No description available.

<p>A series of layered perovskite-based compounds were synthesized and studied as follows.</p> <p>La₅Mo_2.76(4)V_1.25(4)O₁₆ is a new pillared-perovskite synthesized by solid state chemistry method. It has layers of corner-sharing octahedra separated by dimers of edge-sharing octahedra, and is the first Mo-based pillared-perovskite whose magnetic structure was determined by neutron diffraction.</p> <p>Ca₂FeMnO₅ is an oxygen-deficient-perovskite with a brownmillerite-type ordering of oxygen vacancies, resulting in layers of corner-sharing octahedra separated by chains of corner-sharing tetrahedra. The octahedral layer contains mostly (~87%) Mn, while the tetrahedral layer is mainly (~91%) occupied by Fe. Long-range G-type magnetic ordering is present, where the moment on each site is coupled antiferromagnetically relative to all nearest neighbors.</p> <p>Ca₂FeCoO₅ has a brownmillerite superstructure with space group <em>Pcmb</em>, a rare space group for brownmillerites that requires doubling of one unit cell axis. Ca₂FeCoO₅is the first brownmillerite to contain intra-layer cation ordering. It has a long-range G-type ordering, and is the first brownmillerite to show spin re-orientation as function of temperature.</p> <p>Sr₂FeMnO_5+y was synthesized in both air (y~0.5) and argon (y~0), both of which resulted in vacancy-disordered cubic structures. The argon compound has a local brownmillerite structure, i.e. local ordering of vacancies. It has a superparamagnetic state below ~55K, with domains of short range (50Å) G-type ordering at 4K. For the air synthesized compound, y~0.5, long range G-type ordering is observed in ~4% of the sample.</p> <p>Sr₂Fe_1.9M_0.1O_5+y (M=Mn, Cr, Co; y= 0, 0.5) were synthesized in both air(y~0.5), and argon(y~0). All argon materials are brownmillerites with G-type magnetic ordering, but T_N’s are significantly different. The air-synthesized Co-material has long range vacancy ordering and magnetic ordering, while the Mn and Cr-materials (air) lack such orderings and both show spin-glass-like transitions.</p> <p>Sr₂Fe_1.5Cr_0.5O₅ has a vacancy-disordered cubic structure, but contains long range G-type magnetic ordering, unlike the other vacancy-disordered materials studied.</p> / Doctor of Philosophy (PhD)

El tema principal de esta tesis es el desarrollo de técnicas de actualización de precondicionadores para resolver sistemas lineales de gran tamaño y dispersos Ax=b mediante el uso de métodos iterativos de Krylov. Se consideran dos tipos interesantes de problemas. En el primero se estudia la solución iterativa de sistemas lineales no singulares y antisimétricos, donde la matriz de coeficientes A tiene parte antisimétrica de rango bajo o puede aproximarse bien con una matriz antisimétrica de rango bajo. Sistemas como este surgen de la discretización de PDEs con ciertas condiciones de frontera de Neumann, la discretización de ecuaciones integrales y métodos de puntos interiores, por ejemplo, el problema de Bratu y la ecuación integral de Love. El segundo tipo de sistemas lineales considerados son problemas de mínimos cuadrados (LS) que se resuelven considerando la solución del sistema equivalente de ecuaciones normales. Concretamente, consideramos la solución de problemas LS modificados y de rango incompleto. Por problema LS modificado se entiende que el conjunto de ecuaciones lineales se actualiza con alguna información nueva, se agrega una nueva variable o, por el contrario, se elimina alguna información o variable del conjunto. En los problemas LS de rango deficiente, la matriz de coeficientes no tiene rango completo, lo que dificulta el cálculo de una factorización incompleta de las ecuaciones normales. Los problemas LS surgen en muchas aplicaciones a gran escala de la ciencia y la ingeniería como, por ejemplo, redes neuronales, programación lineal, sismología de exploración o procesamiento de imágenes. Los precondicionadores directos para métodos iterativos usados habitualmente son las factorizaciones incompletas LU, o de Cholesky cuando la matriz es simétrica definida positiva. La principal contribución de esta tesis es el desarrollo de técnicas de actualización de precondicionadores. Básicamente, el método consiste en el cálculo de una descomposición incompleta para un sistema lineal aumentado equivalente, que se utiliza como precondicionador para el problema original. El estudio teórico y los resultados numéricos presentados en esta tesis muestran el rendimiento de la técnica de precondicionamiento propuesta y su competitividad en comparación con otros métodos disponibles en la literatura para calcular precondicionadores para los problemas estudiados. / The main topic of this thesis is updating preconditioners for solving large sparse linear systems Ax=b by using Krylov iterative methods. Two interesting types of problems are considered. In the first one is studied the iterative solution of non-singular, non-symmetric linear systems where the coefficient matrix A has a skew-symmetric part of low-rank or can be well approximated with a skew-symmetric low-rank matrix. Systems like this arise from the discretization of PDEs with certain Neumann boundary conditions, the discretization of integral equations as well as path following methods, for example, the Bratu problem and the Love's integral equation. The second type of linear systems considered are least squares (LS) problems that are solved by considering the solution of the equivalent normal equations system. More precisely, we consider the solution of modified and rank deficient LS problems. By modified LS problem, it is understood that the set of linear relations is updated with some new information, a new variable is added or, contrarily, some information or variable is removed from the set. Rank deficient LS problems are characterized by a coefficient matrix that has not full rank, which makes difficult the computation of an incomplete factorization of the normal equations. LS problems arise in many large-scale applications of the science and engineering as for instance neural networks, linear programming, exploration seismology or image processing. Usually, incomplete LU or incomplete Cholesky factorization are used as preconditioners for iterative methods. The main contribution of this thesis is the development of a technique for updating preconditioners by bordering. It consists in the computation of an approximate decomposition for an equivalent augmented linear system, that is used as preconditioner for the original problem. The theoretical study and the results of the numerical experiments presented in this thesis show the performance of the preconditioner technique proposed and its competitiveness compared with other methods available in the literature for computing preconditioners for the problems studied. / El tema principal d'esta tesi és actualitzar precondicionadors per a resoldre sistemes lineals grans i buits Ax=b per mitjà de l'ús de mètodes iteratius de Krylov. Es consideren dos tipus interessants de problemes. En el primer s'estudia la solució iterativa de sistemes lineals no singulars i antisimètrics, on la matriu de coeficients A té una part antisimètrica de baix rang, o bé pot aproximar-se amb una matriu antisimètrica de baix rang. Sistemes com este sorgixen de la discretització de PDEs amb certes condicions de frontera de Neumann, la discretització d'equacions integrals i mètodes de punts interiors, per exemple, el problema de Bratu i l'equació integral de Love. El segon tipus de sistemes lineals considerats, són problemes de mínims quadrats (LS) que es resolen considerant la solució del sistema equivalent d'equacions normals. Concretament, considerem la solució de problemes de LS modificats i de rang incomplet. Per problema LS modificat, s'entén que el conjunt d'equacions lineals s'actualitza amb alguna informació nova, s'agrega una nova variable o, al contrari, s'elimina alguna informació o variable del conjunt. En els problemes LS de rang deficient, la matriu de coeficients no té rang complet, la qual cosa dificultata el calcul d'una factorització incompleta de les equacions normals. Els problemes LS sorgixen en moltes aplicacions a gran escala de la ciència i l'enginyeria com, per exemple, xarxes neuronals, programació lineal, sismologia d'exploració o processament d'imatges. Els precondicionadors directes per a mètodes iteratius utilitzats més a sovint són les factoritzacions incompletes tipus ILU, o la factorització incompleta de Cholesky quan la matriu és simètrica definida positiva. La principal contribució d'esta tesi és el desenvolupament de tècniques d'actualització de precondicionadors. Bàsicament, el mètode consistix en el càlcul d'una descomposició incompleta per a un sistema lineal augmentat equivalent, que s'utilitza com a precondicionador pel problema original. L'estudi teòric i els resultats numèrics presentats en esta tesi mostren el rendiment de la tècnica de precondicionament proposta i la seua competitivitat en comparació amb altres mètodes disponibles en la literatura per a calcular precondicionadors per als problemes considerats. / Guerrero Flores, DJ. (2018). On Updating Preconditioners for the Iterative Solution of Linear Systems [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/104923

No / The interleukin-2-deficient (IL-2¿/¿) mouse model of ulcerative colitis was used to test the hypothesis that colonic epithelial cells (CEC) directly respond to bacterial antigens and that alterations in Toll-like receptor (TLR)-mediated signaling may occur during the development of colitis. TLR expression and activation of TLR-mediated signaling pathways in primary CEC of healthy animals was compared with CEC in IL-2¿/¿ mice during the development of colitis. In healthy animals, CEC expressed functional TLR, and in response to the TLR4 ligand LPS, proliferated and secreted the cytokines IL-6 and monocyte chemoattractant protein-1 (MCP-1). However, the TLR-responsiveness of CEC in IL-2¿/¿ mice was different with decreased TLR4 responsiveness and augmented TLR2 responses that result in IL-6 and MCP-1 secretion. TLR signaling in CEC did not involve NF-B (p65) activation with the inhibitory p50 form of NF-B predominating in CEC in both the healthy and inflamed colon. Development of colitis was, however, associated with the activation of MAPK family members and upregulation of MyD88-independent signaling pathways characterized by increased caspase-1 activity and IL-18 production. These findings identify changes in TLR expression and signaling during the development of colitis that may contribute to changes in the host response to bacterial antigens seen in colitis.

Yes / We report an evaluation of the cytotoxicity of a series of electron-deficient (16-electron) half-sandwich precious metal complexes of ruthenium, osmium and iridium ([Os/Ru(η6-pcymene)( 1,2-dicarba-closo-dodecarborane-1,2-dithiolato)] (1/2), [Ir(η5-pentamethylcyclopentadiene)(1,2-dicarba-closo-dodecarborane- 1,2-dithiolato)] (3), [Os/Ru(η6-p-cymene)(benzene-1, 2-dithiolato)] (4/5) and [Ir(η5-pentamethylcyclopentadiene) (benzene-1,2-dithiolato)] (6)) towards RAW 264.7 murine macrophages and MRC-5 fibroblast cells. Complexes 3 and 6 were found to be non-cytotoxic. The anti-inflammatory activity of 1–6 was evaluated in both cell lines after nitric oxide (NO) production and inflammation response induced by bacterial endotoxin lipopolysaccharide (LPS) as the stimulus. All metal complexes were shown to exhibit dose-dependent inhibitory effects on LPS-induced NO production on both cell lines. Remarkably, the two iridium complexes 3 and 6 trigger a full anti-inflammatory response against LPS-induced NO production, which opens up new avenues for the development of non-cytotoxic anti-inflammatory drug candidates with distinct structures and solution chemistry from that of organic drugs, and as such with potential novel mechanisms of action. / We thank the Royal Society (University Research Fellowship No. UF150295 to NPEB), and the University of Bradford for financial support.

Yes / Carbon monoxide (CO) is both a substance hazardous to health and a side product of a number of industrial processes, such as methanol steam reforming and large-scale oxidation reactions. The separation of CO from nitrogen (N2) in industrial processes is considered to be difficult because of the similarities of their electronic structures, sizes, and physicochemical properties (e.g., boiling points). Carbon monoxide is also a major poison in fuel cells because of its adsorption onto the active sites of the catalysts. It is therefore of the utmost economic importance to discover new materials that enable effective CO capture and release under mild conditions. However, methods to specifically absorb and easily release CO in the presence of contaminants, such as water, nitrogen, carbon dioxide, and oxygen, at ambient temperature are not available. Here, we report the simple and versatile fabrication of a new class of hybrid materials that allows capture and release of carbon monoxide under mild conditions. We found that carborane-containing metal complexes encapsulated in networks made of poly(dimethylsiloxane) react with CO, even when immersed in water, leading to dramatic color and infrared signature changes. Furthermore, we found that the CO can be easily released from the materials by simply dipping the networks into an organic solvent for less than 1 min, at ambient temperature and pressure, which not only offers a straightforward recycling method, but also a new method for the “on-demand” release of carbon monoxide. We illustrated the utilization of the on-demand release of CO from the networks by carrying out a carbonylation reaction on an electron-deficient metal complex that led to the formation of the CO-adduct, with concomitant recycling of the gel. We anticipate that our sponge-like materials and scalable methodology will open up new avenues for the storage, transport, and controlled release of CO, the silent killer and a major industrial poison. / The Royal Society, The Romanian Ministry of Education and Research, The University of Bradford, European Regional Development Fund of the European Union / Research Development Fund Publication Prize Award winner.

No / 4-Chloro-2(H)-pyran-2-one undergoes thermal Diels−Alder cycloaddition with electron-deficient dienophiles to afford, without any significant selectivity, 6-endo- and 5-endo-substituted bicyclic lactone cycloadducts. In contrast to 3- and 5-bromo-2(H)-pyran-2-one, 4-chloro-2(H)-pyran-2-one does not undergo thermal cycloadditions with electron-rich dienophiles. The regio- and stereochemical preferences of the cycloadditions of 4-chloro-2(H)-pyran-2-one and other related 2(H)-pyran-2-ones are investigated computationally. Calculations were carried out on the transition states leading to the four possible regio- and stereoisomeric cycloadducts using density functional theory (B3LYP/6-31G*). These studies allow prediction of the regio- and stereoselectivity in these reactions which are in line with experimental observations.

Title: Instrumental Gait Analysis in the ACL Patient Aim: to present an up to date review on the topic of instrumental analysis of straight ahead gait on a plain surface (both over-ground and on a treadmill) in ACL patients (both deficient and reconstructed). A second aim is to introduce the clinician (especially in the field of physiotherapy/rehabilitation) to the topic of gait analysis and its specific use for the ACL patient. Methods: a systematic review on the topic Results The review answers the questions of what instrumentation, phases of gait and variables is best to use/measure for clinical purposes. It also identifies and discusses three main gait strategies used by ACL patients: quadriceps avoidance, knee stiffening, pivot shift avoidance. Keywords: gait, analysis, walking, clinical, instrumental, anterior cruciate ligament, ACL, deficient, reconstruction, injury

Este trabalho visou a produção de suportes para crescimento celular constituídos de compósitos de poli(L-lactídeo) (PLLA) e diversos tipos de fosfatos de cálcio (CaP). A hidroxiapatita deficiente em cálcio (HAD) e o fosfato octacálcico (OCP) em tamanhos submicrométricos foram sintetizados. Hidroxiapatita (HA) e o &#946;-fosfato tricálcico (&#946;-TCP) foram adquiridos da Sigma-Aldrich. Uma mistura de HAD:&#946;-TCP (7:3) também foi preparada. Para melhorar a dispersão da fase mineral em uma matriz polimérica de PLLA, utilizou-se cloreto de lauroíla para funcionalizar a superfície dos CaP. Os espectros de infravermelho e a análise termogravimétrica confirmaram a presença de laurato na superfície de partículas de CaP. As partículas de HA pura também foram funcionalizadas com cloreto de lauroíla para fins comparativos. Compósitos de PLLA/CaP-laurato foram fabricados utilizando a técnica de eletrofiação. A funcionalização da superfície do CaP com laurato resultou em uma melhoria significativa na dispersão de partículas de CaP na matriz polimérica, permitindo a inclusão de até 40% da fase mineral sem comprometer as propriedades mecânicas. Microscopia eletrônica de varredura (SEM) e microscopia eletrônica de transmissão (TEM) foram utilizadas para investigar a morfologia da fibra. A perda de massa e a liberação de cálcio dos suportes durante a degradação em uma solução salina tamponada com fosfato (PBS) foram medidas. HAD e OCP se mostraram ser mais solúveis do que HA e HAD:&#946;-TCP (7:3). A bioatividade dos compósitos foi investigada por imersão das fibras em um fluido corporal simulado (SBF) a 37 °C e pH 7.4. Embora todos os suportes de PLLA/CaP-laurato foram capazes de formar uma camada de apatita em sua superfície após a exposição em SBF, os resultados demonstraram um aumento significativo na mineralização quando HAD, OCP e HAD:&#946;-TCP (7:3) são a fase mineral no compósito em vez da HA. Além disso, malhas produzidas a partir das fibras eletrofiadas de PLLA/CaP-laurato, utilizadas como suporte para crescimento celular, favoreceram a adesão e proliferação de células de fibroblastos de camundongo (NIH-3T3) e células tronco mesenquimais de dentes decíduos humanos (SHED). Finalmente, suportes a partir das malhas PLLA/HAD-laurato e PLLA/OCP-laurato apresentaram melhor desempenho para acelerar a calcificação in vitro como resultado da osteoindução de células SHED e de células pré-osteoblásticas derivadas de calvária de rato (MC3T3-E1) se comparados aqueles contendo HA e HAD:&#946;-TCP (7:3). Esses novos materiais são propostos como biocompósitos de rápida degradação de CaP, para serem utilizados em aplicações de regeneração óssea em ortodontia e ortopedia. / This work aimed at the generation of scaffolds for cellular growth constituted by poly(L-lactide) (PLLA) and several types of calcium phosphate (CaP). Calcium deficient hydroxyapatite (HAD) and octacalcium phosphate (OCP) were synthesized in submicrometer sizes. Hydroxyapatite (HA) and &#946;-tricalcium phosphate (&#946;-TCP) were purchased from Sigma-Aldrich. A mixture of HAD:&#946;-TCP (7:3) also was prepared. In order to improve the dispersion of the mineral phase in a PLLA polymeric matrix, lauroyl chloride was used to functionalize the surface of CaP. Infrared spectra and thermal gravimetric analysis confirmed the presence of laurate on the surface of CaP particles. Neat HA particles were also functionalized with lauryl chloride for comparative purposes. Composites of PLLA/CaP-laurate were fabricated by electrospinning method. The functionalization of CaP surfaces resulted in significant improvement of the dispersion of CaP particles into the polymeric matrix, allowing inclusion of up to 40% of mineral phase without compromising its mechanical properties. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to investigate the morphology of the fibers. The mass loss and calcium release of the scaffolds during degradation in phosphate buffered saline (PBS) were measured. HAD and OCP are more soluble than HA and HAD:&#946;-TCP (7:3). The bioactivity of the composites was investigated by immersing the fibers in a simulated body fluid (SBF) at 37°C and pH 7.4. Although all PLLA/CaP-laurate can form apatite precipitation on their surface after exposition to SBF, the results demonstrate a significant enhancement in the mineralization when HAD, OCP and HAD:&#946;-TCP (7:3) are the mineral phase in the composite instead of HA. Furthermore, mats obtained from PLLA/CaP-laurate electrospun fibers favored the mouse fibroblast cells (NIH-3T3) and stem cells from human exfoliated deciduous teeth (SHED) attachment and proliferation. Finally, PLLA/HAD-laurate and PLLA/OCP-laurate meshes showed better performance in accelerate the calcium phosphate mineralization on its surface as a result of the in vitro osteoinduction of SHEDs and calvaria derived mouse preosteoblastic cells (MC3T3-E1) if compared of those containing HA and HAD:&#946;-TCP (7:3). These new materials are proposed as fast degradation CaP biocomposites to be used in bone regeneration applications in orthodontics and orthopedics.

<p>Atopic dermatitis (AD) is a common pruritic skin disease in people and domestic animals that can be severely debilitating and stressful to the patient and the caregiver. The diagnosis of AD requires time consuming and expensive procedures, and treatment is often lifelong at considerable cost. Alterations in the lipid composition of the epidermis are a hallmark of the disease, and these may represent changes caused by the inflammation and defects in the lipid barrier. Liquid chromatography tandem mass spectrometry (LC-MS/MS) and, more recently, untargeted profiling using high-resolution time-of-flight instruments have been used to quantify the lipid composition in skin and other tissues, but these approaches are highly demanding in sample preparation and instrument time. In addition, these methods either detect only a limited number of lipids at the time or the identification of detected mass-to-charge ratio (m/z) is problematic when untargeted profiling is used. New lipidomic approaches that generate lipid profiles in a faster and more efficient manner can lead to a better understanding of these lipid changes. </p><p>The mass spectrometry analytical strategy used in this study, multiple reaction monitoring (MRM)-profiling, rapidly identifies discriminant lipids of the epidermis by flow injection. MRM-profiling is a small molecule accelerated discovery workflow performed in two parts using a triple quadrupole mass spectrometer with electrospray ionization as the ion source. Briefly, the first step consists of discovery experiments based on neutral loss and precursor ion scans to detect lipids in pooled samples by targeting class-specific chemical motifs such as polar heads of phospholipids or sphingoid bases of ceramides. The second step of the MRM-profiling is the screening of individual samples for the transitions detected in the discovery phase. </p><p>We first developed the experimental approach of the MRM-profiling methodology using epidermal samples of mice with AD-like inflammatory skin disease (chronic proliferative dermatitis, cpdm). Subsequently, we investigated lipid changes as the disease in mice progressed from minimal to severe. In order to select the most relevant ions, we utilized a two-tiered filter/wrapper feature-selection strategy. First, we built linear models linking the presence of every lipid monitored to disease stage information. The top 10 lipids, ranked based on η2 effect size, were used to build a predictive elastic-net (E-net) regression model linking the lipid ions detected by MRM-profiling with disease progression. The developed model accurately identified disease stages based on the variations in relative amounts of lipid ions corresponding to phosphatidylcholines, cholesterol esters, and glycerolipids-containing and eicosapentaenoic acid fatty acyl residues. Finally, we investigated the lipid profile of the epidermis in dogs with canine AD using the previously developed methodology. Epidermis from client owned patients and healthy controls were collected. Patients were sampled from affected and unaffected skin avoiding areas with secondary infections and the canine atopic dermatitis extent and severity index (CADESI-4) was recorded. The monitored lipids substantially separated the samples of healthy dogs from atopic dogs and distinguished the affected from the unaffected skin of patients. Samples were grouped into two cohorts for low-score and high-score CADESI-4, the first principal component was able to differentiate the control group from the low and high-score group. Differences in the lipid composition associated with low and high score CADESI-4 were significantly different only after separating the samples by sex of the dogs, demonstrating sexual dimorphism in the lipid changes associated with disease. The compositional data was feature extracted using the CADESI-4 to build linear models that identified oleic acid-containing triacylglycerides, long-chain acylcarnitines and sphingolipids as highly predictive lipids and were subsequently used to construct a predictive E-net regression. The lipid fingerprint obtained from the MRM-profiling was highly correlated (R2=0.89) with the classification of the standardized CADESI-4 score. </p><p>This research showed that changes in the lipid composition of the epidermis can be detected by MRM-profiling in atopic dogs even when the skin looks clinically healthy and that sex is a modifying factor in the lipid profile of canine atopic dermatitis (CAD). We expect that this research leads to a better understanding of the lipid changes in the epidermis during the onset of AD and as the chronic inflammatory process develops. The high prediction rate given by the lipid biomarkers for disease progression identified here by the machine learning strategy provides a potential molecular assessment tool for the diagnosis and monitoring of atopic dermatitis and the patient response to treatment.</p><div><br></div>