Synthesis of Robust Hierarchical Silica Monoliths by Surface-Mediated Solution/Precipitation Reactions over Different Scales: Designing Capillary Microreactors for Environmental Applications

A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

Capillary microreactors based on hierarchical SiO2 monoliths incorporating noble metal nanoparticles for the Preferential Oxidation of CO

Novel hierarchical SiO2 monolithic microreactors loaded with either Pd or Pt nanoparticles have been prepared in fused silica capillaries and tested in the Preferential Oxidation of CO (PrOx) reaction. Pd and Pt nanoparticles were prepared by the reduction by solvent method and the support used was a mesoporous SiO2 monolith prepared by a well-established sol–gel methodology. Comparison of the activity with an equivalent powder catalyst indicated that the microreactors show an enhanced catalytic behavior (both in terms of CO conversion and selectivity) due to the superior mass and heat transfer processes that take place inside the microchannel. TOF values at low CO conversions have been found to be ∼2.5 times higher in the microreactors than in the powder catalyst and the residence time seems to have a noticeable influence over the selectivity of the catalysts designed for this reaction. The Pd and Pt flexible microreactors developed in this work have proven to be effective for the CO oxidation reaction both in the presence and absence of H2, standing out as a very interesting and suitable option for the development of CO purification systems of small dimensions for portable and on-board applications.

The mechanisms and qualifications of the selective permeability in transport across biological barriers : the example of kyotorphin

Trabalho Final do Curso de Mestrado Integrado em Medicina, Faculdade de Medicina, Universidade de Lisboa, 2014

Rôles de la protéine tyrosine phosphatase DEP-1 dans l'angiogenèse, la perméabilité vasculaire et la progression tumorale

L’angiogenèse et l’augmentation de la perméabilité vasculaire sont des éléments clés pour la croissance et la progression tumorale. Par conséquent, de nombreux efforts sont déployés à comprendre les mécanismes moléculaires impliqués dans la formation et le remodelage des vaisseaux sanguins de manière à identifier de nouvelles cibles thérapeutiques potentielles. De cette optique, les travaux de cette thèse se sont concentrés sur la protéine tyrosine phosphatase DEP-1, initialement identifiée comme un régulateur négatif de la prolifération et de la phosphorylation du VEGFR2 lorsque fortement exprimée dans les cellules endothéliales. Toutefois, en utilisant une approche d’ARNi, il a été démontré que via sa capacité à déphosphoryler la tyrosine inhibitrice de Src (Y529), DEP-1 était également un régulateur positif de l’activation de Src dans les cellules endothéliales stimulées au VEGF. Puisque Src joue un rôle central dans la promotion de l’angiogenèse et la perméabilité vasculaire, nous avons en plus démontré que DEP-1 était un promoteur de ces fonctions in vitro et que la tyrosine phosphorylation de sa queue C-terminale, permettant l’interaction et l’activation de Src, était requise. Les travaux de recherche présentés dans cette thèse démontrent dans un premier temps à partir d’une souris Dep1 KO, dont le développement ne présente aucun phénotype apparent, que la perte de l’expression de DEP-1 se traduit en une inhibition de l’activation de Src et de l’un de ses substrats, la VE-Cadherine, en réponse au VEGF chez la souris adulte. Nos résultats démontrent donc, pour la première fois, le rôle primordial de DEP-1 dans l’induction de la perméabilité vasculaire et de la formation de capillaires in vivo. Conséquemment, la croissance tumorale et la formation de métastases aux poumons sont réduites due à une inhibition de leur vascularisation ce qui se traduit par une diminution de la prolifération et une augmentation de l’apoptose des cellules cancéreuses. De façon intéressante, l’expression élevée de DEP-1 dans les vaisseaux sanguins tumoraux de patientes atteintes du cancer du sein corrèle avec une vascularisation accrue de la tumeur. En plus du rôle de DEP-1 dans la réponse angiogénqiue à l’âge adulte, nos travaux ont également démontré le rôle important de DEP-1 lors de la vascularisation de la rétine, un modèle in vivo d’angiogenèse développementale. Dans ce contexte, DEP-1 inhibe la prolifération des cellules endothéliales et limite leur bourgeonnement et la complexification du réseau vasculaire rétinien en permettant l’expression adéquate du Dll4, un régulateur crucial de l’organisation de la vascularisation développementale. Cette expression du Dll4 découlerait de la stabilisation de la β-caténine par l’inactivation de la GSK3β, un régulateur important de la dégradation de la β-caténine, en réponse au VEGF selon la voie de signalisation VEGFR2-Src-PI3K-Akt-GSK3β. Ainsi, ces travaux identifient DEP-1 comme un régulateur important de l’organisation vasculaire rétinienne. Les rôles positifs de DEP-1 dans les cellules endothéliales découlent principalement de sa capacité à lier et activer la kinase Src. En plus de contribuer à la réponse angiogénique, Src est également un oncogène bien caractérisé notamment pour sa contribution au programme invasif des cellules cancéreuses mammaires. Les travaux de cette thèse illustrent que DEP-1 est préférentiellement exprimée dans les cellules cancéreuses mammaires invasives et qu’il régule l’activation de Src, de voies de signalisation invasives et, par le fait même, de l’invasivité de ces cellules in vitro et in vivo. De façon intéressante, ces observations corrèlent avec des données cliniques où l’expression modérée de DEP-1 est associée à un mauvais pronostic de survie et de rechute. Ces résultats démontrent donc, pour la première fois, le rôle positif de DEP-1 dans l’activation de Src au niveau des cellules endothéliales et des cellules cancéreuses mammaires ce qui permet la régulation du bourgeonnement endothélial, de la perméabilité vasculaire, de l’angiogenèse normale et pathologique en plus de l’invasion tumorale.

Therapeutic drug monitoring of cefepime with micellar electrokinetic capillary chromatography: Assay improvement, quality assurance, and impact on patient drug levels

The improvement and performance of a micellar electrokinetic capillary chromatography assay for cefepime in human serum and plasma with a 50 μm id fused-silica capillary elongated from 40 to 60 cm is reported. Sample preparation with dodecylsulfate protein precipitation at pH 4.5, the pH 9.1 separation medium and the applied voltage were as reported previously[16]. The change resulted in a significant lower current, higher resolution and increased detection time intervals. The performance of the assay with multi-level internal calibration was assessed with calibration and control samples. Quality assurance data of a two year period assessed under the new conditions demonstrated the robustness of the assay. In serum samples of patients who received both cefepime and sulfamethoxazole, cefepime could not be detected due to the inseparability of the two compounds. The presence of an interference can be recognized by an increased peak width (width > 0.2 min), the appearance of a shoulder or an unresolved double peak. The patient data gathered during a three year period reveal that introduction of therapeutic drug monitoring led to a 50% reduction of the median drug level. The data suggest that therapeutic drug monitoring can help to minimize the risk of major adverse reactions and to increase drug safety on an individual basis. This article is protected by copyright. All rights reserved.

(Table T1) Porosity and permeability of samples from ODP Leg 180 sites

Woodlark Basin, an area of continental extension, is an ideal location to study the evolution of permeability and the development of overpressures within an active rift basin. In this investigation, we measured sediment permeabilities of cores from Woodlark Basin and used numerical modeling to determine if pore fluid overpressures are likely at the base of the rift basin. Constant-rate flow tests were conducted on cores from Site 1108, located in the rift basin, and Sites 1115 and 1118, located on the northern margin of the basin. Results of the laboratory tests indicated permeabilities that range from 1.5 x 10**-18 to 1 x 10**-16 m**2. Results of the numerical modeling of Site 1108 suggest that overpressures due to sedimentation are unlikely.

Petrophysical measurement of ODP Leg 122 and 123 samples (Tables 1, 2)

The capillary-pressure characteristics of 22 samples of lithified post-Paleozoic Indian-Ocean carbonates were compared to published data from older carbonate rocks (lower Paleozoic Hunton Group of Texas and Oklahoma). The Indian-Ocean samples are considerably more porous than are the Paleozoic samples, yet all of the Indian-Ocean samples fit readily into a descriptive petrofacies scheme previously established for the Hunton Group. The Indian-Ocean samples may be assigned to four petrophysical facies (petrofacies) based on the shapes of their capillary-pressure curves, their pore-throat-size distributions, their estimated recovery efficiency values (for nonwetting fluids), and the visual characteristics of their pore systems, as observed with a scanning-electron microscope. Petrofacies assignments for the Indian-Ocean samples are as follows. Petrofacies I includes six samples collected from the coarse basal portions of event deposits (primarily turbidites). These samples have large throats, leptokurtic throat-size distributions, low- to moderate recovery efficiency values, concave cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies II includes two sedimentologically dissimilar samples that have medium-size throats, platykurtic throat-size distributions, moderate- to-high recovery efficiency values, gently sloping cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies III includes two polymictic sandstones and a skeletal packstone that have small throats, polymodal throat-size distributions, moderate recovery efficiency values, gently sloping cumulative-intrusion capillary-pressure curves, and high porosity values. Petrofacies IV includes 11 samples, mostly recrystallized neritic carbonates, that have small throats, leptokurtic throat-size distributions, high recovery efficiency values, convex cumulative-intrusion capillary-pressure curves, and low porosity values. Comparison of petrofacies assignment to core-, thin-section-, and smear-slide data, and to inferred depositional setting, suggests that pore systems in most samples from Holes 765C and 766A result from primary depositional features, whereas pore systems in samples from Hole 761C and one sample from Hole 765C have been strongly influenced by diagenetic processes. For Hole 761C, prediction of petrophysical parameters should be most successful if based on diagenetic facies patterns. By contrast, the distribution of favorable reservoir facies and of permeability barriers in less highly altered rocks collected from Holes 765C and 766A is related to depositional patterns. Recovery efficiency is inversely related to both porosity and median throat size for the present data set. This relationship is similar to that observed for carbonates of the lower Paleozoic Hunton Group and the Ordovician Ellenburger dolomite, but opposite of that observed for some other ancient carbonates. The coarse deposits of the massive basal units of turbidites are petrophysically distinct and form a coherent petrophysical group (Petrofacies I) with substantial reservoir potential. Two samples assigned to Petrofacies I have extremely large throats (median throat size at least 4 ?m, and at least six times that of any other sample) and therefore high permeability values. These two samples come from thin, coarse turbidites that lack or have poorly developed fine divisions and are interpreted to have been deposited on channeled suprafan lobes in a proximal mid-fan setting. The restriction of extremely high permeability values to a single depositional facies suggests that careful facies mapping of deep-sea fans in a deliberate search for such coarse turbidites could dramatically enhance the success of exploration for aquifers or hydrocarbon reservoirs. Such reservoirs should have substantial vertical heterogeneity. They should have high lateral permeability values but low vertical permeability values, and reservoir sections should include numerous thin units having widely differing petrophysical characteristics.

(Table T1) Permeability, electrical resistivity and density of ODP Hole 193-1188A and Site 193-1189 minicores, PACMANUS field

Magmatic fluids, heat fluxes, and fluid/rock interactions associated with hydrothermal systems along spreading centers and convergent margins have a significant impact on the genesis of major sulfide deposits and biological communities. Circulation of hydrothermal fluids is one of the most fundamental processes associated with localized mineralization and is controlled by inherent porous and permeable properties of the ocean crust. Heat from magmatic intrusions drives circulation of seawater through permeable portions of the oceanic crust and upper mantle, discharging at the seafloor as both focused high-temperature (250°-400°C) fluids and diffuse lower-temperature (<250°C) fluids. This complex interaction between the circulating hydrothermal fluids and the oceanic basement greatly influences the physical properties and the composition of the crust (Thompson, 1983; Jacobson, 1992, doi:10.1029/91RG02811; Johnson and Semyan, 1994, doi:10.1029/93JB00717). During Ocean Drilling Program (ODP) Leg 193, 13 holes were drilled in the PACMANUS hydrothermal system (Binns, Barriga, Miller, et al., 2002, doi:10.2973/odp.proc.ir.193.2002). The hydrothermal system consists of isolated hydrothermal deposits lined along the main crest of the Pual Ridge, a 500- to 700-m-high felsic neovolcanic ridge in the eastern Manus Basin. The principal drilling targets were the Snowcap (Site 1188) and Roman Ruins (Site 1189) active hydrothermal fields. Samples from these two sites were used for a series of permeability, electrical resistivity, and X-ray computed tomography measurements.

Effective permeability of spheroidal shells /

"Contract AF33(616)-3220 Project No. 6(7-4600)Task 40572, Wright Air Development Center"

Permeability of covers over low-level radioactive-waste burial trenches, West Valley, Cattaraugus County, New York /

Bibliography: p. 34-35.

Determination of the in situ permeability of base and subbase courses /

Mode of access: Internet.

The capillary structure of softwoods,

Reprinted from Journal of Agricultural research, vol. 38, no. 1.

Apparatus for testing the permeability of samples of unconsolidated sediment in the field /

Mode of access: Internet.