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Sobre a influência de fosfinas e do ligante isocianida de p-Toluenosulfonilmetila na citotoxicidade de compostos de Ru(II)
(Universidade Federal de São Carlos, 2018-08-17) Silveira, Rafael Gomes da; Batista, Alzir Azevedo; https://lattes.cnpq.br/6469642481998660; Moreira, Wania da Conceição; https://lattes.cnpq.br/3016270106775634; https://lattes.cnpq.br/7946573339859677
The main objective of the present work was to obtain new Ru(II) complexes with lingans diimino, phosphinic and isocyanide p-toluenesulfonylmethyl, to characterize them by diverse physical and spectroscopic techniques, to study the interaction with biomolecules DNA and human serum albumin (HSA), besides to evaluated their cytotoxic properties. In this way, we reported the synthesis of fourteen new complexes and the characterization by elemental analysis, cyclic voltammetry, molar conductance, ultraviolet (UV-vis) spectroscopy, infrared spectroscopy (FT-IR), nuclear magnetic resonance (31P{1H}, 1H, 13C {1H}, DEPT-135, COSY, HMBC and HSQC) and Single crystal X-ray diffraction, when possible to obtain single crystal. For the complexes containing only diimine and phosphinic ligands, there were important electronic and steric effects caused by -stacking interactions. Such effect lead to a differentiated behavior in the hydrogens of the phosphinic phenyl groups in the NMR experiments, it was also possible to observe the same effect by crystallography of X-rays and by DFT calculations. Studies of interaction of complexes with DNA by viscosity measurements indicate that the compounds interact poorly with this biomolecule. Two compounds with diiminic phosphinic linker and the p-toluenesulfonylmethyl isocyanate ligand were selected for interaction studies with gel electrophoresis DNA and competitive assay with Hoescht 33258, where the results indicates that compounds interacting electrostatically and/or by the minor groove of the DNA. The HSA interaction studies, carried out by fluorimetric titrations, show that both compounds present interaction constants (Kb) on the order of 104-106, indicating moderate to strong interaction with this protein. For all cases, the interaction mechanism is static. Cytotoxicity data in human tumor cell lines A549 (lung) and DU-157 (prostate) and non-tumor MCR-5 (lung), show that the compounds bearing the p-toluenesulfonylmethyl isocyanide ligand are the most promising, showing up to 140 times more active than the reference drug and up to 3 times more selective.
Envolvimento da neurotransmissão nitrérgica no hipocampo dorsal no controle da função cardiovascular e das respostas autônomas e comportamentais ao estresse social crônico
(Universidade Federal de São Carlos, 2018-08-17) Almeida, Jeferson de; Crestani, Carlos Cesar; https://lattes.cnpq.br/1117432571971568; https://lattes.cnpq.br/8141647386370567
The hippocampus is part of the limbic system, and is directly involved in cognitive processes, anxiety-related defensive behaviors, stress responses, and the neurobiology of depression. Some studies have also reported a role of the hippocampus in the control of cardiovascular function. However, the neurochemical mechanisms involved in the control of behavioral responses and cardiovascular function within the hippocampus are still poorly understood. Nitric oxide (NO) is synthesized from L-arginine by three isoforms of the enzyme nitric oxide synthase (NOS), which are called neuronal (nNOS), endothelial (eNOS) and inducible (iNOS). Thus, one of the hypotheses investigated in the present study was that alterations in the formation of NO from nNOS into the dorsal hippocampus are involved in the cardiovascular and behavioral changes induced by social isolation. A second hypothesis investigated in the present study was that both nNOS, iNOS and eNOS in the dorsal hippocampus are involved in the control of cardiac responses of the baroreflex. We identified that social isolation increased depressive- and anxiety-like behaviors, and the treatment of the dorsal hippocampus with NPLA (selective nNOS inhibitor) or carboxy-PTIO (NO scavenger) reversed the behavioral effect of depressive type. Social isolation did not alter the blood pressure and heart rate increase and the drop in tail skin temperature evoked by restraint stress. However, treatment of the dorsal hippocampus with NPLA increased restraint-evoked pressor and tachycardic responses and decreased tail temperature in isolated, but not control, animals. Social isolation increased levels of nitrotyrosine in the dorsal hippocampus, and a trend of increased nNOS levels was identified. Regarding the cardiac responses of the baroreflex, we observed that treatment of the dorsal hippocampus with carboxy-PTIO decreased the tachycardia to drop in blood pressure. Microinjection of NPLA increased bradycardia to increase in blood pressure, whereas 1400W (selective iNOS inhibitor) decreased reflex tachycardia and increased reflex bradycardia. In addition, administration of L-NAME (non-selective NOS inhibitor) in animals co-treated with NPLA + 1400W (to inhibit nNOS and iNOS) decreased reflex bradycardia. Based on these results, we conclude that nitrergic neurotransmission in the dorsal hippocampus modulates cardiac responses of the baroreflex, and this control is specific to nNOS, iNOS and eNOS. In addition, social isolation increases the release of NO in the dorsal hippocampus, possibly by increasing nNOS expression, and this effect is related to the anxiogenic- and depressive-like behavioral responses evoked by social isolation. Furthermore, this increase in the local formation of NO from nNOS plays an inhibitory role in the increase of arterial pressure and heart rate, in addition to facilitating the sympathetic-mediated vasoconstriction during restraint stress.
Concepções de professores sobre avaliação: estudo de caso de ensino de língua espanhola no CEL de São Carlos
(Universidade Federal de São Carlos, 2018-08-17) Silveira, Milena Ribeiro; Gregolin, Isadora Valencise; https://lattes.cnpq.br/1015869228676997; https://lattes.cnpq.br/7187845905795944
The main goal of this survey is to evaluate the concepts of spanish language teachers evaluation from Study Language Center from São Carlos SP and to compare with proposals described in National Curricular Plans (NCP Brazil, 1998 and 2000) and National Curricular Orientations (OCE Brazil, 1998) and try to discuss possible trends in their didactic practice evaluations described in our survey context. By the way, we use as data collection tool an interview with CEL coordinator with the aim of understanding the principle of the pedagogical project of CEL and a questionnaire to Spanish teachers with the main of chart the conceptions and practices evaluated from the group. From the analysis, we try to discuss what are the conceptions about concepts of express evaluation by teachers to base their practices and how these conceptions relate to the guidelines and national curricular orientation. Our theoretical foundation is based on authors who discuss evaluation in the general field of education in the general field of education (LIBÂNEO, 1991, PERRENOUD, 1999; SACRISTÁN, 2000, HOFFMAN, 2002; LUCKESI, 2011) and in the field of applied linguistics (SCARAMUCCI, 2004, LEFFA, 1998, VIEIRA-ABRAÃO, 2012). Keyword: Evaluate, Study Language Center, Spanish Language.
Sustentabilidade nos projetos de curso de formação de professores: um estudo das licenciaturas da UFSCar Sorocaba
(Universidade Federal de São Carlos, 2018-08-17) Carvalho, Laura Leite de; Fortunato, Ivan; https://lattes.cnpq.br/8293044394759438; Melo, Ismail Barra Nova de; https://lattes.cnpq.br/3576937472687059; https://lattes.cnpq.br/8927115214500186
Since it began activities in 2006, the UFSCar Sorocaba campus has assumed the concept of sustainability as the guiding principle of its development. This position was inserted in the Institutional Development Plan (PDI), a document that guides the functioning of the university. From the PDI, it was verified that the principles of sustainability, from Environmental Education, must be present not only in the physical aspects of the campus, but also in the professional formation of the students, in which each course must work with these principles of some way. In this way, knowing that the courses have a Pedagogical Political Project (PPP), which contains their contents and principles, it was necessary to analyze them to verify if the recommendations of the PDI, regarding Environmental Education, were met. Therefore, the objective of this research is to analyze the approach of Environmental Education and the presence of the principles of sustainability in the PDI and PPP. In this work, the seven undergraduate courses at UFSCar Sorocaba were analyzed, with the purpose of verifying how the initial formation of campus teachers should deal with issues related to sustainability. The methodology used was documentary research of the eight documents: PDI and PPP of the seven undergraduate courses. The results pointed out that although the PDI presents the principles of Sustainability as guiding the campus, does not deepen these contents and does not present proposals for their implementation. In addition, of the seven undergraduate courses, only three refer to differentiated course formation, focused on sustainability and offer a specific discipline, the other four courses refer to this proposal in a very superficial way and do not offer specific discipline for environmental studies. Thus, it can be seen that the focus for sustainability in all areas of the campus, including vocational training, according to the PDI, is not addressed in the pedagogical projects of all courses, and in some, it is spoken in a shallow way, not making clear, from the analysis of these documents, if UFSCar Sorocaba is fully aligned with the principles of sustainability in the training of its students.
Estudo das propriedades estruturais, ópticas e fotoluminescentes do Sistema α-(Ag2-3x-yTRxLiy)WO4 (TR = Pr, Sm, Eu, Tb, Dy e Tm)
(Universidade Federal de São Carlos, 2018-08-17) Pinatti, Ivo Mateus; Longo, Elson; https://lattes.cnpq.br/9848311210578810; Rosa, Ieda Lúcia Viana Rosa; https://lattes.cnpq.br/8086262254116449; https://lattes.cnpq.br/8338530279475392
Luminescent materials of different colors emission are of great interest for development of new or more efficient optical devices. Although many materials have been reported using different approaches, green synthesis and nanosized phosphors of high color rendering is still very limited. Tungstate matrix can be considered as ideal host lattice for dopants as they possess high thermal, chemical and physical stability. In addition, silver compounds can be an excellent material for biomedical application due to its low toxicity and bacteriostatic properties, which in turn can be used in the health area. This thesis aims to investigate the structural, optical and photoluminescent properties of the system α-(Ag2-3x-yRExLiy)WO4 (RE = Pr, Sm, Eu, Tb, Dy e Tm) prepared by the coprecipitation methodology. This experimental procedure was fast, simple, and efficient to prepare these inorganic materials. The samples were investigated by X-ray diffraction with Rietveld refinement analysis, Raman and Ultraviolet-visible spectroscopy, and Photoluminescence measurements. The morphology was analyzed by Field-Emission Scanning Electron Microscopy and Transmission Electron Microscopy. X-ray Photoelectron Spectroscopy was performed to verify the superficial composition and details. The phase of the nanocrystals was confirmed and the structural and optical properties were dependent of the Rare Earth and Lithium ions. The nanomaterials presented excellent photoluminescent behavior due to the combined matrix and Rare Earth luminescence as well as temperature and co-doping dependence. The nanorod morphology reinforces the preferred alignment, dense packing and directional emission characteristics. Inspired by the above considerations, these new materials may present new applications and superior characteristics for luminescent compounds as well as for biological purpose.
Catalisadores Pt/Al2O3 e CeO2/Pt/Al2O3 aplicados à reação deslocamento gás-água: efeito da composição nas propriedades estruturais e catalíticas
(Universidade Federal de São Carlos, 2018-08-17) Borges, Laís Reis; Bueno, José Maria Corrêa; https://lattes.cnpq.br/0157452280626031; https://lattes.cnpq.br/9219091363286049
Alumina-supported platinum catalysts were synthesized via conventional impregnation varying the metal contents (0.3 to 2% Pt; 6 to 20% Ce, m / m) and the Pt precursors (H2PtCl6 and [Pt(NH3)4] (NO3)2), were evaluated for the structure-activity relationship in the water gas shift reaction (WGS). The results of the X-ray absorption spectroscopy analysis for the Pt/Al2O3 catalysts indicated different average sizes of metal platinum nanoparticles supported on alumina (0.7 and 1.4nm) as a function of the metal precursor, and an increase in the oxygen under the surface and/or under the metal-support interface with decreasing platinum/nanoparticle size. However, the inside and surface electron density has not been modified as indicated by the same Pt-Pt (2.75Å) and Pt-O (2.00Å) bond distances for all of the catalysts. Theoretical mechanical-quantum calculations indicated an insensitivity of the bond distances in clusters of Pt greater than 13 atoms with the addition of oxygen under the surface, suggesting that the synthesized samples are larger than this one, corroborating with the analysis of transmission electron microscopy. Infrared spectroscopy with CO adsorption (FTIR-CO) showed a distribution of metallic and slightly oxidized platinum species under the surface, and an increase of Pt0 sites of low coordination with the platinum content due to a lower coverage of the oxygen. These sites of low coordination presented a greater thermal stability of CO. As for the activity in the WGS reaction of the Pt/Al2O3 catalysts, the reaction frequency (TOF) decreased (0.5 to 0.2 s-1) with increasing platinum content (0.3 to 2% Pt), suggesting that fractions of the active sites under the samples with high platinum content, calculated by FTIR-CO, do not participate in the reaction due to the strong adsorption of CO. The addition of ceria on the Pt/Al2O3 catalysts decreased the number of Pt-Pt coordination and increased Pt-O, indicating a greater stabilization of the nanoparticles (average size ≤ 1nm) and a strong interaction of the Pt particles with CeOx species. However, in spite of the structural changes, there was no change in the surface electronic density of the Pt nanoparticles. The increase in the activity (TOF) of up to 10 times with the cerium content in relation to the non-promoted catalysts suggested that the activity was controlled by sites of Pt-O-Ce interface, which modified the reaction path. The presence of Cl under the promoted samples affected the redox properties of ceria, making it difficult to transfer oxygen and thus to increase the activity. Therefore, it can be affirmed that the structural properties allowed to identify the active sites that determine the catalytic performance in the WGS reaction.
Espanhol para alunos brasileiros: estratégias de aprendizagem sugeridas pelas orientações ao professor do livro didático Cercanía Joven
(Universidade Federal de São Carlos, 2018-08-17) Nordi, Cristiane; Gregolin, Isadora Valencise; https://lattes.cnpq.br/1015869228676997; https://lattes.cnpq.br/9031749271012154
The general objective of this research was to identify bridges in the guidelines contained in the handbook and in the textbook teacher that analyzed the mother tongue (Portuguese) and the foreign language (Spanish), classify the types of strategies proposed and discuss the indicators which characterize a specific approach to working with languages close to Basic Education. When we take the guidelines to the teacher as an object of analysis, we seek to understand how the Spanish language teaching is characterized or proposed to Brazilian Basic Education students today, starting from the hypothesis that there is some specificity in relation to the other materials existing in the market because it is a textbook approved by the PNLD of 2015 and therefore "comply" with the "official requirements" of what is considered appropriate at the moment, in terms of methodological guidelines. Therefore, we assume that the didactic textbook, the object of our research, because it was written for the Brazilian context of Basic Education, should offer guidance to the teacher (both in the section called the Teacher's Handbook and along the teacher's copy ) that relate the Portuguese language and the Spanish language. More specifically, we seek to identify which learning strategies (OXFORD, 1990; O'MALLEY and CHAMOT, 1990; WENDEN, 1991) that relate Portuguese and Spanish are proposed by orientations to the teacher and to analyze if they characterize a specific approach to Education Basic, based on previous discussions in the relevant literature. In order to do so, we proceed to a qualitative study of the case, which starts with a bibliographical review on the themes of teaching Spanish to Brazilian and nearby languages (ALMEIDA FILHO, 2001, 2002, 2004, 2007, 2012, 2013; GONZÁLEZ 1989, 2008; DURÃO, 1999, 2002, 2004; ERES FERNÁNDEZ, 2001, 2003, 2004, 2017; FANJUL, 2012, 2014, SERRANI-INFANTE, 1998, 2005; CELADA, 2002, ORTIZ ALVAREZ, 2002,2007). As a result, our research has identified that teacher orientation generally emphasizes the use of knowledge-based learning strategies that students already have in their own mother tongue and, less prominently, in the other foreign language taught at school (English) and the Plural Approaches (CUMMINS, 1979, 1983, DOLZ, GAGNON and MOSQUERA, 2009, SIMARD, 1997, CANDELIER, 2007, DEGACHE, 2006, CAROLA and ALBUQUERQUE COSTA, 2014). Among the strategies proposed, the guidelines emphasize the use of cognitive and social strategies, but the compensatory strategy, which helps the student to overcome learning gaps and which is pointed out by the PCNEMs (1999) as the most important to be taught, can be in several of the guidelines throughout the Teacher's Manual.