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Item type:Item, Competências do professor de Português Língua Estrangeira (PLE) em formação : (re)construção e reflexão(Universidade Federal de São Carlos, 2014-03-26) ;Negri, Marcia Fanti ;Viana, Nelson ;https://lattes.cnpq.br/6252579012192711https://lattes.cnpq.br/0126666263989130This research aims to analyze the performance of teachers (in the process of education) of Portuguese as a foreign language, based on a range of theoretical models of competence. Therefore, a brief summary of the term competence was outlined, starting with the concept of communicative competence and their approaches related to foreign language teachers. This research is based upon theories of competence, communicative competence and competence for foreign language teachers. It includes the following authors teachers: Chomsky (1960), Hymes (1972), Savignon (1972), Widdowson (1978), Canale e Swain (1980), Canale (1983), Bachman (1990), Celce-Murcia et al (1995), as well as Perrenoud (1999), Basso (2001) and Almeida Filho (1993 e 1999). In order to collect data, the following instruments/procedures were used in this investigation: an initial questionnaire which aimed to obtain the teachers’ profile; audio recorded lessons; field notes and a final questionnaire. Afterwards, some criteria were established to analyze the data. Some excerpts of the recorded lessons were selected due to the fact that they show evidence of some competences. Based upon Almeida Filho (1993 e 1999) it is considered that the competences of foreign language teachers can be reconstructed through reflection upon their performance. With this work we aim to contribute to the process of reflection in teacher education in the field of foreign languages, as well as, to the literature regarding foreign language teaching and learning process and, more specifically, to the area of Portuguese as a Foreign Language teaching.Item type:Item, O carnaval de Antares: fantástico e carnavalização literária em Incidente em Antares(Universidade Federal de São Carlos, 2014-03-26) ;Silva, Valeria Cristina da ;Pellegrini, Tânia ;https://lattes.cnpq.br/0280434883580627https://lattes.cnpq.br/2580476743625445In extremely turbulent period corresponding to the decades of 1960-1970 in Brazil, literature has found curious ways. The authors of that period, trying to express the disjunction of Brazilian society, due to the military dictatorship, and aware of the inability to represent the world as a whole, found in the fragmentation of narrative and the use of other narrative resources - as cinema, advertising etc - an esthetic answer for such complex moment. In this scenario, however, stands the figure of Erico Verissimo, who chooses different ways. Respecting his own conception of literature, the author constructed a work averse to these esthetic renovations. Based on the pillars of "realism" Incidente em Antares innovates by introducing the supernatural element, well know by Todorov as "fantastic". Based on some studies related to fantastic literature and the historical moment, in which Incident em Antares was produced, our work has two specific objectives: first of all, to reveal how the fantastic element is articulated in the novel; secondly, to demonstrate how this fantastic element acquires specific characteristics, allowing the emergence of what Mikhail Bakhtin called literary carnivalization. Our main hypothesis is that the literary carnavalization in Incidente em Antares is responsible for its critical feature.Item type:Item, Caracterização morfológica e molecular de Campoletis Foerster, 1869 (Hymenoptera, Ichneumonidae, Campopleginae), parasitoides de Spodoptera frugiperda (Smith, 1797) (Lepidoptera, Noctuidae)(Universidade Federal de São Carlos, 2014-03-26) ;Camargo, Luiza Figueiredo ;Dias, Angélica Maria Penteado Martins ;https://lattes.cnpq.br/8637344058859147https://lattes.cnpq.br/7659288914273973The fall armyworm Spodoptera frugiperda (SMITH, 1797) is a voracious pest of numerous crops of economic importance throughout the New World. In Brazil, their larvae can be attacked by several species of parasitic wasps, which are candidate to biological control agents against this pest. Surveying the parasitoid fauna on S. frugiperda in maize throughout Brazil two very morphological similar species of Campoletis are found. To ensure the efficiency of the biological control works, the knowledge about the taxonomy of the species related is necessary. Campoletis specimens emerged from Spodoptera frugiperda were studied mofologically and molecularly, in order to solve taxonomic problems among C. sonorensis (CAMERON, 1886) and C. flavicincta (ASHMEAD,1890). The samples came from three regions of Brazil: Santa Maria, RS; Ribeirão Preto, SP; Sete Lagoas, MG. Pictures from the type material of the two species were studied, besides the original descriptions of them. A possible sinonimy is indicated between the both species, for which the name C. sonorensis will be used based on the priority law for species names. A redescription is made to Campoletis sonorensis from Brazil, using morphological characters and DNA Barcoding.Item type:Item, Estudo da variação do perfil químico de citros com HLB e sadios, buscando informações sobre mecanismo de defesa(Universidade Federal de São Carlos, 2014-03-26) ;Bellete, Barbara Sayuri ;Silva, Maria Fátima das Graças Fernandes da ;https://lattes.cnpq.br/0457632122660653https://lattes.cnpq.br/5893633998701597This paper describes the variation of the chemical profile study of citros after inoculation of the bacterium "Candidatus Liberibacter asiaticus", responsible for Huanglongbing (ex greening), one of the most serious diseases causing several losses in the Brazilian citrus industry. The bacterium "Ca. Liberibacter " was inoculated in seedlings of the" Valencia "(Citrus sinensis (L.) Osbeck) grafted on "Swingle" (Poncirus trifoliata x Citrus paradisi) and was evaluated the change of secondary metabolites by the development of analytical methods such as HPLC-UV, LC-MS/MS, LC-UVSPE- NMR and chemometric tools. The chemometric methods PCA and S-PLOT applied to data obtained in the studies by LC-MSE allowed to discriminate infected plants from healthy plants, and also allowed the characterization of the compounds that most contribute to this differentiation. By analyzing the change in the chemical profile of citrus studied by HPLC-UV-SPE-NMR, it was able to detect the change of some coumarins in the roots and stem from rootstock, and glycosides flavonoid in leaves, indicating that these compounds may be involved in defense mechanism of the plant, and may be acting as a Phytoanticipins. Aiming to better interpret this change observed, also performed a quantitative variation of some secondary metabolites, as coumarin identified in the roots, and flavonoids identified in leaves. This technique showed an increase of coumarins in infected plants, while there was a decrease in all the flavonoids in the leaves in infected treatment, indicating that the plant defense is in the roots. Finally, a phytochemical study of citrus was performed aiming obtain patterns compounds, and this study resulted in the isolation of 13 substances, from several classes of secondary metabolites.Item type:Item, Participação social e estratégia saúde da família : desvelando fragilidades e possibilidades(Universidade Federal de São Carlos, 2014-03-26) ;Furlanetto, Camila Fressatti ;Ogata, Márcia Niituma ;https://lattes.cnpq.br/3274294833403570 ;Machado, Maria Lúcia Teixeirahttps://lattes.cnpq.br/5703683100332513The participation and the social control are guiding principles of SUS and for democratization of the system. The health acting and services management should express joint definitions between the government and population. The 8.142/1990 Law establishes as instances for participation and social control in the Health the counsels and the conferences. The Family Health Strategy (FHS) could be considered an easier locus of the materialization of the social participation because of the link possibility with the user population. Considering this hypothesis, the research sought to analyze the users and Health worker’s perceptions of the Family for the social participation, seeking for the social effective control in health. It was held with workers and users of two Family Health Units in the São Carlos county, from the qualitative analysis, up with the application of semi structured interviews and thematic analysis, whose origins three categories(i) challenges for the effectiveness of the social participation in the FHS; (ii) participation spaces or just completion of formalities?; (iii) FHS: potentiality for social participation. The results of this study allowed unveiling various fragilities that figures as challenges for the social participation in the researching field, such as: lack of information/comprehension, exposition and power relations and welfares/accommodation. The institutionalized spaces for the participation and social control addressed in this study were the Municipal Health Conferences and the locals Management Councils, the effectiveness of them were analyzed negatively due lack of support and government participation. The research allowed unveiling also potentials as the counsels’ effort and the capacity spaces done between the team and the users members of the Management Councils in the Family Heath Units. Lastly, the participants perception strengthens the challenge that is the social participation in the SUS. As contribution, the needing pointing of more investment and attention to this spaces from the recognition of their potentialities.Item type:Item, Catalisadores à base de Cu, Zn, Al e Ce aplicados à reação deslocamento gás-água(Universidade Federal de São Carlos, 2014-03-26) ;Borges, Laís Reis ;Assaf, José Mansur ;https://lattes.cnpq.br/9563312407691130https://lattes.cnpq.br/9219091363286049The water gas-shift reaction (WGS) is an important step in the production process and purification of H2 from hydrocarbon. Commercially, to overcome the thermodynamic and kinetic limitations, this reaction occurs in two steps, one at higher temperature (450º C to 320ºC) and another step at lower temperature (190º C to 250ºC). The catalyst Cu/ZnO/Al2O3 is used industrially for water gas-shift reaction at low temperature in the chemical and petrochemical industry. Although widely used, are disagreements about the role of each metal in the catalyst, the role of Zn and Al as promoter or stabilizer is not clear and controversies about the influence of some parameters in the activity. This study verified the activity of the catalyst Cu/ZnO/Al2O3 in water gas-shift reaction in the range of temperature, 150ºC to 350ºC, and the feed molar ratio of CO: H2 equal to 1:5. The catalysts were prepared by co-precipitation method, and the effects of content of Al, ratio Cu/Zn and the CeO2 addition was investigated. There was a synergistic effect between the metals Cu-Zn-Al at a ratio (6:3:1), which led to a larger surface area of Cu metallic, and a higher activity compared to the catalysts bimetallics: CuAl (6:1) and CuZn (6:1). By adding Ce to the tri-metallic compound a greater activity was observed at higher temperature than 250ºC, caused by the activation of the effect of oxygen storage characteristic of cerium oxide, however it has been a reduction on stability. The quantity of Al influenced the precursor structure whith formation of rosasita and malachite with low levels of Al, and hydrotalcite structure was observed when the Al content was higher than 11.4% (mass concentration). A great quantity of Al (16% (mass concentration)) was found among the hydrotalcite catalysts, which led to a higher conversion of CO and higher crystallinity, however this activity is almost the same of the catalyst derived from the structures malachite and rosasita (CuZnAl/6:3:1) at high temperature. The catalyst whith Cu/Zn=2 presented higher activity at temperatures below 250ºC, probably due to the higher metallic area, while at high temperature, catalysts with high ratios of Cu/Zn achieved higher conversions. Therefore, this study verifies that TOF (turn over frequency) isn t directly related with surface area of Cu0, the crystallinity and quantity of Cu are factors that influenced the activity of the WGS reaction.Item type:Item, Integração e segurança na Amazônia transnacional(Universidade Federal de São Carlos, 2014-03-26) ;Correa, Paulo Gustavo Pellegrino ;Martins Filho, João Robertohttps://lattes.cnpq.br/4935704081469903This study aims to understand the dynamics of integration and security in the transnational Amazon and its importance to South America and also it analyzes the role of Brazil as the largest amazon country in the binomial integration/ security in the region . The theoretical approach adopted by this research is called the " Copenhagen School " which is based on three analytical pillars : the concept of securitization and desecuritização , multisectoral approach to security and the concept of regional security complexes . Our time frame is concentrated between 2000 - the date of the first summit of South American countries where major integration initiatives have been launched - and 2013 , the year of completion of our research . Since the Amazon region covers more than 50 % of the South American subcontinent and involves nine countries , it is possible to identify axes of countries that comprise different dynamics in the binomial integration / security. Considering the importance of this dynamic to Brazil , we will highlight our work on two axes within the transnational Amazon : Peru - Brazil - Bolivia and the Guiana Plateau axis. The first stands out for having an integration process that brings Brazil to the Pacific and presents a specific secutity constellation within the transnational Amazon . The second represents the path of integration between Brazil and northern of the subcontinent and the Caribbean and also demonstrates a specific regional security dynamics in Amazon region.Item type:Item, Estratégia competitiva e estratégia de produção: estudos de caso na produção de embalagens obtidas a partir de polietileno proveniente de fontes sucroalcooleiras(Universidade Federal de São Carlos, 2014-03-27) ;Motta, Gabriela Azevedo ;Alves Filho, Alceu Gomes ;https://lattes.cnpq.br/7885557554922569https://lattes.cnpq.br/7250712374641353In the search for new positions in the market, many companies have sought to differentiate their products and services, possibly reformulating their strategies. One of the possible strategies for modification is related to sustainability of the materials used in products and processes, such as plastic from sugarcane sources. The objective of this work is tried to identify the competitive strategies and manufacturing strategies adopted by companies that use plastic from sugarcane in package. To achieve this objective was opted for conducting case studies of two companies leader in their segments: a producer for the staffing industry, perfumery and cosmetics and other packaging supplier to the food industry. The first company competes with a focus on differentiation in only one segment, and its manufacturing strategy of horizontal integration of its packaging. The second company adopts a competitive strategy of differentiation in the context of the industry, and a manufacturing strategy of vertical integration of its products.Item type:Item, Aprender a aprender: uma trajetória possível para os trabalhadores do SUS?(Universidade Federal de São Carlos, 2014-03-27) ;Costa, Ana Clara Lopes ;Lima, Valéria Vernaschi ;https://lattes.cnpq.br/7945420582384290https://lattes.cnpq.br/2140918293527948The main goal in this study is to analyze the learning process of the Brazilian Unified Health System (SUS) staff when exposed to an interactionist educational initiative. Such initiative aims the transformation of health practices by focusing on clinical management and qualifying care for the users of SUS in 33 hospitals from the 5 Brazilian geographical regions. This study used a specialization course that was developed in 2009-10 that focused on the articulated development of management abilities, support and education in health. The study was based on the principles of qualitative research and the completion of course work drawn by the attendees of the specialization course on Clinical Management was also used as a source of data. The content was analyzed for data interpretation aiming to identify and explain the causes and interactions for the production of the phenomenon. The novelty of the proposal was not an obstacle for the learning process. Student focused learning and the appreciation of previous knowledge where related to the practical application of such content and the broaden of autonomy, especially on what concerns recently acquired information. It was also observed that the participants actions were related to the three areas: clinical management; health awareness and education. The interaction in small groups, communication, integration and open dialogue were valued as fundamental e facilitating elements of learning, group work development and qualification of care. Transformation on practices on health related to management, attention and education were observed and were part of the knowledge that define the profile of clinical management built and developed through the course.Item type:Item, Efeitos do exercício intervalado na expressão de proteínas inflamatórias e catabólicas na musculatura esquelética de ratos tratados com dexametasona(Universidade Federal de São Carlos, 2014-03-27) ;Martuscelli, Aline Mio ;Cardoso, Sandra Lia do Amaral ;https://lattes.cnpq.br/2030708742766455https://lattes.cnpq.br/3580215119041185Dexamethasone is widely used in clinical use due to its potent anti-allergic and antiinflammatory effects, but it has been shown that its chronic use can induce several side effects such as hyperglycemia, hypertension, hypercholesterolemia and muscle atrophy. Muscle atrophy occurs by an imbalance between catabolic and anabolic protein levels. Among catabolic proteins, FOXO3a, MuRF-1 and Atrogin-1 are directly related to muscle atrophy induced by dexamethasone. Furthermore, it is known that some inflammatory proteins (TNF-α and IL-6) also participate in reduction of muscle weight. We have shown that aerobic exercise attenuates some of the side effects of dexamethasone, but nothing is known about interval training (IT) performed before and concomitant dexamethasone treatment. This study investigated if interval training is effective in attenuating muscle atrophy induced by dexamethasone and if the proteins FOXO3a, MuRF-1, Atrogina-1, TNF-αand IL-6 are involved in this response. Rats were distributed into 4 groups: sedentary control (SC), sedentary + Dexa (SD), trained control (TC), and trained + Dexa (TD), and underwent an interval training period (50% and 80% of maximal capacity, 2 and 1 min, respectively, 1h/day, 5 days / week, 70 days) or remained sedentary. Dexamethasone was administered during the last 10 days (0.5mg/kg per day i.p.). The rats were weighed weekly during training and daily during the treatment. The tibialis anterior (TA), soleus (SOL) and flexor hallucis longus (FHL) were collected, weighed and stored for analysis of TNF-α, IL-6, FOXO3a, MuRF-1 and Atrogin-1protein levels using electrophoresis method, Western Blotting. Administration of dexamethasone resulted in a significant decrease in body weight (-17%) followed by reduction in TA (-22%) and FHL (-19%) muscles weight. This reduction in muscle weight involved a significant increase in MuRF-1 protein levels in TA (+27%) and FHL (+18%) muscles, although TNF-α (-37%FHL and -15% SOL) and IL-6 (-26% TA, - 24% FHL and -18% SOL) protein levels were reduced. Interval training was effective in blocking the increase of MuRF-1protein level in TA and FHL muscles, moreover interval training significantly reduced FOXO3a production level in TA muscle, in both groups, TC (-27%) and TD (-32%).This response was followed by an attenuation of TA muscle mass after training. Chronic treatment with dexamethasone, as well as training, did not change Atrogin-1protein level. The results of the present study allow us to conclude that MuRF-1 seems to be involved in TA and FHL muscle atrophy induced by dexamethasone treatment, independent of inflammatory proteins signaling. On the other side, interval training determined TA muscle atrophy attenuation by decreasing MuRF-1 and FOXO3a without changes in TNF-α e IL-6 protein levels.Item type:Item, Biotransformação de cicloadutos de Diels-Alder por células intactas de Penicillium brasilianum, endofítico de Melia azedarach(Universidade Federal de São Carlos, 2014-03-27) ;Santos, Ana Carolina Alves dos ;Rodrigues Filho, Edson ;https://lattes.cnpq.br/3667941735597178https://lattes.cnpq.br/6169045230374129Endophytic microorganisms have a great enzymatic potential to biotransformate substances of natural and synthetic origin due to strategies developed during colonization to coexist with the plant in an initial hostile environment. Microbial transformation of Diels-Alder cycloadducts were trailed by the endophyte P. brasilianum using intact cells and resulted in the production of several products (17). These products were identified as products of chlorination (Q4_F2_15), epoxidation (Q1A_CR_16, Q2A_CR_6, Q3A_CR_5), epoxidation and reduction of conjugated double bond (Q2A_CR_5), reduction of conjugated double bond (Q2A_CR_9, Q3A_CR_7_pico2, Q3A_CR_8, Q4A_CR_23), reduction of isolated double bond (Q1A_CR_26), oxidation of allilic methyl group and reduction of conjugated double bond (Q4A_CR_10), reduction of carbonyl and conjugated double bond (Q4A_CR_20), reduction of carbonyl and ether formation (Q5A_CR_15) and finally, reduction of carbonyl group (Q4A_CR_15 e Q5A_CR_18). The reduction of conjugated double bond can be performed by enzymes called Old Yellow Enzymes (OYE), also known as enoate reductase enzymes. The products of carbonilic or double bond reduction were also synthesized chemically and the enantioselectivity of both in vitro and in vivo process were compared. In all cases, microbiological transformations were more enantioselectivity.Item type:Item, O uso de instrumentos de análise ergonômica no processo de trabalho agrícola: o caso da colheita mecanizada da cana-de-açúcar(Universidade Federal de São Carlos, 2014-03-27) ;Ferreira, Ana Lucy Rodrigues ;Alves, Francisco José da Costa ;https://lattes.cnpq.br/9183120186518337https://lattes.cnpq.br/1604837309190395The changing in the labor dynamics of the sugarcane harvesting, occasioned by integration of mechanical harvesters, has subjected workers to new working conditions, increasing the interactions with machines, and consequently causing new diseases and work accidents. For improving the performance of work so that this becomes less destructive of human capabilities, is important the use of instruments that allow the identification of risks from man-labor ratio, which are identified through the study of literature in Ergonomics. This study aimed to verify the applicability of the checkpoints of the instrument Ergonomic Checkpoints in Agriculture to the work situation in the context of mechanized harvesting of cane sugar. A review of the relevant issues related to the study was accomplished, considering the themes: Ergonomics, ergonomic analysis tools and working conditions; process of mechanized production of cane sugar, with a focus on the process of harvesting and working conditions; and, finally, the study of the instrument Ergonomic Checkpoints in Agriculture. Subsequently, the analysis of the instrument was accomplished, which was constituted of the following principal stages. Initially, the checkpoints of the instrument were classified considering the workloads, and the similarity of content. Posteriorly, the checkpoints were analysed with respect the applicability in the job functions found in mechanical harvesting of cane sugar process. As a result, 84 checkpoints were classified into 23 clusters and 16 checkpoints were not grouped, among which 11 clusters and 8 checkpoints, which represent 53% of the content of the instrument, were identified with potential of application in the sugarcane mechanical harvesting. The checkpoints identified may assist in the evaluation and implementation of better working conditions, considering the ergonomic point of view, in the mechanical harvesting of sugarcane.Item type:Item, Os ensinamentos de Confúcio e a formação contemporânea de professores de língua inglesa em Taiwan : relações entre variáveis socioculturais e competências(Universidade Federal de São Carlos, 2014-03-27) ;Tsai, Yun Hsien ;Viana, Nelson ;https://lattes.cnpq.br/6252579012192711https://lattes.cnpq.br/5857492244010306This work aims to study the profile of English teacher education in Taiwan through a more specific discussion of language teacher’s competence. For this, we chose to analyze an English undergraduate teacher education program at a public university in this country, and, considering time constraints, we limit the study, focusing on the perspective of the teacher educators. Therefore, the program curriculum and the transcriptions of interview with the teachers educators will comprise the data set for analysis. Once teacher education process is based on the social system of the country, we also include the contextual factors or socio-historical elements in the study, by considering them as constituents of social constructions factors.Item type:Item, Identificação de regiões genômicas e genes candidatos associados com qualidade de carne e conteúdo de minerais no músculo em bovinos da raça Nelore(Universidade Federal de São Carlos, 2014-03-27) ;Tizioto, Polyana Cristine ;Regitano, Luciana Correia de Almeidahttps://lattes.cnpq.br/4754030540306395This thesis is divided into three chapters in order to facilitate the understanding of the experiments that will be presented. The first chapter refers to a concise literature review, which covers the main theoretical themes and justifications regarding the developed experiments presented in the following chapters. The second chapter presents two genome-wide association studies in Nellore cattle, being the first for meat quality traits and the second for the mineral content of the Longissimus dorsi muscle. Considering the importance of beef tenderness for producer, the third chapter deals with the strategy used to identify candidate genes that explain the variation in this trait in Nellore breed. The experimental results suggested that meat quality traits and mineral content of skeletal muscle is at least partially genetically determined. Most quantitative trait loci (QTLs) identified is of small effects, revealing the polygenic background of those traits and the importance of applications that consider variation at the genomic level. However, some major effect QTLs were found for muscle pH , iron, selenium , zinc and calcium content in muscle, which accounted for 4.01 , 6.53 , 3.53 , 2.59 and 2.55% of the additive genetic variance , respectively. Through these studies, we produced an extensive list of candidates genes and metabolic pathways related to economic interest traits in beef cattle, which should contribute to the understanding of the their underlying genetic mechanisms. A genome-wide association approach still not economically feasible for beef producers, therefore candidate genes strategy is interesting because of its major accessibility. KCNJ11, MyoD1 and ASAP1 candidate genes were identified as explaining part of the variation in meat tenderness of Nellore breed. The validation of genomic regions and candidate genes identified in this study and future mapping of causal mutations should contribute to the implementation of marker-assisted selection and for the genomic selection of traits of economic interest in Nellore cattle.Item type:Item, Complexos de vanádio contendo bases de Schiff como catalisadores na oxidação do cicloexano(Universidade Federal de São Carlos, 2014-03-27) ;Cantanhede, Leonardo Baltazar ;Marques, Clélia Mara de Paula ;https://lattes.cnpq.br/0451284088402660https://lattes.cnpq.br/0740032606397506The vanadium complexes of the type [VO(acac)2], [VO(acac)(apftsc)], [VO(acac)(apmtsc)], [VO(acac)(aptsc)], [VO(acac)(apf)], vanadium (IV) and [VO2(apftsc)], [VO2(apmtsc)], [VO2(aptsc)] e [VO2(apf)], vanadium (V), were used as catalysts for cyclohexane oxidation using 30% hydrogen peroxide (H2O2) as oxidizing agent in acetonitrile at 40ºC. The cyclohexanol (OL) and cyclohexanone (ONA) were quantified by means of gas chromatography by the internal padronization method. Variation in the molar ratio of oxidizing, substrate and nitric acid with catalyst, as well as the effect of the addition of triphenylphosphine in catalytic properties were studied for all complexes. For the complex [VO(acac)(apftsc)], yielded the kinetic parameters with rate constant (k = 3,87 x 10-1 L.mol-1.min-1), reaction order relative to catalysts (nCat = 0,8) and to substrate (nS = 0,6); the thermodynamic parameters of activation Eap = 11 kcal.mol-1, ΔG# = + 0.6 kcal.mol-1, ΔH# = + 10.2 kcal.mol-1, ΔS# = + 30.8 cal.mol-1.K-1. The EPR spectrum data using 5,5-dimethyl-1-pyrroline Noxide (DMPO) as spin trap confirm that the mechanism the formation of radicals. The radicals ( acac) and hydroxyl ( OH) from the acetylacetonate e and hydrogen peroxide, respectively, was identified by forming the respective adduct, DMPO-Acac and DMPO-OH. From the mass spectrometry data it was possible to suggest a synthetic route for the formation of the oxo(peroxo)vanadate complex, an important intermediate in the catalytic cycle. It has been proposed also a mechanism for cyclohexane oxidation.Item type:Item, Síntese e estudo das propriedades físicas de grafite ferromagnético fluido nanoestruturado(Universidade Federal de São Carlos, 2014-03-28) ;Souza, Nicolau Silva de ;Moreira, Fernando Manuel Araújo ;https://lattes.cnpq.br/1809254923092721https://lattes.cnpq.br/6301084663879270Item type:Item, Complexos de rutênio bioativos: síntese, caracterização e ensaios biológicos(Universidade Federal de São Carlos, 2014-03-28) ;Cardoso, Carolina Riverin ;Carlos, Rose Maria ;https://lattes.cnpq.br/1589143355309943https://lattes.cnpq.br/4278751614890163Ru(II) polypyridyl anticancer compounds is drawing increasing attention to drug development. The luminescence of this type of complex open wide possibilities of using molecular systems in biological applications. Herein we investigated, the synthesis, characterization and biologic studies of the complex cis-[Ru(LL) 2L2]2+ where, L-L = 2,2-bipyridine (bpy) and phen = 1,10-phenanthroline (phen) and L = imidazole (ImH) and 1-methyl-imidazole (1MeIm). The complexes which can be easily prepared are stable in solid state and in water solution (without light) and resistant to hydrolysis at pH range from 2 to 10. The complexes display strong absorption in the visible region (490 nm, ε = 15000 mol-1Lcm-1) and an intense and long lived emission at 660 nm with a large Stokes shift (5500 cm-1). Spectroscopic (CD, STD-NMR and DOSY-NMR) and ITC studies indicate binding of cis-[Ru(phen)2(ImH)2]2+ and HSA occurs via non-covalent interactions. Accordingly, the complexes showed marked cell proliferation inhibition against the cancer cells HCT116p53+/+, HCT116p53-/- and A2780 with IC50 values below 10 μmol L-1. The Complex induces G1 cell arrest in both cells although it is more expressive in P53+/+ and activates the proapoptotic protein PARP in only p53-/- suggesting diferent pathway with p53- dependent and p53-independent modes of action. The complexes presents unique features for potential diagnostic and therapeutic applications of cancer.Item type:Item, Catalisadores de Fe2O3, NiO e Fe2O3 - NiO Suportados in situ em Ce0,5Zr0,5O2 e Ce0,2Zr0,8O2 – Avaliação na Redução de NO com CO(Universidade Federal de São Carlos, 2014-03-28) ;Souza, Bruna Gonçalves de ;Urquieta-González, Ernesto Antonio ;https://lattes.cnpq.br/2389975677904655https://lattes.cnpq.br/3039069125760711The increasing use of fossil fuels in combustion enginees and power generation plants has caused a large increase in the emission of sulfur oxides, nitrogen oxides (NOx) and carbon monoxide into the atmosphere which creates serious environmental problems. Catalytic processes are used in the abatement of NOx and a promising alternative is the reduction of NOx using CO as reducing agent on catalysts containing supported transition metal oxides. Taking this into account, the aim of this study was to prepare catalysts based on Fe2O3, NiO or Fe2O3-NiO supported on ceria-zirconia (molar ratios Ce:Zr equal to 1:1 and 1:4), incorporating the metal precursor salt in the sun of the support (in situ addition). The results of XRD data, Rietveld refinement and TEM indicated the formation of a solid solution CeO2-ZrO2 with cubic structure fluorite type; furthermore, it was not observed diffraction peaks of intense X-ray of Fe or Ni oxide as a consequence of a proper distribution of these oxides in the supports. The addition of Fe2O3 and/or NiO led to a decrease of the average crystallite size, causing an increase in SBET of the catalysts compared to the pure support. N2 physisorption measurements showed that the catalysts showed significant mesoporosity, which was attributed to the addition of Tween 80 during the sol-gel preparation, moreover, RTPH2 results confirm that the Fe2O3 reduction occurs at lower temperatures in the presence NiO. In addition, the catalysts showed satisfactory performance in the reduction of NO to N2 with CO, suggesting that the sol-gel method is adequate in their preparation. Furthermore, the catalyst 0,90Fe - 1Ce:1Zr reached the highest values of CO conversion to CO2 and NO to N2 at lower temperatures. The Fe2O3 catalysts were more selective to N2 formation compared to those containing NiO. In conclusion, the conversion NO to N2 was significantly affected when in contact with O2 and H2O interferences; however, this conversion did not change significantly in the presence of SO2. The catalysts showed a more significant reduction in conversion of NO to N2 when evaluated in the simultaneous presence of O2, SO2 and H2O.Item type:Item, Determinação da força de adesão entre partícula e superfícies rugosas através da técnica centrífuga(Universidade Federal de São Carlos, 2014-03-28) ;Petean, Paula Garcia da Costa ;Aguiar, Mônica Lopes ;https://lattes.cnpq.br/0431688649128529https://lattes.cnpq.br/6642626992981985Adhesion between powders and surfaces plays an important role in various technological areas and processes, such as paste drying operations, fluidization of fine particles, microencapsulation, xerography and in food and pharmaceutical processes. Adhesion of small particles to solid surfaces is a phenomenon closely associated with industrial hygiene and air pollution studies. The centrifuge technique to determine adhesion force is based on the detachment of particles from a substrate surface due to centrifugal force. In this technique, a substrate with particles deposited on its surface is rotated at successively increasing speeds, and after each rotation at a given speed, the number of particles remaining on the surface is determined. This technique uses imaging analysis to determine the number of adhered particles on the proof disk surface before and after each centrifugation. After applying a specific press-on, images of the substrates containing particles from the pulverized materials were taken by optical microscope Olympus BX60 (Olympus Co. Tokyo Japan and processed by an image analyzer (Image-Pro Plus 7.0).The results were treated statistically to obtain the mean particle adhesive force. The powder used was a polydisperse sample of microcrystalline cellulose (ρ=1.62 kg m−3). The materials used as substrates were a membrane of cellulose ester 0.2 μm of porosity, brand Shleicher & Shuell - Filtration Life Science, and a compressed particulate (tablets) made of microcrystalline cellulose (Sigma-Aldrich). A microcentrifuge that reached a maximum rotation speed of 14000 rpm which contained specially designed centrifuge tubes was used in the adhesion force measurements. Compression speeds (presson) were applied to each of the experimental runs at 1000, 2000 and 5000 rpm. To detach the particles from the substrate surface, eight cleaning speeds (spin-off) were used. Detachment was done at the centrifugal speeds of: 1000, 3000, 5000, 7000, 9000, 11000, 13000, and 14000 rpm for 1 min. Five particle diameter sizes were studied: 9 15, 15.1 22, 22.1 30, 30.1 42, and 42.1 60 μm. It was observed that the adhesion force increases linearly with the particle diameter, within the range studied and that increased compression speed has an influence on the process of particles detaching. It was possible to obtain a relationship between the adhesion force and diameter of the particles adhered to substrates analyzed The adhesion force experimental results and the adhesion force theoretical values using the models proposed by Derjaguin, Muller and Toporov (DMT) and Johnson, Kendall and Roberts (JKR) were compared. Although the JKR Model was the closest one to the experimental results, the adhesion force theoretical values were far higher than the experimental values. Finally a correction constant (kc) was proposed in order to correlate the theoretical values of adhesion force to the experimental values.Item type:Item, Modelos mistos semiparamétricos parcialmente não lineares(Universidade Federal de São Carlos, 2014-03-28) ;Machado, Robson José Mariano ;Novelli, Cibele Maria Russo ;https://lattes.cnpq.br/1011098065426388https://lattes.cnpq.br/4313549163258792Correlated data sets with nonlinear structure are common in many areas such as biostatistics, pharmacokinetics and longitudinal studies. Nonlinear mixed-effects models are useful tools to analyse those type of problems. In this dissertation, a generalization to this models is proposed, namely by semiparametric partially nonlinear mixed-effects model (MMSPNL), with a nonparametric function to model the mean of the response variable. It assumes that the mean of the interest variable is explained by a nonlinear function, which depends on fixed effects parameters and explanatory variables, and by a nonparametric function. Such nonparametic function is quite flexible, allowing a better adequacy to the functional form that underlies the data. The random effects are included linearly to the model, which simplify the expression of the response variable distribution and enables the model to take into account the within-group correlation structure. It is assumed that the random errors and the random effects jointly follow a multivariate normal distribution. Relate to the nonparametric function, it is deal with the P-splines smoothing technique. The methodology to obtain the parameters estimates is penalized maximum likelihood method. The random effects may be obtained by using the Empirical Bayes method. The goodness of the model and identification of potencial influent observation is verified with the local influence method and a residual analysis. The pharmacokinetic data set, in which the anti-asthmatic drug theophylline was administered to 12 subjects and serum concentrations were taken at 11 time points over the 25 hours (after being administered), was re-analysed with the proposed model, exemplifying its uses and properties.