928 resultados para reaction analysis
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The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L-1 of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L-1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.
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The present paper describes the one-pot procedure for the formation of self-assembled thin films of two silanes on the model oxidized silicon wafer, SiO2/Si. SiO2/Si is a model system for other surfaces, such as glass, quartz, aerosol, and silica gel. MALDI-TOF MS with and without a matrix, XPS, and AFM have confirmed the formation of self-assembled thin films of both 3-imidazolylpropyltrimethoxysilane (3-IPTS) and 4-(N- propyltriethoxysilane-imino)pyridine (4-PTSIP) on the SiO2/Si surface after 30 min. Longer adsorption times lead to the deposition of nonreacted 3-IPTS precursors and the formation of agglomerates on the 3-IPTS monolayer. The formation of 4-PTSIP self-assembled layers on SiO2/Si is also demonstrated. The present results for the flat SiO2/Si surface can lead to a better understanding of the formation of a stationary phase for affinity chromatography as well as transition-metal-supported catalysts on silica and their relationship with surface roughness and ordering. The 3-IPTS and 4-PTSIP modified SiO2/Si wafers can also be envisaged as possible built-on-silicon thin-layer chromatography (TLC) extraction devices for metal determination or N-heterocycle analytes, such as histidine and histamine, with on-spot MALDI-TOF MS detection. © 2005 Elsevier Inc. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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The zero-valent iron (ZVI) mediated degradation of the antibiotic ciprofloxacin (CIP) was studied under oxic condition. Operational parameters such as ZVI concentration and initial pH value were evaluated. Increase of the ZVI concentration from 1 to 5 g L−1 resulted in a sharp increase of the observed pseudo-first order rate constant of CIP degradation, reaching a plateau at around 10 g L−1. The contribution of adsorption to the overall removal of CIP and dissolved organic carbon (DOC) was evaluated after a procedure of acidification to pH 2.5 with sulfuric acid and sonication for 2 min. Adsorption increased as pH increased, while degradation decreased, showing that adsorption is not important for degradation. Contribution of adsorption was much more important for DOC removal than for CIP. Degradation of CIP resulted in partial defluorination since the fluoride measured corresponded to 34% of the theoretical value after 120 min of reaction. Analysis by liquid chromatography coupled to mass spectrometry showed the presence of products of hydroxylation on both piperazine and quinolonic rings generating fluorinated and defluorinated compounds as well as a product of the piperazine ring cleavage.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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The aim of the present thesis was to investigate the influence of lower-limb joint models on musculoskeletal model predictions during gait. We started our analysis by using a baseline model, i.e., the state-of-the-art lower-limb model (spherical joint at the hip and hinge joints at the knee and ankle) created from MRI of a healthy subject in the Medical Technology Laboratory of the Rizzoli Orthopaedic Institute. We varied the models of knee and ankle joints, including: knee- and ankle joints with mean instantaneous axis of rotation, universal joint at the ankle, scaled-generic-derived planar knee, subject-specific planar knee model, subject-specific planar ankle model, spherical knee, spherical ankle. The joint model combinations corresponding to 10 musculoskeletal models were implemented into a typical inverse dynamics problem, including inverse kinematics, inverse dynamics, static optimization and joint reaction analysis algorithms solved using the OpenSim software to calculate joint angles, joint moments, muscle forces and activations, joint reaction forces during 5 walking trials. The predicted muscle activations were qualitatively compared to experimental EMG, to evaluate the accuracy of model predictions. Planar joint at the knee, universal joint at the ankle and spherical joints at the knee and at the ankle produced appreciable variations in model predictions during gait trials. The planar knee joint model reduced the discrepancy between the predicted activation of the Rectus Femoris and the EMG (with respect to the baseline model), and the reduced peak knee reaction force was considered more accurate. The use of the universal joint, with the introduction of the subtalar joint, worsened the muscle activation agreement with the EMG, and increased ankle and knee reaction forces were predicted. The spherical joints, in particular at the knee, worsened the muscle activation agreement with the EMG. A substantial increase of joint reaction forces at all joints was predicted despite of the good agreement in joint kinematics with those of the baseline model. The introduction of the universal joint had a negative effect on the model predictions. The cause of this discrepancy is likely to be found in the definition of the subtalar joint and thus, in the particular subject’s anthropometry, used to create the model and define the joint pose. We concluded that the implementation of complex joint models do not have marked effects on the joint reaction forces during gait. Computed results were similar in magnitude and in pattern to those reported in literature. Nonetheless, the introduction of planar joint model at the knee had positive effect upon the predictions, while the use of spherical joint at the knee and/or at the ankle is absolutely unadvisable, because it predicted unrealistic joint reaction forces.
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BACKGROUND: Acne inversa (hidradenitis suppurativa) is a chronic inflammatory and cicatricial disorder that affects skin areas rich in apocrine glands and terminal hairs, such as perineum and axillae. The exact pathogenesis of the disease is not well understood and the mechanisms by which bacterial superinfection contributes to the disease progression are not clear. Toll-like receptors (TLRs) expressed by inflammatory cells play a crucial role in the innate immune response to bacteria. OBJECTIVES: We sought to investigate the role of TLR2 in the pathogenesis of acne inversa. METHODS: We investigated the expression of TLR2 using real-time polymerase chain reaction analysis and immunohistochemical stainings of tissue samples from patients with acne inversa. Furthermore, we phenotypically characterized the infiltrating cells and their expression of TLR2. RESULTS: Compared with normal skin, a highly increased in situ expression of TLR2 in acne inversa skin lesions was found at both the mRNA and the protein level. The most abundant cells in the dermal infiltrate of acne inversa were CD68+ macrophages, CD209+ dendritic cells (DCs) and CD3+ T cells. CD19+ B cells and CD56+ natural killer cells were found only in small numbers. Double staining with fluorescence-labelled antibodies showed that TLR2 was expressed by infiltrating macrophages (CD68+) and DCs (CD209+). Flow cytometric analysis of isolated infiltrating cells further confirmed surface expression of TLR2 by macrophages and DCs. CONCLUSIONS: These data indicate that the enhanced expression of TLR2 by infiltrating macrophages and DCs may contribute to the pathogenesis of inflammatory lesions of acne inversa.
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The corpus luteum (CL) is a temporary organ involved in the maintenance of pregnancy. In the course of its life-cycle, the CL undergoes two distinct and consecutive processes for its inevitable removal through apoptosis: functional and structural luteolysis. We isolated a gene encoding for a novel rat zinc finger protein (ZFP), named rat ZFP96 (rZFP96) from an ovarian lambda cDNA library. Sequence analysis revealed close sequence and structural similarity to mouse ZFP96 and human zinc finger protein 305 (ZNF305). Quantitative reverse transcription-polymerase chain reaction analysis revealed a positive correlation with the end of pregnancy, that is, the onset of structural luteolysis of the CL. Messenger RNA levels increased 3-fold (P < 0.01) between days 13 and 22 of pregnancy and 8-fold (P < 0.01) between day 13 of pregnancy and day 1 post-partum. In addition, we detected rZFP96 expression in mammary, placenta, heart, kidney and skeletal muscle. Sequence analysis predicted that rZFP96 has a high probability of localizing to the nuclear compartment. The presence of both a perfect consensus TGEKP linker sequence between zinc fingers 2 and 3 as well as several similar sequences between the other zinc fingers suggests physical interaction with DNA. Speculatively, rZFP96 may therefore function as a transcription factor, switching-off pro-survival genes and/or upregulating pro-apoptotic genes and thereby contributing to the demise of the CL.
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OBJECTIVE: This study sought to characterize the inflammatory infiltrate in ascending thoracic aortic aneurysm in patients with Marfan syndrome, familial thoracic aortic aneurysm, or nonfamilial thoracic aortic aneurysm. BACKGROUND: Thoracic aortic aneurysms are associated with a pathologic lesion termed "medial degeneration," which is described as a noninflammatory lesion. Thoracic aortic aneurysms are a complication of Marfan syndrome and can be inherited in an autosomal dominant manner of familial thoracic aortic aneurysm. METHODS: Full aortic segments were collected from patients undergoing elective repair with Marfan syndrome (n = 5), familial thoracic aortic aneurysm (n = 6), and thoracic aortic aneurysms (n = 9), along with control aortas (n = 5). Immunohistochemistry staining was performed using antibodies directed against markers of lymphocytes and macrophages. Real-time polymerase chain reaction analysis was performed to quantify the expression level of the T-cell receptor beta-chain variable region gene. RESULTS: Immunohistochemistry of thoracic aortic aneurysm aortas demonstrated that the media and adventitia from Marfan syndrome, familial thoracic aortic aneurysm, and sporadic cases had increased numbers of T lymphocytes and macrophages when compared with control aortas. The number of T cells and macrophages in the aortic media of the aneurysm correlated inversely with the patient's age at the time of prophylactic surgical repair of the aorta. T-cell receptor profiling indicated a similar clonal nature of the T cells in the aortic wall in a majority of aneurysms, whether the patient had Marfan syndrome, familial thoracic aortic aneurysm, or sporadic disease. CONCLUSION: These results indicate that the infiltration of inflammatory cells contributes to the pathogenesis of thoracic aortic aneurysms. Superantigen-driven stimulation of T lymphocytes in the aortic tissues of patients with thoracic aortic aneurysms may contribute to the initial immune response.
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The primary objective of this study has been to investigate the effects at the molecular level of trisomy of mouse chromosome 7 in chemically induced skin tumors. It was previously proposed that the initiation event in the mouse skin carcinogenesis model is a heterozygous mutation of the Ha-ras-1 gene, mapped to chromosome 7. Previous studies in this laboratory identified trisomy 7 as one of the primary nonrandom cytogenetic abnormalities found in the majority of severely dysplastic papillomas and squamous cell carcinomas induced in SENCAR mice by an initiation-promotion protocol. Therefore, the first hypothesis tested was that trisomy 7 occurs by specific duplication of the chromosome carrying a mutated Ha-ras-1 allele. Results of a quantitative analysis of normal/mutated allelic ratios of the Ha-ras-1 gene confirmed this hypothesis, showing that most of the tumors exhibited overrepresentation of the mutated allele in the form of 1/2, 0/3, and 0/2 (normal/mutated) ratios. In addition, histopathological analysis of the tumors showed an apparent association between the degree of malignancy and the dosage of the mutated Ha-ras-1 allele. To determine the mechanism for loss of the normal Ha-ras-1 allele, found in 30% of the tumors, a comparison of constitutional and tumor genotypes was performed at different informative loci of chromosome 7. By combining Southern blot and polymerase chain reaction fragment length polymorphism analyses of DNAs extracted from squamous cell carcinomas, complete loss of heterozygosity was detected in 15 of 20 tumors at the Hbb locus, and in 5 of 5 tumors at the int-2 locus, both distal to Ha-ras-1. In addition, polymerase chain reaction analysis of DNA extracted from papillomas indicated that loss of heterozygosity occurs in late-stage lesions exhibiting a high degree of dysplasia and areas of microinvasion, suggesting that this event may be associated to the acquisition of the malignant phenotype. Allelic dosage analysis of tumors that had become homozygous at Hbb but retained heterozygosis at Ha-ras-1, indicated that loss of heterozygosity on mouse chromosome 7 occurs by a mitotic recombination mechanism. Overall, these findings suggest the presence of a putative tumor suppressor locus on the 7F1-ter region of mouse chromosome 7. Thus, loss of function by homozygosis at this putative suppressor locus may complement activation of the Ha-ras-1 gene during tumor progression, and might be associated with the malignant conversion stage of mouse skin carcinogenesis. ^
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Trichinellosis is one of the most important foodborne parasitic zoonoses, caused by nematodes of the genus Trichinella. Pigs and other domestic and wild animals, including red foxes (Vulpes vulpes), are sources of Trichinella infection for human beings. Trichinella britovi is the major agent of infection in sylvatic animals and the most important species circulating in the European wildlife. The present study aimed at assessing Trichinella spp. infection in red foxes from the North of Portugal. Forty-seven carcasses of wild red foxes shot during the official hunting season or killed in road accidents were obtained between November 2008 and March 2010. In order to identify the presence of Trichinella spp. larvae in red foxes, an individual artificial digestion was performed using approximately 30g of muscle samples. Larvae of Trichinella spp. were detected in one (2.1%) out of the 47 assessed foxes. After a multiplex polymerase chain reaction analysis, T. britovi was molecularly identified as the infecting species. The recognition of T. britovi in a red fox confirms that a sylvatic cycle is present in the North of Portugal and that the local prevalence of Trichinella infection in wildlife must not be ignored due to its underlying zoonotic risks.
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A high resolution focused beam line has been recently installed on the AIFIRA (“Applications Interdisciplinaires des Faisceaux d’Ions en Région Aquitaine”) facility at CENBG. This nanobeam line, based on a doublet–triplet configuration of Oxford Microbeam Ltd. OM-50™ quadrupoles, offers the opportunity to focus protons, deuterons and alpha particles in the MeV energy range to a sub-micrometer beam spot. The beam optics design has been studied in detail and optimized using detailed ray-tracing simulations and the full mechanical design of the beam line was reported in the Debrecen ICNMTA conference in 2008. During the last two years, the lenses have been carefully aligned and the target chamber has been fully equipped with particle and X-ray detectors, microscopes and precise positioning stages. The beam line is now operational and has been used for its firstapplications to ion beam analysis. Interestingly, this set-up turned out to be a very versatile tool for a wide range of applications. Indeed, even if it was not intended during the design phase, the ion optics configuration offers the opportunity to work either with a high current microbeam (using the triplet only) or with a lower current beam presenting a sub-micrometer resolution (using the doublet–triplet configuration). The performances of the CENBGnanobeam line are presented for both configurations. Quantitative data concerning the beam lateral resolutions at different beam currents are provided. Finally, the firstresults obtained for different types of application are shown, including nuclear reaction analysis at the micrometer scale and the firstresults on biological samples
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In future power plants (i.e. DEMO), the nuclear fusion of hydrogen isotopes will be used for energy production. The behaviour of hydrogen isotopes in lithium-enriched ceramics for breeder blankets (BBs) is one of the most important items to be understood. In this paper we present the chemical, microstructural and morphological features of Li4SiO4, Li2TiO3 and a third ceramic candidate with a higher Li:Si proportion (3:1), implanted with D at an energy of 100 keV and at room temperature at a fluence of 1 × 1017 cm−2. The D depth-profile in as-implanted and annealed ceramics (at T ⩽ 200 °C) was characterised by Resonance Nuclear Reaction Analysis (RNRA). The RNRA data indicate that the total amount of D is retained at room temperature, while annealing at 100 °C promotes D release and annealing at T ⩾ 150 °C drives D to completely desorb from all the studied ceramics. D release will be discussed as a function of the microstructurural and morphological features of each material.