Water activity in aqueous amino acid solutions containing ammonium sulfate at 298.2 K

Water activity in aqueous solutions of DL-alanine, glycine, or L-serine, with ammonium sulfate, molality ranging from 0.5 to 5.0, have been measured at 298.2 K. The new experimental data was correlated using three different theoretical schemes such as Zdanovskii-Stokes-Robinson, its extension, or the Clegg-Seinfeld-Brimblecombe approach, with global average absolute deviations in the calculation of the osmotic coefficient of 3.46 %, 0.93 % and 1.95 %, respectively. The extended Zdanovskii-Stokes-Robinson method also enabled the prediction of unsymmetric molal activity coefficients of the electrolyte, in fair agreement with the experimental values found from literature measured by an electrochemical method. It is evidenced the usefulness of the experimental ternary data measured to extend the capabilities of thermodynamic models to higher salt and amino acid concentrations.

Direct Observation of Tetragonal Distortion in Epitaxial Structures through Secondary Peak Split in a Synchrotron Radiation Renninger Scan

This paper reports a direct observation of an interesting split of the (022)(022) four-beam secondary peak into two (022) and (022) three-beam peaks, in a synchrotron radiation Renninger scan (phi-scan), as an evidence of the layer tetragonal distortion in two InGaP/GaAs (001) epitaxial structures with different thicknesses. The thickness, composition, (a perpendicular to) perpendicular lattice parameter, and (01) in-plane lattice parameter of the two epitaxial ternary layers were obtained from rocking curves (omega-scan) as well as from the simulation of the (022)(022) split, and then, it allowed for the determination of the perpendicular and parallel (in-plane) strains. Furthermore, (022)(022) omega:phi mappings were measured in order to exhibit the multiple diffraction condition of this four-beam case with their split measurement.

Estudo da incorporação de cascalho proveniente da perfuração de poços de petróleo em formulações para tijolos de solo-cimento

The present work is to study the characteristics and technological properties of soil-cement bricks made from binary and ternary mixtures of Portland cement, sand, water, with or without addition of gravel from the drilling of oil wells, which could be used by industry, aiming to improve its performance and reduce cost by using the residue and, consequently, increasing its useful life. The soil-cement bricks are one of the alternatives to masonry construction. These elements, after a short curing period, provide compressive strength similar to that of solid bricks and ceramic blocks, and the higher the resistance the higher the amount of cement used. We used the soil from the city of São José do Mipibu / RN, the banks of the River Baldun, cement CPIIZ-32 and residue of drill cuttings from oil wells drilling onshore wells in the town of Mossley, RN, provided Petrobras. To determine the optimum mix, we studied the inclusion of different residues (100%, 80%, 70%, 60% and 50%) where 15 bodies were made of the test piece. The assessment was made of bricks made from simple compression tests, mass loss by immersion and water absorption. The experimental results proved the efficiency and high utilization of the waste from the drilling of oil wells, making the brick-cement-soil residue with a higher strength and lower water absorption. The best result in terms of mechanical strength and water absorption for the ternary mixture was 10% soil, 14% cement and 80% residue. In terms of binary mixtures, we obtained the best result for the mix-cement residue, which was 14% cement incorporated in the residue

Estudo da incorporação da cal em composições binárias de solo-cimento para produção de tijolos maciços

The use of binders in the soil for the production of solid bricks is an old construction technique that has been used by several civilizations over time. At the same time, the need for environmental preservation and the tendency of scarcity of natural resources make the construction invest in researching new concepts, methods and materials for building systems for the sustainability of their economic activities. Thus arises the need to obtain building materials with low power consumption, capable of reducing the growing housing shortage of rural and urban population. Currently, research has been conducted on this topic to better understand the cementitious and pozzolanic reactions that occur in the formation of the microstructure of the soil-cement when added to other materials such as, for example, lime, and the relationship between microstructure and formed interfaces with the physical, mechanical and chemical analysis in compounds made from these ternary compositions. In this context, this study aimed to analyze the results of the influence of the incorporation of lime to the soil-cement to form a ternary mixture to produce soil-cement bricks and mortar without structural purposes. From the inclusion of contents of 6 %, 8 %, 10% and 12% lime to the soil, and soil-cement mixes in amounts of 2 %, 3 %, 4 % and 5 % were shaped-bodies of -cylindrical specimens to determine the optimum moisture content and maximum dry apparent specific weight. Then they were cured, and subjected to the tests of compressive strength, absorption and durability modified. Compositions obtained the best results in the tests performed on the bodies-of-proof cylindrical served as a parameter for molding of solid bricks, which underwent the same experimental methodology previously cited. The raw materials used, as well as compositions in which the bricks were molded solid, were characterized by physical and chemical tests, X-ray diffraction and scanning electron microscopy. The results obtained in the study indicate that the compositions studied, that showed the best results in terms of compressive strength, water absorption and durability ternary composition was soil, 10 % cement and 2 % lime

Formulação de bloco intertravado cerâmico com adição de resíduos urbanos e industriais

The production of waste from urban and industrial activities is one of the factors of environmental contamination and has aroused attention of the scientific community, in the sense of its reuse. On the other hand, the city of Salvador/Ba, with approximately 262 channels, responsible for storm water runoff, produces every year, by the intervention of cleaning and clearing channels, a significant volume of sediments (dredged mud), and thus an appropriate methodology for their final destination. This study aims to assess the influence of incorporation of these tailings in arrays of clay for production of interlocked block ceramic, also known as ceramic paver. All the raw materials from the metropolitan region of Salvador (RMS) were characterized by x-ray fluorescence, x-ray diffraction, thermal analysis (TG and TDA), particle size analysis and dilatometry. With the use of statistical experimental planning technique, ternary diagram was defined in the study region and the analyzed formulations. The specimens were prepared with dimensions of 60x20x5mm³, by uniaxial pressing of 30 MPa and after sintering at temperatures of 900°, 1000º and 1100ºC the technological properties were evaluated: linear shrinkage, water absorption, apparent porosity, apparent specifies mass, flexural rupture and module. For the uniaxial compression strength used cylindrical probe body with Ø 50 mm. The standard mass (MP) was prepared with 90% by weight of clay and 10% by weight of Channel sediment (SCP), not being verified significant variations in the properties of the final product. With the incorporation of 10% by weight of manganese residue (PFM) and 10% by weight of the Ceramic waste (RCB) in the mass default, in addition to adjusting the plasticity due to less waste clay content, provided increased linear firing shrinkage, due the significant concentration of K2O, forming liquid phase at low temperature, contributing to decreased porosity and mechanical resistance, being 92,5 MPa maximum compressive strength verified. After extract test leachate and soluble, the piece containing 10% of the PFM, was classified as non-hazardous and inert material according to NBR10004/04 ABNT. The results showed the feasibility on using waste, SCP, RCB and PFM clay mass, at temperatures above 900ºC, paver ceramic production, according to the specifications of the technical standards, so that to exceed the 10% of the PFM, it becomes imperative to conduct studies of environmental impacts

Conformational states of HIV-1 reverse transcriptase for nucleotide incorporation vs. pyrophosphorolysis – binding of foscarnet

HIV-1 reverse transcriptase (RT) catalytically incorporates individual nucleotides into a viral DNA strand complementing an RNA or DNA template strand; the polymerase active site of RT adopts multiple conformational and structural states while performing this task. The states associated are dNTP binding at the N site, catalytic incorporation of a nucleotide, release of a pyrophosphate, and translocation of the primer 3′-end to the P site. Structural characterization of each of these states may help in understanding the molecular mechanisms of drug activity and resistance and in developing new RT inhibitors. Using a 38-mer DNA template-primer aptamer as the substrate mimic, we crystallized an RT/dsDNA complex that is catalytically active, yet translocation-incompetent in crystals. The ability of RT to perform dNTP binding and incorporation in crystals permitted obtaining a series of structures: (I) RT/DNA (P-site), (II) RT/DNA/AZTTP ternary, (III) RT/AZT-terminated DNA (N-site), and (IV) RT/AZT-terminated DNA (N-site)/foscarnet complexes. The stable N-site complex permitted the binding of foscarnet as a pyrophosphate mimic. The Mg2+ ions dissociated after catalytic addition of AZTMP in the pretranslocated structure III, whereas ions A and B had re-entered the active site to bind foscarnet in structure IV. The binding of foscarnet involves chelation with the Mg2+ (B) ion and interactions with K65 and R72. The analysis of interactions of foscarnet and the recently discovered nucleotide-competing RT inhibitor (NcRTI) α-T-CNP in two different conformational states of the enzyme provides insights for developing new classes of polymerase active site RT inhibitors.

Performance of concrete incorporating amorphous silica residue and biomass fly ash

L'industrie du ciment est l'une des principales sources d'émission de dioxyde de carbone. L'industrie mondiale du ciment contribue à environ 7% des émissions de gaz à effet de serre dans l'atmosphère. Afin d'aborder les effets environnementaux associés à la fabrication de ciment exploitant en permanence les ressources naturelles, il est nécessaire de développer des liants alternatifs pour fabriquer du béton durable. Ainsi, de nombreux sous-produits industriels ont été utilisés pour remplacer partiellement le ciment dans le béton afin de générer plus d'économie et de durabilité. La performance d'un additif de ciment est dans la cinétique d'hydratation et de la synergie entre les additions et de ciment Portland. Dans ce projet, deux sous-produits industriels sont étudiés comme des matériaux cimentaires alternatifs: le résidu de silice amorphe (RSA) et les cendres des boues de désencrage. Le RSA est un sous-produit de la production de magnésium provenant de l'Alliance Magnésium des villes d'Asbestos et Thedford Mines, et les cendres des boues de désencrage est un sous-produit de la combustion des boues de désencrage, l'écorce et les résidus de bois dans le système à lit fluidisé de l'usine de Brompton située près de Sherbrooke, Québec, Canada. Récemment, les cendres des boues de désencrage ont été utilisées comme des matériaux cimentaires alternatifs. L'utilisation de ces cendres comme matériau cimentaire dans la fabrication du béton conduit à réduire la qualité des bétons. Ces problèmes sont causés par des produits d'hydratation perturbateurs des cendres volantes de la biomasse quand ces cendres sont partiellement mélangées avec du ciment dans la fabrication du béton. Le processus de pré-mouillage de la cendre de boue de désencrage avant la fabrication du béton réduit les produits d'hydratation perturbateurs et par conséquent les propriétés mécaniques du béton sont améliorées. Les approches pour étudier la cendre de boue de désencrage dans ce projet sont : 1) caractérisation de cette cendre volante régulière et pré-humidifiée, 2) l'étude de la performance du mortier et du béton incorporant cette cendre volante régulière et pré-humidifiée. Le RSA est un nouveau sous-produit industriel. La haute teneur en silice amorphe en RSA est un excellent potentiel en tant que matériau cimentaire dans le béton. Dans ce projet, l'évaluation des RSA comme matériaux cimentaires alternatifs compose trois étapes. Tout d'abord, la caractérisation par la détermination des propriétés minéralogiques, physiques et chimiques des RSA, ensuite, l'optimisation du taux de remplacement du ciment par le RSA dans le mortier, et enfin l'évaluation du RSA en remplacement partiel du ciment dans différents types de béton dans le système binaire et ternaire. Cette étude a révélé que le béton de haute performance (BHP) incorporant le RSA a montré des propriétés mécaniques et la durabilité, similaire du contrôle. Le RSA a amélioré les propriétés des mécaniques et la durabilité du béton ordinaire (BO). Le béton autoplaçant (BAP) incorporant le RSA est stable, homogène et a montré de bonnes propriétés mécaniques et la durabilité. Le RSA avait une bonne synergie en combinaison de liant ternaire avec d'autres matériaux cimentaires supplémentaires. Cette étude a montré que le RSA peut être utilisé comme nouveaux matériaux cimentaires dans le béton.

Exploring New Material and Analytical Method for Characterization and Conservation of Artifacts

In this dissertation, we focus on developing new green bio-based gel systems and evaluating both the cleaning efficiency and the release of residues on the treated surface, different micro or no destructive techniques, such as optical microscopy, TGA, FTIR spectroscopy, HS-SPME and micro-Spatially Offset Raman spectroscopy (micro-SORS) were tested, proposing advanced analytical protocols. In the first part, a ternary PHB-DMC/BD gel system composed by biodiesel, dimethyl carbonate and poly-3 hydroxybutyrate was developed for cleaning of wax-based coatings applied on indoor bronze. The evaluation of the cleaning efficacy of the gel was carried out on a standard bronze sample which covered a layer of beeswax by restores of Opificio delle Pietre Dure in Florence, and a real case precious indoor bronze sculpture Pulpito della Passione attributed to Donatello. Results obtained by FTIR analysis showed an efficient removal of the wax coating. In the second part, two new kinds of combined gels based on electrospun tissues (PVA and nylon) and PHB-GVL gel were developed for removal of dammar varnish from painting. The electrospun tissue combined gels exhibited good mechanical property, and showed good efficient in cleaning over normal gel. In the third part, green deep eutectic solvent which consists urea and choline chloride was proposed to produce the rigid gel with agar for the removal of proteinaceous coating from oil painting. Rabbit glue and whole egg decorated oil painting mock-ups were selected for evaluating its cleaning efficiency, results obtained by ATR analysis showed the DES-agar gel has good cleaning performance. Furthermore, we proposed micro-SORS as a valuable alternative non-destructive method to explore the DES diffusion on painting mock-up. As a result, the micro-SORS was successful applied for monitoring the liquid diffusion behavior in painting sub-layer, providing a great and useful instrument for noninvasive residues detection in the conservation field.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

Decompositions of powers of quadratic forms

We analyze the Waring decompositions of the powers of any quadratic form over the field of complex numbers. Our main objective is to provide detailed information about their rank and border rank. These forms are of significant importance because of the classical decomposition expressing the space of polynomials of a fixed degree as a direct sum of the spaces of harmonic polynomials multiplied by a power of the quadratic form. Using the fact that the spaces of harmonic polynomials are irreducible representations of the special orthogonal group over the field of complex numbers, we show that the apolar ideal of the s-th power of a non-degenerate quadratic form in n variables is generated by the set of harmonic polynomials of degree s+1. We also generalize and improve upon some of the results about real decompositions, provided by B. Reznick in his notes from 1992, focusing on possibly minimal decompositions and providing new ones, both real and complex. We investigate the rank of the second power of a non-degenerate quadratic form in n variables, which is equal to (n^2+n+2)/2 in most cases. We also study the border rank of any power of an arbitrary ternary non-degenerate quadratic form, which we determine explicitly using techniques of apolarity and a specific subscheme contained in its apolar ideal. Based on results about smoothability, we prove that the smoothable rank of the s-th power of such form corresponds exactly to its border rank and to the rank of its middle catalecticant matrix, which is equal to (s+1)(s+2)/2.