Determinação do perfil de compostos voláteis e avaliação do sabor e aroma de bebidas produzidas a partir da erva-mate (Ilex paraguariensis)

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

Propriedades física de molécilas orgânicas e compostos do tipo perovskita CdSiO3 e CaPbO3

In the first part of this work our concern was to investigate the thermal effects in organic crystals using the theory of the polarons. To analyse such effect, we used the Fröhlich s Hamiltonian, that describes the dynamics of the polarons, using a treatment based on the quantum mechanics, to elucidate the electron-phonon interaction. Many are the forms to analyzing the polaronic phenomenon. However, the measure of the dielectric function can supply important information about the small polarons hopping process. Besides, the dielectric function measures the answer to an applied external electric field, and it is an important tool for the understanding of the many-body effects in the normal state of a polaronic system. We calculate the dielectric function and its dependence on temperature using the Hartree-Fock decoupling method. The dieletric function s dependence on the temperature is depicted by through a 3D graph. We also analyzed the so called Arrhenius resistivity, as a functionof the temperature, which is an important tool to characterize the conductivity of an organic molecule. In the second part we analyzed two perovskita type crystalline oxides, namely the cadmium silicate triclinic (CdSiO3) and the calcium plumbate orthorhombic (CaPbO3), respectively. These materials are normally denominated ABO3 and they have been especially investigated for displaying ferroelectric, piezoelectric, dielectrics, semiconductors and superconductors properties. We found our results through ab initio method within the functional density theory (DFT) in the GGA-PBE and LDA-CAPZ approximations. After the geometry optimization for the two structure using the in two approximations, we found the structure parameters and compared them with the experimental data. We still determined further the angles of connection for the two analyzed cases. Soon after the convergence of the energy, we determined their band structures, fundamental information to characterize the nature of the material, as well as their dielectrics functions, optical absorption, partial density of states and effective masses of electrons and holes

Estudo de propriedades elétricas em compostos de Bario

Este trabalho tem como objetivo estudar a influência da adição de diversos aditivos tais como óxido de silício (SiO2), óxido de bismuto (BiO2), óxido de cério (CeO2) e óxido de lantânio (La2O3) nas propriedades elétricas e dielétricas do titanato de bário (BaTiO3) policristalino. As amostras de titanato de bário foram compactadas e sinterizadas no Laboratório de Tecnologia dos Pós, do Departamento de Física da Universidade Federal do Rio Grande do Norte. Foram realizadas medidas de resistividade elétrica e constante dielétrica em função da temperatura, bem como ensaios de difração de raios-X e análise microestrutural através da microscopia eletrônica de varredura. A análise dos resultados permitiu avaliar a influência dos aditivos nas propriedades elétricas e dielétricas, e propor a utilização de cerâmicas eletrônicas a base de titanato de bário com propriedades superiores as do material existente atualmente

Comparação das respostas fisiológicas entre diferentes testes funcionais em obesos

obesity affects rightly functional capacity diminishing the cardiovascular system efficiency and oxygen uptake (VO2). Field tests, such as, Incremental Shuttle Walking Test (ISWT) and Six Minute Walk Test (6MWT) has been employed as alternative of Cardiopulmonary Exercise Test (CPX), to functional assessing for conditions which transport of oxygen to peripheral is diminished. Nevertheless, the knowing about metabolic variables response in real time and it comparing among different maximal and submaximal tests in obese is absent. Aim: to compare cardiopulmonary, metabolic response during CPX, ISWT and 6MWT and to analyse it influence of adiposity markers in obese. Material e Method: crosssectional, prospective study. Obese included if: (BMI>30Kg/m2; FVC>80%), were assessed as clinical, anthropometric (BMI, body adiposity index-BAI, waist-WC, hip- HC and neck-NC circumferences) and spirometry (forced vital capacity-FVC, Forced expiratory volume-1°second-FEV1, maximal voluntary ventilation-MVV) variables. Obese performed the sequence of tests: CPX, ISWT and 6MWT. Throughout tests was assessed breath-by-breath by telemetry system (Cortex-Biophysik-Metamax3B) variables; oxygen uptake on peak of activity (VO2peak); carbon dioxide production (VCO2); Volume Expiratory (VE); ventilatory equivalents for VO2 (VE/VO2) and CO2 (VE/VCO2); respiratory exchange rate (RER) and perceived effort-Borg6-20). Results: 15 obese (10women) 39.4+10.1years, normal spirometry (%CVF=93.7+9.7) finished all test. They have BMI (43.5+6.6kg/m2) and different as %adiposity (BAI=50.0+10.5% and 48.8+16.9% respectively women and men). Difference of VO2ml/kg/min and %VO2 were finding between CPX (18.6+4.0) and 6MWT (13.2+2.5) but not between ISWT (15.4+2.9). Agreement was found for ISWT and CPX on VO2Peak (3.2ml/kg/min; 95%; IC-3.0 9.4) and %VO2 (16.4%). VCO2(l/min) confirms similarity in production for CPX (2.3+1.0) and ISWT (1.7+0.7) and difference for 6MWT (1.4+0.6). WC explains more the response of CPX and ISWT than other adiposity markers. Adiposity diminishes 3.2% duration of CPX. Conclusion: ISWT promotes similar metabolic and cardiovascular response than CPX in obese. It suggesting that ISWT could be useful and reliable to assess oxygen uptake and functional capacity in obese

Associação entre polimorfismos funcionais nos genes da MMP-7 e MMP-9 e o perfil clinicopatológico do carcinoma epidermóide de língua

Matrix metalloproteinase-7 (MMP-7) and -9 (MMP-9) modulate important functions strictly related to the development, invasion and metastasis of several human cancers among them the squamous cell carcinoma of the tongue (SCCT). However, individual genetic factors such as the functional single nucleotide polymorphisms (SNPs) influence the pattern of protein expression of these MMPs and thus may be related to the variability observed in the clinical behavior of patients with SCCT. In this context, the present cross-sectional study aimed to evaluate the association between the frequency of the functional SNPs MMP-7 -181 A/G and MMP-9 -1562 C/T and the clinical (age, gender and metastasis) and pathological (malignancy histological grading and immunohistochemistry expression) features of SCCT cases. Genotyping of these SNPs were performed by PCR-RFLP on DNA samples from 71 cases of SCCT and 60 individuals without cancer who constitute the control group. Among the results of this research, it was observed that the frequency of the polymorphic alleles MMP-7 -181 G and MMP-9 -1562 T in SCCT patients was 28% and 12%, respectively, and the frequency of the heterozygotes A/G (PR = 2.00; p < 0.001) and C/T (PR = 1.54; p = 0.014) were significantly higher in the patient group than in the controls. The prevalence of patients carrying the combination of SNPs studied was significantly associated with SCCT cases (PR = 2.00; p = 0.011) and metastasis (PR = 2.00; p < 0.001). Furthermore, with the frequency of SNPs analyzed, the age, gender, histological grading and immunoreactivity of MMP-7 and MMP-9 formed clinical and pathological parameters relevant to the identification of population subgroups more related to the development of SCCT and metastasis. Based on these results, it is suggested that the protein expression levels of MMP-7 and -9 substantially influence the balance between their pro- and anticancer biological functions and hence the clinicopathological profile of the squamous cell carcinoma of the tongue

Diferenças funcionais das regiões hipocampais na formação da memória do tipo o quê", "quando" e "onde" em ratos

Episodic memory refers to the recollection of what, where and when a specific event occurred. Hippocampus is a key structure in this type of memory. Computational models suggest that the dentate gyrus (DG) and the CA3 hippocampal subregions are involved in pattern separation and the rapid acquisition of episodic memories, while CA1 is involved in memory consolidation. However there are few studies with animal models that access simultaneously the aspects ‗what-where-when . Recently, an object recognition episodic-like memory task in rodents was proposed. This task consists of two sample trials and a test phase. In sample trial one, the rat is exposed to four copies of an object. In sample trial two, one hour later, the rat is exposed to four copies of a different object. In the test phase, 1 h later, two copies of each of the objects previously used are presented. One copy of the object used in sample trial one is located in a different place, and therefore it is expected to be the most explored object.However, the short retention delay of the task narrows its applications. This study verifies if this task can be evoked after 24h and whether the pharmacological inactivation of the DG/CA3 and CA1 subregions could differentially impair the acquisition of the task described. Validation of the task with a longer interval (24h) was accomplished (animals showed spatiotemporal object discrimination and scopolamine (1 mg/kg, ip) injected pos-training impaired performance). Afterwards, the GABA agonist muscimol, (0,250 μg/μl; volume = 0,5 μl) or saline were injected in the hippocampal subregions fifteen minutes before training. Pre-training inactivation of the DG/CA3 subregions impaired the spatial discrimination of the objects (‗where ), while the temporal discrimination (‗when ) was preserved. Rats treated with muscimol in the CA1 subregion explored all the objects equally well, irrespective of place or presentation time. Our results corroborate the computational models that postulate a role for DG/CA3 in spatial pattern separation, and a role for CA1 in the consolidation process of different mnemonic episodes

Reconhecimento de seqüências de atividades funcionais em pacientes com acidente cascular encefálico

During the motor rehabilitation of patients with neurological pathologies, there are many factors that have an influence on the therapeutical process. It is possible that the demonstration using videotapes or photographs of movements that will be learned can assist the codification, classification and reorganization of the elements of the task in familiar diagrams and thus facilitate the process of motor rehabilitation. The aim of this study was to analyze the performance in the test of recognition of sequences of functional activities such as water drinking and hair combing presented partially (by photos) and completely (by video) to the patients with encephalic vascular accident . The sample was generated from 12 patients (62 ± 8 years) and 10 healthy subjects (53 ± 5 years), of both sex, divided in two groups for which 5 functional activities were presented partially and completely, in 4 sequences that varied between reached and not reached objectives and correct and incorrect movements, during 24 trials. The test t'Student was applied to verify differences in the recognition time between the groups, and to compare the performance between the tests carried through at 9:00 am and retests at 9:00 am and 4:00 pm. To compare the frequency between the types of reply, the test Qui-square was used. It was verified that the patients presented a greater recognition time and a lower number of correct answers than the healthy subjects, and had better performances in the recognition of the complete sequence than the partial one. Bigger frequency was observed in the reply that the objective and the movement were being presented correctly, however the healthy subjects had soon indicated the correct reply in the first trials. An improvement tendency was observed in the performance, when the stages of tests and retests had been carried through in the same schedule. According to the results, it is suggested that the patients with stroke can better recognize the correct movements of a functional activity when it is presented completely in video form, what can influence the choice of the therapeutical strategy during the process of motor rehabilitation

Reconhecimento de seqüências de atividades funcionais em pacientes com acidente cascular encefálico

During the motor rehabilitation of patients with neurological pathologies, there are many factors that have an influence on the therapeutical process. It is possible that the demonstration using videotapes or photographs of movements that will be learned can assist the codification, classification and reorganization of the elements of the task in familiar diagrams and thus facilitate the process of motor rehabilitation. The aim of this study was to analyze the performance in the test of recognition of sequences of functional activities such as water drinking and hair combing presented partially (by photos) and completely (by video) to the patients with encephalic vascular accident . The sample was generated from 12 patients (62 ± 8 years) and 10 healthy subjects (53 ± 5 years), of both sex, divided in two groups for which 5 functional activities were presented partially and completely, in 4 sequences that varied between reached and not reached objectives and correct and incorrect movements, during 24 trials. The test t'Student was applied to verify differences in the recognition time between the groups, and to compare the performance between the tests carried through at 9:00 am and retests at 9:00 am and 4:00 pm. To compare the frequency between the types of reply, the test Qui-square was used. It was verified that the patients presented a greater recognition time and a lower number of correct answers than the healthy subjects, and had better performances in the recognition of the complete sequence than the partial one. Bigger frequency was observed in the reply that the objective and the movement were being presented correctly, however the healthy subjects had soon indicated the correct reply in the first trials. An improvement tendency was observed in the performance, when the stages of tests and retests had been carried through in the same schedule. According to the results, it is suggested that the patients with stroke can better recognize the correct movements of a functional activity when it is presented completely in video form, what can influence the choice of the therapeutical strategy during the process of motor rehabilitation

Determinação do teor de cálcio através da termogravimetria, em medicamentos utilizados no tratamento da osteoporose: um estudo comparativo

The present study utilized the thermogravimetry (TG) and optical emission spectroscopy with inductively coupled plasma - ICP / OES to determine the calcium content in tablets of carbonate, citrate and calcium lactate used in the treatment of osteoporosis. The samples were characterized by IR, SEM, TG / DTG, DTA, DSC and XRD. The thermal analysis evaluated the thermal stability and physical-chemical events and showed that the excipients influence the decomposition of active ingredients. The results of thermogravimetry indicated that the decomposition temperature of the active CaCO3 (T = 630.2 °C) is lower compared to that obtained in samples of the tablets (633.4 to 655.2 °C) except for sample AM 2 (Ti = 613.8 oC). In 500.0 °C in the samples of citrate and calcium lactate, as well as their respective active principles had already been formed calcium carbonate. The use of N2 atmosphere resulted in shifting the initial and final temperature related to the decomposition of CaCO3. In the DTA and DSC curves were observed endo and exothermic events for the samples of tablets and active ingredients studied. The infrared spectra identified the main functional groups in all samples of active ingredients, excipients and tablets studied, such as symmetric and asymmetric stretches of the groups OH, CH, C = O. Analysis by X-ray diffraction showed that all samples are crystalline and that the final residue showed peaks indicative of the presence of calcium hydroxide by the reaction of calcium oxide with moisture of the air. Although the samples AM 1, AM 2, AM 3 and AM 6 in their formulations have TiO2 and SiO2 peaks were not observed in X-ray diffractograms of these compounds. The results obtained by TGA to determine the calcium content of the drugs studied were satisfactory when compared with those obtained by ICP-OES. In the AM 1 tablet was obtained the content of 35.37% and 32.62% for TG by ICP-OES, at 6 AM a percentage of 17.77% and 16.82% and for AM 7 results obtained were 8.93% for both techniques, showing that the thermogravimetry can be used to determine the percentage of calcium in tablets. The technique offers speed, economy in the use of samples and procedures eliminating the use of acid reagents in the process of the sample and efficiency results.

Degradação de compostos orgânicos voláteis usando o catalisador SBA-15 contendo titânio

The groundwater pollution arising due to fuel leaks gas stations has presented a problem aggravating. Increasingly studies related to environmental problems such accidents and seek to propose some solutions for the treatment of groundwater and soils that are contaminated by gasoline. This study evaluated the use of molecular sieve TiSBA-15 as a catalyst for the reaction of removing of volatile organic compounds, particularly benzene, toluene, ethylbenzene and xylenes, known as BTEX, one of the main pollutants found in groundwater. The catalyst was synthesized by the method post-synthesis techniques and characterized by XSD, TG/DTG, adsorption/desorption of N2, XRF-EDX, for checking the incorporation of titanium and formation of the structure of the catalyst. The reaction occurred with the presence of hydrogen peroxide, H2O2, in aqueous medium to form hydroxyl radicals, which are needed in the process of removal of BTEX compounds. The catalytic reaction was carried out for 5 hours at 60 °C, pH to 3.0, and analyzes of the compounds were made in a gas chromatograph with a flame detection means photoionization static headspace (HS-GC-PID). The catalytic tests have shown the efficacy of using this type of catalyst for the removal of these volatile organic compounds, having a removal rate of 90.60% in the range where the catalyst was studied TiSBA-15(5,0)

Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Utilização de uma coluna de flotação para remoção de compostos orgânicos da água de produção

Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1° order.

Síntese e caracterização de compostos de coordenação homolépticos e heterolépticos com o ligante ácido kójico

The present work has as main objective to contribute to the coordination chemistry of the ligand kojic acid, with the synthesis and characterization of the homoleptic compounds [Al(kj)3], [Fe(kj)3], [Fe(kj)2], [Cu(kj)2] e [Ru(kj)3], and the new heteroleptic complexes, trans- K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2]. The obtained compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). The infrared results indicated the coordination of the bidentate ligand kojic acid, due to reductions in the values of the stretching frequencies of the carbonyl and double bonds, compared to the free ligand for all complexes obtained. The presence of new vibrational modes indicated the change of symmetry of the molecules in the new compounds synthesized. Additionally, the presence of vibrational modes assigned to metal-oxygen also contributed to confirm the ligand coordinating to the metal ions. Through this technique, was also possible to perform correlations of the numbers of vibrational modes, in the region 1400-900 cm-1 and the compounds geometry. The heteroleptic compounds exhibited υC≡N in 2065 and 2053 cm-1, respectively, for the trans-K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2], indicating coordination of the cyano ligand to metal ions FeII e RuII. Comparing the obtained values with literature data was possible to identify the complex isomerism as trans. In relation to the results of electronic spectroscopy, studies of pH variation of kojic acid provided information on the distribution of electron density in the molecule, showing characteristic spectral profile of kojic ion and its protonated form (Hkj, kojic acid), with two bands at 215 and 269 nm, or deprotonated (kj-), with bands at 226 and 315 nm. The electronic spectra obtained for all complexes in aqueous medium, in the ultraviolet region, exhibited variations of the energies assigned to kojic acid intraligand transitions while in the visible region, only transitions assigned to charge transfer of iron and ruthenium complex have been identified

Avaliação da remoção catalítica de compostos orgânicos monoaromáticos em água utilizando materiais nanoestruturados de sílica

Statistics of environmental protection agencies show that the soil has been contaminated with problems often resulting from leaks, spills and accidents during exploration, refining, transportation and storage oil operations and its derivatives. These, gasoline noteworthy, verified by releasing, to get in touch with the groundwater, the compounds BTEX (benzene, toluene, ethylbenzene and xylenes), substances which are central nervous system depressants and causing leukemia. Among the processes used in remediation of soil and groundwater contaminated with organic pollutants, we highlight those that use hydrogen peroxide because they are characterized by the rapid generation of chemical species of high oxidation power, especially the hydroxyl radical ( OH), superoxide (O2 -) and peridroxil (HO2 ), among other reactive species that are capable of transforming or decomposing organic chemicals. The pH has a strong effect on the chemistry of hydrogen peroxide because the formation of different radicals directly depends on the pH of the medium. In this work, the materials MCM-41 and Co-MCM-41 were synthesized and used in the reaction of BTEX removal in aqueous media using H2O2. These materials were synthesized by the hydrothermal method and the techniques used to characterize were: XRD, TG/DTG, adsorption/desorption N2, TEM and X-Ray Fluorescence. The catalytic tests were for 5 h of reaction were carried out in reactors of 20 mL, which was accompanied by the decomposition of hydrogen peroxide by molecular absorption spectrophotometry in the UV-Vis, in addition to removal of organic compounds BTEX was performed as gas chromatography with detection photoionization and flame ionization and by static headspace sampler. The characterizations proved that the materials were successfully synthesized. The catalytic tests showed satisfactory results, and the reactions containing BTEX + Co-MCM-41 + H2O2 at pH = 12.0 had the highest percentages of removal for the compounds studied

STREAM-AP: um processo para sistematizar a escolha de padrões arquiteturais baseado em requisitos não-funcionais

The importance of non-functional requirements for computer systems is increasing. Satisfying these requirements requires special attention to the software architecture, since an unsuitable architecture introduces greater complexity in addition to the intrinsic complexity of the system. Some studies have shown that, despite requirements engineering and software architecture activities act on different aspects of development, they must be performed iteratively and intertwined to produce satisfactory software systems. The STREAM process presents a systematic approach to reduce the gap between requirements and architecture development, emphasizing the functional requirements, but using the non-functional requirements in an ad hoc way. However, non-functional requirements typically influence the system as a whole. Thus, the STREAM uses Architectural Patterns to refine the software architecture. These patterns are chosen by using non-functional requirements in an ad hoc way. This master thesis presents a process to improve STREAM in making the choice of architectural patterns systematic by using non-functional requirements, in order to guide the refinement of a software architecture