The role of hydration on the mechanism of allosteric regulation: In situ measurements of the oxygen-linked kinetics of water binding to hemoglobin

We report here the first direct measurements of changes in protein hydration triggered by a functional binding. This task is achieved by weighing hemoglobin (Hb) and myoglobin films exposed to an atmosphere of 98%, relative humidity during oxygenation. The binding of the first oxygen molecules to Hb tetramer triggers a change in protein conformation, which increases binding affinity to the remaining empty sites giving rise to the appearance of cooperative phenomena. Although crystallographic data have evidenced that this structural change increases the protein water-accessible surface area, isobaric osmotic stress experiments in aqueous cosolutions have shown that water binding is linked to Hb oxygenation. Now we show that the differential hydration between fully oxygenated and fully deoxygenated states of these proteins, determined by weighing protein films with a quartz crystal microbalance, agree with the ones determined by osmotic stress in aqueous cosolutions, from the linkage between protein oxygen affinity and water activity. The agreements prove that the changes in water activity brought about by adding osmolytes to the buffer solution shift biochemical equilibrium in proportion to the number of water molecules associated with the reaction. The concomitant kinetics of oxygen and of water binding to Hb have been also determined. The data show that the binding of water molecules to the extra protein surface exposed on the transition from the low-affinity T to the high-affinity R conformations of hemoglobin is the rate-limiting step of Hb cooperative reaction. This evidences that water binding is a crucial step on the allosteric mechanism regulating cooperative interactions, and suggests the possibility that environmental water activity might be engaged in the kinetic control of some important reactions in vivo.

Influence of microwave polymerization method and thickness on porosity of acrylic resin

Purpose: This study evaluated the influence of polymerization cycle and thickness of maxillary complete denture bases on the porosity of acrylic resin. Materials and Methods: Two heat-activated denture base resins - one conventional (Clássico) and one designed for microwave polymerization (Onda-Cryl) - were used. Four groups were established, according to polymerization cycles: A (Onda-Cryl, short microwave cycle), B (Onda-Cryl, long microwave cycle), C (Onda-Cryl, manufacturing microwave cycle), and T (Clássico, water bath). Porosity was evaluated for different thicknesses (2.0, 3.5, and 5.0 mm; thicknesses I, II, and III, respectively) by measurement of the specimen volume before and after its immersion in water. The percent porosity data were submitted to Kruskal-Wallis for comparison among the groups. Results: The Kruskal-Wallis test detected that the combinations of the different cycles and thicknesses showed significant differences, and the mean ranks of percent porosity showed differences only in the thinnest (2.0 mm) microwave-polymerized specimens (A = 53.55, B = 40.80, and C = 90.70). Thickness did not affect the results for cycle T (I = 96.15, II = 70.20, and III = 82.70), because porosity values were similar in the three thicknesses. Conclusions: Microwave polymerization cycles and the specimen thickness of acrylic resin influenced porosity. Porosity differences were not observed in the polymerized resin bases in the water bath cycle for any thickness. © 2007 by The American College of Prosthodontists.

Variation of soil and water volumes in riparian jungle soils of Brazil

The objective of this work is to study the relation between humidity, density, porosity and shrinkage of the floodplain soil and riparian vegetation and their ability to store water. For this purpose, two locations for every type of soils were evaluated. Both were placed at the Agronomy University (Faculdade de Ciências Agronômicas) in São Manuel, State of São Paulo, Brazil. The floodplain soil was vegetated with Southern Cattail (Typha domingensis). In both places, soil samples were collected from several depths: 0, 30, 60 and 100 cm. Results show that lower soil density values (0.15 g/cm3) with organic texture and high porosities values (up to 86.2%) were found in samples with the highest organic material content in the floodplain soil. For this field experiment, flood plains soils (characterised as basin gley soils) presented high volumetric instability with a retratibility of 67.49% and higher water storage capacities compared to riparian stands soils (characterised as fluvic neosoils).

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Quantification of water content across a cement-clay interface using high resolution neutron radiography

In many designs for radioactive waste repositories, cement and clay will come into direct contact. The geochemical contrast between cement and clay will lead to mass fluxes across the interface, which consequently results in alteration of structural and transport properties of both materials that may affect the performance of the multi-barrier system. We present an experimental approach to study cement-clay interactions with a cell to accommodate small samples of cement and clay. The cell design allows both in situ measurement of water content across the sample using neutron radiography and measurement of transport parameters using through-diffusion tracer experiments. The aim of the high- resolution neutron radiography experiments was to monitor changes in water content (porosity) and their spatial extent. Neutron radiographs of several evolving cement-clay interfaces delivered quantitative data which allow resolving local water contents within the sample domain. In the present work we explored the uncertainties of the derived water contents with regard to various input parameters and with regard to the applied image correction procedures. Temporal variation of measurement conditions created absolute uncertainty of the water content in the order of ±0.1 (m3/m3), which could not be fully accounted for by correction procedures. Smaller relative changes in water content between two images can be derived by specific calibrations to two sample regions with different, invariant water contents.

Stabilization of soil hydraulic properties under a long term no-till system

The area under the no-tillage system (NT) has been increasing over the last few years. Some authors indicate that stabilization of soil physical properties is reached after some years under NT while other authors debate this. The objective of this study was to determine the effect of the last crop in the rotation sequence (1st year: maize, 2nd year: soybean, 3rd year: wheat/soybean) on soil pore configuration and hydraulic properties in two different soils (site 1: loam, site 2: sandy loam) from the Argentinean Pampas region under long-term NT treatments in order to determine if stabilization of soil physical properties is reached apart from a specific time in the crop sequence. In addition, we compared two procedures for evaluating water-conducting macroporosities, and evaluated the efficiency of the pedotransfer function ROSETTA in estimating the parameters of the van Genuchten-Mualem (VGM) model in these soils. Soil pore configuration and hydraulic properties were not stable and changed according to the crop sequence and the last crop grown in both sites. For both sites, saturated hydraulic conductivity, K0, water-conducting macroporosity, εma, and flow-weighted mean pore radius, R0ma, increased from the 1st to the 2nd year of the crop sequence, and this was attributed to the creation of water-conducting macropores by the maize roots. The VGM model adequately described the water retention curve (WRC) for these soils, but not the hydraulic conductivity (K) vs tension (h) curve. The ROSETTA function failed in the estimation of these parameters. In summary, mean values of K0 ranged from 0.74 to 3.88 cm h-1. In studies on NT effects on soil physical properties, the crop effect must be considered.

Freeze-Thaw Durability of Concretes with and without Class C Fly Ash, MLR-94-9 Phase I, 1997

The freeze-thaw resistance of concretes was studied. Nine concrete mixes, made with five cements and cement-Class C fly ash combinations, were exposed to freeze-thaw cycling following 110 to 222 days of moist curing. Prior to the freeze-thaw cycling, the specimens were examined by a low-vacuum scanning electron microscope (SEM) for their microstructure. The influence of a wet/dry treatment was also studied. Infilling of ettringite in entrained air voids was observed in the concretes tested. The extent of the infilling depends on the period of moist curing as well as the wet/dry treatment. The concretes with 15% Class C fly ash replacement show more infilling in their air voids. It was found that the influence of the infilling on the freeze-thaw durability relates to the air spacing factor. The greater the spacing factor, the more expansion under the freeze-thaw cycling. The infilling seems to decrease effective air content and to increase effective spacing factor. The infilling also implies that the filled air voids are water-accessible. These might lead to concrete more vulnerable to the freeze-thaw attack. By combining the above results with field observations, one may conclude that the freeze-thaw damage is a factor related to premature deterioration of portland cement concrete pavements in Iowa.

Estudo de massa cerâmica triaxial visando à otimização do ciclo de queima da indústria de cerâmica estrutural

Over recent years the structural ceramics industry in Brazil has found a very favorable market for growth. However, difficulties related to productivity and product quality are partially inhibiting this possible growth. An alternative for trying to solve these problems and, thus, provide the pottery industry the feasibility of full development, is the substitution of firewood used in the burning process by natural gas. In order to contribute to this process of technological innovation, this paper studies the effect of co-use of ceramic phyllite and kaolin waste on the properties of a clay matrix, verifying the possible benefits that these raw materials can give to the final product, as well as the possibility of such materials to reduce the heat load necessary to obtain products with equal or superior quality. The study was divided into two steps: characterization of materials and study of formulations. Two clays, a phyllite and a residue of kaolin were characterized by the following techniques: laser granulometry, plasticity index by Atterberg limits, X-ray fluorescence, X-ray diffraction, mineralogical composition by Rietveld, thermogravimetric and differential thermal analysis. To study the formulations, specifically for evaluation of technological properties of the parts, was performed an experimental model that combined planning involving a mixture of three components (standard mass x phyllite x kaolin waste) and a 23 factorial design with central point associated with thermal processing parameters. The experiment was performed with restricted strip-plot randomization. In total, 13 compositional points were investigated within the following constraints: phyllite ≤ 20% by weight, kaolin waste ≤ 40% by weight, and standard mass ≥ 60% by weight. The thermal parameters were used at the following levels: 750 and 950 °C to the firing temperature, 5 and 15 °C/min at the heating rate, 15 and 45min to the baseline. The results showed that the introduction of phyllite and/or kaolin waste in ceramic body produced a number of benefits in properties of the final product, such as: decreased absorption of water, apparent porosity and linear retraction at burn; besides the increase in apparent specific mass and mechanical properties of parts. The best results were obtained in the compositional points where the sum of the levels of kaolin waste and phyllite was maximal (40% by weight), as well as conditions which were used in firing temperatures of 950 °C. Regarding the prospect of savings in heat energy required to form the desired microstructure, the phyllite and the residue of kaolin, for having small particle sizes and constitutions mineralogical phases with the presence of fluxes, contributed to the optimization of the firing cycle.

Avaliação do concreto de cimento portland com resíduo da produção de scheelita em substituição ao agregado miúdo

From the 70`s, with the publication of the Manifesto for Environment UN Conference, held in Stockholm, in Sweden (1972), defend and improve the environment became part of our daily lives. Thus, several studies have emerged in several segments in order to reuse the waste. Some examples of waste incorporated in portland cement concrete are: rice husk ash, bagasse ash of cane sugar, powder-stone, microsilica, tire rubber, among others. This research used the residue of the mining industry Scheelite, to evaluate the incorporation of the residue composition of Portland cement concrete, replacing the natural sand. The percentage of residue were incorporated from 0% to 100%, with a variation of 10%, 11 being produced concrete mix in the ratio 1:2:3:0.60, by mass. We evaluated the following characteristics of concrete: slump test, compressive strength, tensile strength by diametral compression, water absorption, porosity and density, based on the ABNT, through tests performed in the Laboratory of Civil Construction, UFRN. The trace with the addition of 60% scheelite residue was obtained which better performance. Therefore, the use of the waste from the production of Scheelite is feasible due to the durability parameters (water absorption and porosity), sustainability, and the good results of the resistance of the concrete

Aproveitamento de resíduos de cinza da cana de açúcar em massas cerâmicas

This study aimed to investigate the use of cane sugar ashes from small-scale stills of Eunápolis region, state of Bahia, in pottery mass that can be developed as porcelain stoneware. Bahia is the second largest producer of rum distillery in Brazil. In the production of rum is produced residue called bagasse, which is used to generate electricity in Power plants and in the distillery itself, generating ashes as residue, which is played in nature, causing environmental damage. We studied 5 (five) formulations of 0% 10% 20%, 30% and 40% by weight of the ash, without ignition and 3 (three) formulations of 10%, 20% and 30% with gray ash temperature of 1250ºC. The formulation at 0% by weight of ash was used for a comparison between the traditional mass of porcelain stoneware and the masses with the addition of ash calcined, replacing feldspar. The percentage by weight of kaolin and of Clay was kept the same, 30%, and all raw materials were derived from the state of Bahia. The samples were made in uniaxial array with dimensions of (60 x 20 x 5) mm and compressed to a pressure of 45 MPa. Assays were performed to characterize the raw by X-ray fluorescence, X-ray diffraction, ATD and ATG and Dilatometric analysis. The samples were sintered at temperatures of 1100°C, 1150°C, 1200°C and 1250°C, for the specimens with the ashes without ash and 1150° C and 1200° C for specimens with the gray level of calcined 60 minutes. and then we made a cooling ramp with the same rate of warming until reach ambient temperature. The sintered bodies were characterized by water absorption, porosity, linear shrinkage, bending strength and XRD of the fracture surface and the results analyzed. It was proven, after results of tests performed, that it is possible to use the ash residue of sugar cane bagasse on ceramic coating with the addition of up to 10% wt of the residue ash

The primary sources of carbon loss during the crop-establishment period in a subtropical Oxisol under contrasting tillage systems

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Determinação da entalpia e da entropia de solvatação da superfície protéica a partir da energética de oxigenação de hemoglobinas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Reciclagem de resíduo a partir de cinzas de carvão mineral: produção de argamassas

Este trabalho tem como objetivo avaliar a possibilidade de aproveitamento do resíduo obtido a partir da combustão do carvão mineral em caldeiras de leito fluidizado, de uma refinaria de alumina no estado do Pará. Neste contexto, foi avaliada a incorporação de cinzas volantes, como pozolana, em substituição parcial do cimento na produção de argamassas. Para tanto, foram elaborados corpos de prova utilizando-se o cimento do tipo Portland CPII-E-32. As misturas foram definidas na proporção 4:1, ou seja, 4 partes de agregado (sílica) e 1 parte de aglomerante (cimento e cinza), com a inserção de cinza nos teores de 10, 20, 30, 40 e 50 em porcentagem com relação ao cimento, além da argamassa sem adição. Foram definidas duas relações água/aglomerante, 0,4 e 0,8. Após tempo de cura de 7 e 28 dias, foram feitos testes de resistência à compressão para análise de comportamento. Além disso, as argamassas com a relação água/aglomerante 0,8 foram sujeitas a análises complementares de Difração de Raios-X, Microscopia Eletrônica de Varredura, absorção de água, porosidade aparente e massa específica aparente, cujos resultados obtidos mostraram-se compatíveis quando comparados com os dados da literatura, demonstrando ser viável a aplicação das cinzas estudadas na indústria da construção civil.

Geotechnical properties of sediments at DSDP Leg 84 Holes

The geotechnical characteristics of 22 sediment samples from Leg 84 sites were studied in an effort to associate these with processes active along the Middle America slope and with sedimentation mechanisms. Geotechnical properties measured include water content, porosity, bulk density, Atterberg limits, consolidation characteristics, permeability, and vane shear strength. A majority of samples obtained from Sites 565, 568, and 570 show significant disturbance resulting from degassing. This disturbance apparently results in underconsolidation, although other mechanisms such as excess pore pressures generated from the subduction process can also contribute to this state. Overconsolidated sediments were found at Sites 565, 566, and 569. The overconsolidated sediments at Sites 565 and 569 may result from downslope transport mechanisms rearranging and stressing the sediment mass under consideration. The sediment condition at Site 566 is probably a result of eroded overburden: an estimated 87 m of overlying sediments may have been removed. Geotechnical and permeability relationships with depth are consistent with those found for other hemipelagic sediments of silty clay to clayey silt textures.