L-(tryptophyl)-L-glycinate-copper(II), C13H13CuN3O3, a model compound to get information to interpret spectroscopic data available for blues proteins, is orthorhombic, P212121, a=8,284(6), b=9,345(2). c=16.503(2)&#197, Z=4, Dc=1.678 gcm-3, V=1277(2)&#1973. The Cu-ion is coordinated by one oxygen and two nitrogen atoms of the one dípeptide and with an oxygen of a symmetrically related ligand. The resulting polymeric structure is aligned with the b-axis and is further stabilized by an H-bond between the carbonyl-oxygen of the one dipeptide and the tryptophan side-chain nitrogen of the neighboring ligand. The coordination is essentially square-planar. The complex of picrate with Ce3+, CeO33N9C18H30, was analyzed within a broader research program to study the chemistry of coordination of the lantanoids. Two crystalline forms are studied: one is monoclinic, P21/n, a=7,799(2), b=26,925(2), c=17,465(2)&#197, &#946=98,93(3)&#176 , Z=4, Dc= 1,908 gcm-3, V=3623(2)޵ and the other is monoclinic, C2/c, a=40,225(5), b=8,08(4), c=24,35l(9), &#946=111,46(2), Z=8, Dc= 1,893 gcm-3, V=7300(8)&#1973. The former is relatively unstable under the X-rays and although the measured intensities presented significant systematic errors, the structure could be solved. The coordination number of the two complexes is 9 and the coordination polyedra are intermediate between mono-coupled square antiprism and tri-coupled trigonal prism

Ce travail a porté sur la synthèse et l'étude de nanoparticules à transition de spin du réseau tridimensionnel Fe(pyrazine)[Pt(CN)4]. L'objectif principal de ce travail était d’étudier l’effet de l'environnement (matrice) sur les propriétés de transition de spin des nanoparticules de Fe(pyrazine)[Pt(CN)4]. Dans un premier temps, la synthèse en microémulsion et l’étude de quelques paramètres permettant de varier la taille des particules ont été menées. La morphologie de deux tailles de particules a été étudiée en particulier par tomographie électronique. Les propriétés des particules de Fe(pyrazine)[Pt(CN)4] de 10 nm récupérées sans enrobage sont présentées et révèlent une coopérativité comparable au composé massif. L’étude a ensuite été poursuivie en modifiant uniquement l'environnement des particules en gardant les autres paramètres (taille, composition, forme) constants. Des particules de Fe(pyrazine)[Pt(CN)4] de 10 nm ont été protégées par différentes molécules telles qu’un dérivé calix-8-arène comportant des pyridines, le para-nitrobenzylpyridine (pNBP), un polymère (PVP) ou encore par croissance par voie sol-gel d’une coquille de silice de différentes épaisseurs. L’effet de l’environnement des nanoparticules sur les propriétés de transition de spin a été mis en évidence de manière très claire et la compressibilité de la matrice a été proposée comme élément permettant de moduler cette coopérativité. Par ailleurs, l'influence de la nature du réseau inorganique modifié par insertion d’iode dans le réseau de Fe(pyrazine) [Pt(CN)4] des nanoparticules a été étudiée, afin d’augmenter la température de transition autour de l’ambiante. Un effet particulièrement important été observé sur la coopérativité de la transition de spin des particules enrobées. Les résultats ont été discutés dans le contexte de récentes études de modélisation. / This work is focused on the synthesis and study of the spin crossover nanoparticles of 3D Fe (pyrazine) [Pt(CN)4] network. The main objective of this work was to study the environment (matrix) effects on the spin crossover (SCO) behavior of the Fe(pyrazine)[Pt(CN)4] nanoparticles. At first, microemulsion synthesis and study of some parameters affecting the size of the particles have been conducted. The morphology of particles of two sizes has been studied in particular using Electron Tomography. The properties of the 10 nm Fe(pyrazine)[Pt(CN)4] particles recovered without coating are presented and reveal cooperativity comparable to the bulk compound. The study was followed by changing only the environment and keeping other parameters (size, composition, shape) constant. 10 nm Fe(pyrazine)[Pt(CN)4] nanoparticles were protected by different molecules such as a derivative of calix-8-arene having pyridine groups, para-nitrobenzylpyridine (pNBP), a polymer (PVP) or a silica shell of different thicknesses grown via sol-gel process. The effect of the environment of nanoparticles on the spin transition properties has been demonstrated very clearly and the compressibility of the matrix has been proposed as an element to modulate the cooperativity. In addition, the influence of the nature of the inorganic network modified by insertion of iodine in the network Fe(pyrazine)[Pt(CN)4] nanoparticles has been studied to increase the transition temperature around ambient temperature. A particularly significant effect was observed on the cooperativity of the spin transition of the coated particles. The results were discussed in the context of recent modelisation studies.