Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

Dispersões sólidas de sinvastatina: preparação, caracterização, no estado sólido utilizando técnicas emergentes e estudo de estabilidade

This thesis aimed to assess the increase in solubility of simvastatin (SINV) with solid dispersions using techniques such as kneading (MA), co-solvent evaporation (ES), melting carrier (FC) and spray dryer (SD). Soluplus (SOL), PEG 6000 (PEG), PVP K-30 (PVP) e sodium lauryl sulphate (LSS) were used as carriers. The solid dispersions containing PEG [PEG-2(SD)], Soluplus [SOL-2(MA)] and sodium lauryl sulphate [LSS-2(ES)] were presented with a greater increase in solubility (5.02, 5.60 and 5.43 times respectively); analyses by ANOVA between the three groups did not present significant difference (p<0.05). In the phase solubility study, the calculation of the Gibbs free energy (ΔG) revealed that the spontaneity of solubilisation of SINV occurred in the order SOL>PEG >PVP 75%>LSS, always 80%. The phase diagrams of PEG and LSS presented solubilization stoichiometry of type 1:1 (type AL). The diagrams with PVP and SOL tend to 1:2 stoichiometry (type AL + AP). The stability coefficients (Ks) of the phase diagrams revealed that the most stable reactions occurred with LSS and PVP. The solid dispersions were characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), particle size distribution (PSD), near-infrared spectroscopy imaging (NIR-CI) and X-ray diffraction of the powder using the Topas software (PDRX-TOPAS). The solid dispersion PEG-2(SD) presented the greatest homogeneity and the lowest degree of crystallinity (18.2%). The accelerated stability study revealed that the solid dispersions are less stable than SINV, with PEG-2(SD) being the least stable, confirmed by FTIR and DSC. The analyses by PDRX-TOPAS revealed the amorphous character of the dispersions and the mechanism of increasing solubility

Desenvolvimento de um destilador solar para tratamento de águas de produção de petróleo com vistas a sua utilização na agricultura e geração de vapor

The production of petroleum is frequently accomplished with great volumes of water, that it is carried of the underground with the oil. It is a challenge of the present century the development of technologies that allow the use of waste water for purposes that consume great amounts of water and don't demand as rigid as the one of the drinking water requirements. The solar distillation has been configuring as an alternative of clean technology for desalination of brine and saline. Besides causing the minimum possible damage to the environment, it takes advantage of an abundant and free energy source: the solar energy. That study aims to develop a Solar Distillator for treatment of the produced water of the oil wells, to obtain an efluent to use in agriculture and vapor generation. The methodology for collection, conservation and analysis of the physical-chemical parameters obeyed the norms in APHA (1995). The sampling was of the composed type. Experiments were accomplished in the solar distillation pilot and simulation in thermostatic bathing. The operation was in batch system and for periods of 4, 6 and 12 h. The developed Distillator is of the type simple effect of two waters. It was still tested two inclination angles for covering; 20º and 45º. The Distillator presented minimum of 2,85 L/m2d revenues and maximum of 7,14 L/m2d. The removals of salts were great than 98%. The removal of TOC in the simulation was great than 90%. In agreement with the data of energy and mass balance, it was verified that the developed solar Distillator presented compatible revenues with those found in literature for similar types. It can be inferred that the obtained distilled water assists to the requirements CONAMA in almost all the points and could be used for irrigation of cultures such as cotton and mamona. As the distilled water has characteristics of fresh water it can be used in the generation of vapor

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams

Efeito Kerr magneto-óptico; Ressonância ferromagnética; Acoplamento bilinear; Acoplamento biquadrático

In this work, we investigated the magnetic properties of a monocrystalline Fe thin film and of Fe(80 Å)/Cr(t)/Fe(80 Å) tri-layers, with the nonmagnetic metallic Cr spacer layer thickness varying between 9 Å < t < 40 Å. The samples were deposited by the DC Sputtering on Magnesium Oxide (MgO) substrates, with (100) crystal orientation. For this investigation, experimental magneto-optical Kerr effect (MOKE) magnetometry and ferromagnetic resonance (FMR) techniques were employeed. In this case, these techniques allowed us to study the static and dynamical magnetization properties of our tri-layers. The experimental results were interpreted based on the phenomenological model that takes into account the relevant energy terms to the magnetic free energy to describe the system behavior. In the case of the monocrystalline Fe film, we performed an analytical discussion on the magnetization curves and developed a numerical simulation based on the Stoner-Wohlfarth model, that enables the numerical adjustment of the experimental magnetization curves and obtainment of the anisotropy field values. On the other hand, for the tri-layers, we analyzed the existence of bilinear and biquadratic couplings between the magnetizations of adjacent ferromagnetic layers from measurements of magnetization curves. With the FMR fields and line width angular dependencies, information on the anisotropy in three layers was obtained and the effects of different magnetic relaxation mechanisms were evidenced. It was also possible to observe the dependence of the epitaxy of the multilayers with growth and sputtering parameters. Additionally it was developed the technique of AC magnetic susceptibility in order to obtain further information during the investigation of magnetic thin films

Caracterização e aplicação de sistemas micelares e microemulsionados como inibidores de corrosão

Corrosion is an important phenomenon that frequently occurs in the oil industry, causing surface ablation, such as it happens on the internal surfaces of oil pipes. This work aims to obtain new systems to reduce this specific problem. The surfactants SDS, CTAB, and UNITOL L90 (in micellar and microemulsionated systems) were used as corrosion inhibitors. The systems were obtained using a C/S ratio of 2, butanol as cosorfactant, kerosene as oil phase and, as water phase, NaCl solutions of 0.5M with pH = 2, 4, and 7. Microemulsion regions were found both for direct and inverse micelles. SDS had the higher microemulsion region and the area was not dependent of pH. The study of micellization of these surfactans in the liquid-gas interface was carried out via the determination of CMC from surface tension measurements. Regarding microemulsionated systems, in the case of CTAB, CMC increased when pH was increased, being constant for SDS and UNITOL L90. Concerning micellar systems, increase in pH caused decrease and increase in CMC for SDC and CTAB, respectively. In the case of UNITOL L90, CMC was practically constant, but increased for pH = 4. The microemulsionated systems presented higher CMC values, except for UNITOL L90 L90. The negative values of free energy of micellization indicated that the process of adsorption was spontaneous. The results also indicated that, comparing microemulsionated to systems, adsorption was less spontaneous in the case of SDS and CTAB, while it did not change for UNITOL L90. SAXS experiments indicated that micelle geometry was spherical, existing also as halter and flat micelles, resuting in a better inght on the adsorption at the liquid-solid interface. Efficiency of corrosion inhibition as determined by electrochemical measurements, from corrosion currents calculated from Tafel extrapolation indicuting heat showed surfactants to be efficient even at low concentrations. Equilibrium isotherm data were fitted to the Freundlich model, indicating that surfactant adsorption occurs in the form of multilayers

Aplicação de sabões de ácidos graxos epoxidados como inibidores de corrosão em oleoduto

Corrosion usually occurs in pipelines, so that it is necessary to develop new surface treatments to control it. Surfactants have played an outstanding role in this field due to its capacity of adsorbing on metal surfaces, resulting in interfaces with structures that protect the metal at low surfactant concentrations. The appearance of new surfactants is a contribution to the area, as they increase the possibility of corrosion control at specific conditions that a particular oil field presents. The aim of this work is to synthesize the surfactants sodium 12 hydroxyocadecenoate (SAR), sodium 9,10-epoxy-12 hydroxyocadecanoate (SEAR), and sodium 9,10:12,13-diepoxy-octadecanoate (SEAL) and apply them as corrosion inhibitors, studying their action in environments with different salinities and at different temperatures. The conditions used in this work were chosen in order to reproduce oil field reality. The study of the micellization of these surfactants in the liquid-gas interface was carried out using surface tensiometry. It was observed that cmc increased as salt concentration was increased, and temperature and pH were decreased, while cmc decreased with the addition of two epoxy groups in the molecule. Using the values of cmc and the Gibbs equation, the values of Gibbs free energy of adsorption, area per adsorbed molecule, and surface excess were calculated. The surface excess increases as salt concentration and temperature decreases, increasing as pH is increased. The area per adsorbed molecule and the free energy of adsorption decrease with salt concentration, temperature, and pH increase. SAXS results showed that the addition of epoxy group in surfactant structure results in a decrease in the repulsion between the micelles, favoring the formation of more oblong micellar structures, ensuring a better efficiency of metal coverage. The increase in salt and surfactant concentrations provides an increase in micellar diameter. It was shown that the increase in temperature does not influence micellar structure, indicating thermal stability that is advantageous for use as corrosion inhibitor. The results of inhibition efficiency for the surfactants SEAR and SEAL were considered the best ones. Above cmc, adsorption occurred by the migration of micelles from the bulk of the solution to the metal surface, while at concentrations below cmc film formation must be due to the adsorption of semi-micellar and monomeric structures, certainly due to the presence of the epoxy group, which allows side interactions of the molecule with the metal surface. The metal resistance to corrosion presented values of 90% of efficiency. The application of Langmuir and Frumkin isotherms showed that the later gives a better description of adsorption because the model takes into account side interactions from the adsorbing molecules. Wettability results showed that micelle formation on the solid surface occurs at concentrations in the magnitude of 10-3 M, which isthe value found in the cmc study. This value also justifies the maximum efficiencies obtained for the measurements of corrosion resistance at this concentration. The values of contact angle as a function of time suggest that adsorption increases with time, due to the formation of micellar structures on metal surface

Estudos de sorção de um corante aniônico modelo em partículas de quitosana reticulada

Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process

Estudo teórico de intermediários tetraédricos acidez / basicidade e estereosseletividade enzimáticos

The present work aimed first, the theoretical study of tetrahedral intermediate stability formed from carbonyl addition reactions using the second (MP2) and third (MP3) order Møller–Plesset perturbation theory. Linear correlations between electronic energy difference of reactions with Wiberg Indexes and C-O bond lengths were obtained, and was observed that the stability of adducts formed depends directly of electronic density involved between these atoms. The knowing of electronic parameters of these structures has an important hole due to the large use on reactions that in his course forms this tetrahedral intermediate. Employing the ONIOM (B3LYP:AMBER) methodology, was evaluated the stereoselectivity of a enzymatic reaction between CAL B enzyme and a long chain ester. In this study, were obtained the electronic energies of ground state and intermediate state of transesterification rate-determing step from two possible proquirals faces Re and Si. The objective was study the enantioselectivity of CAL B and rationalizes it using quantum theory of atoms in molecules (QTAIM). A theoretical study employing inorganic compounds was performed using ab initio CBS-QB3 method aiming to find a link between thermodynamic and equilibrium involving acids and bases. The results observed showed an excellent relationship between difference in Gibbs free energy, ΔG of acid dissociation reaction and ΔG of hydrolysis reaction of the corresponding conjugate base. It was also observed, a relationship between ΔG of hydrolysis reaction of conjugate acids and their corresponding atomic radius showing that stability plays an important role in hydrolysis reactions. The importance of solvation in acid/base behavior when compared to theoretical and experimental ΔG´s also was evaluated.

Síntese e caracterização de materiais mesoporosos para a captura de CO2: influência do óxido de níquel

Several materials are currently under study for the CO2 capture process, like the metal oxides and mixed metal oxides, zeolites, carbonaceous materials, metal-organic frameworks (MOF's) organosilica and modified silica surfaces. In this work, evaluated the adsorption capacity of CO2 in mesoporous materials of different structures, such as MCM-48 and SBA- 15 without impregnating and impregnated with nickel in the proportions 5 %, 10 % and 20 % (m/m), known as 5Ni-MCM-48, 10Ni-MCM-48, 20Ni-MCM-48 and 5Ni-SBA-15, 10NiSBA-15, 20Ni-SBA-15. The materials were characterized by means of X-ray diffraction (XRD), thermal analysis (TG and DTG), Fourier transform infrared spectroscopy (FT-IR), N2 adsorption and desorption (BET) and scanning electron microscopy (SEM) with EDS. The adsorption process was performed varying the pressure of 100 - 4000 kPa and keeping the temperature constant and equal to 298 K. At a pressure of 100 kPa, higher concentrations of adsorption occurred for the materials 5Ni-MCM-48 (0.795 mmol g-1 ) and SBA-15 (0.914 mmol g-1 ) is not impregnated, and at a pressure of 4000 kPa for MCM-48 materials (14.89 mmol g-1) and SBA-15 (9.97 mmol g-1) not impregnated. The results showed that the adsorption capacity varies positively with the specific area, however, has a direct dependency on the type and geometry of the porous structure of channels. The data were fitted using the Langmuir and Freundlich models and were evaluated thermodynamic parameters Gibbs free energy and entropy of the adsorption system

Contribuição ao estudo de treliças não lineares considerando efeitos térmicos

This work presents the numerical analysis of nonlinear trusses summited to thermomechanical actions with Finite Element Method (FEM). The proposed formulation is so-called positional FEM and it is based on the minimum potential energy theorem written according to nodal positions, instead of displacements. The study herein presented considers the effects of geometric and material nonlinearities. Related to dynamic problems, a comparison between different time integration algorithms is performed. The formulation is extended to impact problems between trusses and rigid wall, where the nodal positions are constrained considering nullpenetration condition. In addition, it is presented a thermodynamically consistent formulation, based on the first and second law of thermodynamics and the Helmholtz free-energy for analyzing dynamic problems of truss structures with thermoelastic and thermoplastic behavior. The numerical results of the proposed formulation are compared with examples found in the literature.