Este trabalho teve como objetivo produzir e caracterizar membranas de quitosana e de N,O-carboximetilquitosana reticuladas, que apresentassem propriedades físicas e químicas adequadas para desempenhar o papel de matriz para proliferação das células mesoteliais. As características estruturais e morfológicas das amostras purificadas de quitosana (amostra Q, adquirida da Yue Planting, China) e carboximetilquitosana na forma sódica (amostra NaCMQH, adquirida da Heppe Medical, Alemanha, e amostra NaCMQD, adquirida da Dayang Chemicals, China) foram investigadas através da espectroscopias de ressonância magnética nuclear e no infravermelho, condutimetria, solubilidade em função do pH e viscosimetria. As membranas de carboximetilquitosanas (amostras M-CMQHs e M-CMQDs) foram confeccionadas via liofilização, e glutaraldeído foi empregado como agente reticulante em diferentes concentrações para avaliar o seu efeito sobre o grau de reticulação e propriedades das membranas. As membranas foram caracterizadas quanto ao grau de reticulação, grau de hidratação, microscopia eletrônica de varredura (MEV), termogravimetria, teste mecânico de tração e quanto a susceptibilidade à degradação enzimática. A amostra Q apresentou grau médio de acetilação (<span style=\"text-decoration: overline\">GA) de 23,60%, sendo solúvel em pH &le; 6,5. A amostra NaCMQH apresentou <span style=\"text-decoration: overline\">GA = 16,32% e grau médio de substituição (<span style=\"text-decoration: overline\">GS) de 1,68, sendo insolúvel no intervalo 2,5 &le; pH &le; 6,5, a amostra de NaCMQD apresentou <span style=\"text-decoration: overline\">GA = 3,31% e <span style=\"text-decoration: overline\">GS = 1,43, sendo insolúvel no intervalo 3,0 &le; pH &le; 7,0. A reticulação das membranas de carboximetilquitosana (amostras M-CMQHs e M-CMQDs) foi realizada com a finalidade de reduzir sua solubilidade e melhorar as propriedades mecânicas. O grau médio de reticulação (<span style=\"text-decoration: overline\">GR) foi tanto maior quanto maior a concentração de glutaraldeído empregada na reação, variando de <span style=\"text-decoration: overline\">GR = 10,39 &plusmn; 0,37% ([glutaraldeído] = 2,5x10-3 mol L-1) a <span style=\"text-decoration: overline\">GR = 62,38 &plusmn; 1,71% ([glutaraldeído] = 5,0x10-3 mol L-1). As características morfológicas das amostras M-Q, M-CMQHs e M-CMQDs foram observadas pelo emprego de MEV, sendo observada a formação de estruturas porosas, com maior quantidade de poros aparentes quanto maior o <span style=\"text-decoration: overline\">GM de 175 poros mm-2 a 291 poros mm-2 com o aumento do grau de reticulação de 12,30% (amostra M-CMQH-2,5) para 35,82%, (amostra M-CMQH-50). A amostra M-Q apresentou baixa taxa de hidratação (321,16 &plusmn; 18,68%) e alto percentual de massa recuperada (90,62 &plusmn; 2,13%) após imersão por 24 horas em solução PBS, quando comparada às amostras M-CMQHs e M-CMQDs. As amostras M-CMQHs e M-CMQDs apresentaram aumento da resistência máxima à tração com o aumento de <span style=\"text-decoration: overline\"> <span style=\"text-decoration: overline\">GR, aumentando de 0,21 &plusmn; 0,16 MPa (amostra M-CMQD-2,5; <span style=\"text-decoration: overline\">GR &asymp; 10,39%) para 0,82 &plusmn; 0,33 MPa (amostra M-CMQH-50; <span style=\"text-decoration: overline\">GR &asymp; 62,38%). Entretanto, amostras com menor <span style=\"text-decoration: overline\">GR apresentaram aumento dos valores de percentual de elongação, sendo que a amostra M-CMQH-2,5 (<span style=\"text-decoration: overline\">GR &asymp; 12,30%) apresentou elongação máxima de 73,08 &plusmn; 2,20%. A amostra M-Q foi pouco susceptível à hidrólise enzimática ([GlcN] = 47x10-4 &plusmn; 1x10-4 mol L-1) devido à baixa solubilidade da quitosana em pH &gt; 6,5. Já com relação ao efeito do <span style=\"text-decoration: overline\">GR, houve redução da taxa de hidrólise enzimática de [GlcN] = 449x10-4 &plusmn; 15x10-4 mol L-1 para [GlcN] = 105x10-4 &plusmn; 11x10-4 mol L-1, quando o <span style=\"text-decoration: overline\">GR aumentou de 12,30% (amostra M-CMQH-2,5) para 28,64% (amostra M-CMQH-25). As amostras M-CMQH-5, M-CMQH-10, M-CMQD-10 e M-CMQD-25 apresentam as propriedades mais adequadas para o emprego como membranas para a prevenção das adesões pericárdicas, pois apresentam superfícies altamente porosas, com baixas taxa de hidratação e de solubilidade, resistência máxima à tração superior a 0,67 MPa, percentual de elongação superior à 30%, e degradação enzimática inferior a [GlcN] = 400x10-4 mol L-1 após 15 dias de incubação. / The aim of this study was to produce and characterize membranes of chitosan and cross-linked N,O-carboxymethylchitosan, displaying appropriate physical and chemical properties to act as matrices for the proliferation of mesothelial cells. The structural and morphological characteristics of the purified samples of chitosan (sample Q, acquired from Yue Planting, China) and sodium carboxymethylchitosan (sample NaCMQH, acquired from Heppe Medical, Germany, and sample NaCMQD, acquired from Dayang Chemicals, China) were determined by nuclear magnetic resonance spectroscopy (NMR1H), infrared spectroscopy, conductometry, viscometry and pH-solubility tests. The carboxymethylchitosan membranes (M-CMQHs and M-CMQDs) were made up by means of lyophilization, with glutaraldehyde being used as a cross-linking agent at different concentrations to evaluate its effect on the cross-linking degree and on the membranes properties. The membranes were characterized in terms of cross-linking degree and hydration rate, by scanning electronic microscopy (SEM), thermogravimetry, ultimate tensile strength and the susceptibility to enzymatic degradation. The sample Q showed average degree of acetylation (<span style=\"text-decoration: overline\">DA) of 23.60%, being soluble at pH &le; 6.5. The sample NaCMQH presented <span style=\"text-decoration: overline\">DA=16.32% and average degree of substitution (<span style=\"text-decoration: overline\">DS) of 1.68, being insoluble in the region of 2.5 &le; pH &le; 6.5. The sample NaCMQD presented <span style=\"text-decoration: overline\">DA=3.31% and <span style=\"text-decoration: overline\">DS=1.43, being insoluble in the region of 3.0 &le; pH &le; 7.0. The cross-linking of carboxymethylchitosan membranes (M-CMQHs and M-CMQDs) was carried out to reduce its solubility and to improve its the physical properties. The higher the glutaraldehyde concentration employed in the reaction, the higher average cross-linking degree (<span style=\"text-decoration: overline\">CD), which ranged from 10.39 &plusmn; 0.37% ([glutaraldehyde] = 2,5x10-3 mol L-1) to 62.38 &plusmn; 1.71% ([glutaraldehyde] = 2,5x10-3 mol L-1). The morphological characteristics of the samples M-Q, M-CMQHs M-CMQDs were observed through SEM, evidencing the formation of porous structures with a larger quantity of apparent pores as <span style=\"text-decoration: overline\">DC increased, ranging from 175 pores mm-2 to 291 pores mm-2 when <span style=\"text-decoration: overline\">DC increased from 12.30% (sample CMQH-M-2.5) to 35.82% (sample M-CMQH-50). The sample M-Q showed low hydration rate (321.16 &plusmn; 18.68%) and high percentage of recovered mass (90.62 &plusmn; 2.13%) after immersion for 24 hours, when compared to samples M-CMQHs and M-CMQDs. Increasing the <span style=\"text-decoration: overline\">DC of the samples M-CMQHs and M-CMQDs resulted in improved mechanical properties as the ultimate tensile strength increased from 0.21 &plusmn; 0.16 MPa (M-CMQD-2.5, <span style=\"text-decoration: overline\">DC &asymp; 10.39%) to 0.82 &plusmn; 0.33 MPa (M-CMQH-50, <span style=\"text-decoration: overline\">DC &asymp; 62.38%). However, those samples with lower <span style=\"text-decoration: overline\">DC values presented an increase in strain at fracture, as the CMQH-M-2.5 sample (<span style=\"text-decoration: overline\">DC &asymp; 12.30%), which registered a strain at fracture of 73.08 &plusmn; 2.20%. The sample M-Q showed a low rate of enzymatic hydrolysis ([GlcN] = 47x10-4 &plusmn; 1x10-4 mol L-1) as a consequence of the low solubility of chitosan at pH &gt; 6.5. Concerning the effects of cross-linked degree, there was a reduction in the enzymatic hydrolysis rate from [GlcN] = 449x10-4 &plusmn; 15x10-4 mol L-1 to [GlcN] = 105x10-4 &plusmn; 11x10-4 mol L-1, when <span style=\"text-decoration: overline\">DC increased from 12.30% (M-CMQH-2.5) to 28.64% (M-CMQH-25). The samples M-CMQH-5, M-CMQH-10, M-CMQD-10 and M-CMQD-25 exhibit appropriate properties to act in the prevention of pericardial adhesions, owing to its highly porous surfaces, low hydration rate and insolubility, ultimate tensile strength exceeding 0.67 MPa, strain at fracture higher than 30% and enzymatic degradation rate lower than [GlcN] = 400x10-4 mol L-1 after 15 days of incubation.

Este trabalho teve como objetivo produzir e caracterizar membranas de quitosana e de N,O-carboximetilquitosana reticuladas, que apresentassem propriedades físicas e químicas adequadas para desempenhar o papel de matriz para proliferação das células mesoteliais. As características estruturais e morfológicas das amostras purificadas de quitosana (amostra Q, adquirida da Yue Planting, China) e carboximetilquitosana na forma sódica (amostra NaCMQH, adquirida da Heppe Medical, Alemanha, e amostra NaCMQD, adquirida da Dayang Chemicals, China) foram investigadas através da espectroscopias de ressonância magnética nuclear e no infravermelho, condutimetria, solubilidade em função do pH e viscosimetria. As membranas de carboximetilquitosanas (amostras M-CMQHs e M-CMQDs) foram confeccionadas via liofilização, e glutaraldeído foi empregado como agente reticulante em diferentes concentrações para avaliar o seu efeito sobre o grau de reticulação e propriedades das membranas. As membranas foram caracterizadas quanto ao grau de reticulação, grau de hidratação, microscopia eletrônica de varredura (MEV), termogravimetria, teste mecânico de tração e quanto a susceptibilidade à degradação enzimática. A amostra Q apresentou grau médio de acetilação (<span style=\"text-decoration: overline\">GA) de 23,60%, sendo solúvel em pH &le; 6,5. A amostra NaCMQH apresentou <span style=\"text-decoration: overline\">GA = 16,32% e grau médio de substituição (<span style=\"text-decoration: overline\">GS) de 1,68, sendo insolúvel no intervalo 2,5 &le; pH &le; 6,5, a amostra de NaCMQD apresentou <span style=\"text-decoration: overline\">GA = 3,31% e <span style=\"text-decoration: overline\">GS = 1,43, sendo insolúvel no intervalo 3,0 &le; pH &le; 7,0. A reticulação das membranas de carboximetilquitosana (amostras M-CMQHs e M-CMQDs) foi realizada com a finalidade de reduzir sua solubilidade e melhorar as propriedades mecânicas. O grau médio de reticulação (<span style=\"text-decoration: overline\">GR) foi tanto maior quanto maior a concentração de glutaraldeído empregada na reação, variando de <span style=\"text-decoration: overline\">GR = 10,39 &plusmn; 0,37% ([glutaraldeído] = 2,5x10-3 mol L-1) a <span style=\"text-decoration: overline\">GR = 62,38 &plusmn; 1,71% ([glutaraldeído] = 5,0x10-3 mol L-1). As características morfológicas das amostras M-Q, M-CMQHs e M-CMQDs foram observadas pelo emprego de MEV, sendo observada a formação de estruturas porosas, com maior quantidade de poros aparentes quanto maior o <span style=\"text-decoration: overline\">GM de 175 poros mm-2 a 291 poros mm-2 com o aumento do grau de reticulação de 12,30% (amostra M-CMQH-2,5) para 35,82%, (amostra M-CMQH-50). A amostra M-Q apresentou baixa taxa de hidratação (321,16 &plusmn; 18,68%) e alto percentual de massa recuperada (90,62 &plusmn; 2,13%) após imersão por 24 horas em solução PBS, quando comparada às amostras M-CMQHs e M-CMQDs. As amostras M-CMQHs e M-CMQDs apresentaram aumento da resistência máxima à tração com o aumento de <span style=\"text-decoration: overline\"> <span style=\"text-decoration: overline\">GR, aumentando de 0,21 &plusmn; 0,16 MPa (amostra M-CMQD-2,5; <span style=\"text-decoration: overline\">GR &asymp; 10,39%) para 0,82 &plusmn; 0,33 MPa (amostra M-CMQH-50; <span style=\"text-decoration: overline\">GR &asymp; 62,38%). Entretanto, amostras com menor <span style=\"text-decoration: overline\">GR apresentaram aumento dos valores de percentual de elongação, sendo que a amostra M-CMQH-2,5 (<span style=\"text-decoration: overline\">GR &asymp; 12,30%) apresentou elongação máxima de 73,08 &plusmn; 2,20%. A amostra M-Q foi pouco susceptível à hidrólise enzimática ([GlcN] = 47x10-4 &plusmn; 1x10-4 mol L-1) devido à baixa solubilidade da quitosana em pH &gt; 6,5. Já com relação ao efeito do <span style=\"text-decoration: overline\">GR, houve redução da taxa de hidrólise enzimática de [GlcN] = 449x10-4 &plusmn; 15x10-4 mol L-1 para [GlcN] = 105x10-4 &plusmn; 11x10-4 mol L-1, quando o <span style=\"text-decoration: overline\">GR aumentou de 12,30% (amostra M-CMQH-2,5) para 28,64% (amostra M-CMQH-25). As amostras M-CMQH-5, M-CMQH-10, M-CMQD-10 e M-CMQD-25 apresentam as propriedades mais adequadas para o emprego como membranas para a prevenção das adesões pericárdicas, pois apresentam superfícies altamente porosas, com baixas taxa de hidratação e de solubilidade, resistência máxima à tração superior a 0,67 MPa, percentual de elongação superior à 30%, e degradação enzimática inferior a [GlcN] = 400x10-4 mol L-1 após 15 dias de incubação. / The aim of this study was to produce and characterize membranes of chitosan and cross-linked N,O-carboxymethylchitosan, displaying appropriate physical and chemical properties to act as matrices for the proliferation of mesothelial cells. The structural and morphological characteristics of the purified samples of chitosan (sample Q, acquired from Yue Planting, China) and sodium carboxymethylchitosan (sample NaCMQH, acquired from Heppe Medical, Germany, and sample NaCMQD, acquired from Dayang Chemicals, China) were determined by nuclear magnetic resonance spectroscopy (NMR1H), infrared spectroscopy, conductometry, viscometry and pH-solubility tests. The carboxymethylchitosan membranes (M-CMQHs and M-CMQDs) were made up by means of lyophilization, with glutaraldehyde being used as a cross-linking agent at different concentrations to evaluate its effect on the cross-linking degree and on the membranes properties. The membranes were characterized in terms of cross-linking degree and hydration rate, by scanning electronic microscopy (SEM), thermogravimetry, ultimate tensile strength and the susceptibility to enzymatic degradation. The sample Q showed average degree of acetylation (<span style=\"text-decoration: overline\">DA) of 23.60%, being soluble at pH &le; 6.5. The sample NaCMQH presented <span style=\"text-decoration: overline\">DA=16.32% and average degree of substitution (<span style=\"text-decoration: overline\">DS) of 1.68, being insoluble in the region of 2.5 &le; pH &le; 6.5. The sample NaCMQD presented <span style=\"text-decoration: overline\">DA=3.31% and <span style=\"text-decoration: overline\">DS=1.43, being insoluble in the region of 3.0 &le; pH &le; 7.0. The cross-linking of carboxymethylchitosan membranes (M-CMQHs and M-CMQDs) was carried out to reduce its solubility and to improve its the physical properties. The higher the glutaraldehyde concentration employed in the reaction, the higher average cross-linking degree (<span style=\"text-decoration: overline\">CD), which ranged from 10.39 &plusmn; 0.37% ([glutaraldehyde] = 2,5x10-3 mol L-1) to 62.38 &plusmn; 1.71% ([glutaraldehyde] = 2,5x10-3 mol L-1). The morphological characteristics of the samples M-Q, M-CMQHs M-CMQDs were observed through SEM, evidencing the formation of porous structures with a larger quantity of apparent pores as <span style=\"text-decoration: overline\">DC increased, ranging from 175 pores mm-2 to 291 pores mm-2 when <span style=\"text-decoration: overline\">DC increased from 12.30% (sample CMQH-M-2.5) to 35.82% (sample M-CMQH-50). The sample M-Q showed low hydration rate (321.16 &plusmn; 18.68%) and high percentage of recovered mass (90.62 &plusmn; 2.13%) after immersion for 24 hours, when compared to samples M-CMQHs and M-CMQDs. Increasing the <span style=\"text-decoration: overline\">DC of the samples M-CMQHs and M-CMQDs resulted in improved mechanical properties as the ultimate tensile strength increased from 0.21 &plusmn; 0.16 MPa (M-CMQD-2.5, <span style=\"text-decoration: overline\">DC &asymp; 10.39%) to 0.82 &plusmn; 0.33 MPa (M-CMQH-50, <span style=\"text-decoration: overline\">DC &asymp; 62.38%). However, those samples with lower <span style=\"text-decoration: overline\">DC values presented an increase in strain at fracture, as the CMQH-M-2.5 sample (<span style=\"text-decoration: overline\">DC &asymp; 12.30%), which registered a strain at fracture of 73.08 &plusmn; 2.20%. The sample M-Q showed a low rate of enzymatic hydrolysis ([GlcN] = 47x10-4 &plusmn; 1x10-4 mol L-1) as a consequence of the low solubility of chitosan at pH &gt; 6.5. Concerning the effects of cross-linked degree, there was a reduction in the enzymatic hydrolysis rate from [GlcN] = 449x10-4 &plusmn; 15x10-4 mol L-1 to [GlcN] = 105x10-4 &plusmn; 11x10-4 mol L-1, when <span style=\"text-decoration: overline\">DC increased from 12.30% (M-CMQH-2.5) to 28.64% (M-CMQH-25). The samples M-CMQH-5, M-CMQH-10, M-CMQD-10 and M-CMQD-25 exhibit appropriate properties to act in the prevention of pericardial adhesions, owing to its highly porous surfaces, low hydration rate and insolubility, ultimate tensile strength exceeding 0.67 MPa, strain at fracture higher than 30% and enzymatic degradation rate lower than [GlcN] = 400x10-4 mol L-1 after 15 days of incubation.

Thesis (Ph. D.)--Vanderbilt University, 1936. / Bibliography: p. [53]-57; "Appendix: Supplementary bibliography of N.O. Losskys̓ works": p. [59]-68.

Adolescents and young adults use more tobacco than all other adults, yet the percentage of this younger population eventually quitting the use of tobacco is lower. There is little evidence-based research to support adolescent smoking cessation programs. Using social learning theory (SLT) and the stages of change model, the purpose of this project was to evaluate the effectiveness of the Not-On-Tobacco (N-O-T) program, an evidence-based adolescent smoking cessation program, in reducing or preventing the number of cigarettes smoked by high school boarding students and to evaluate how best to individualize the program for this high school going forward. The DNP questions were asked to see to what extent the N-O-T program would reduce the prevalence of student smoking and what changes to the current program curriculum should be made to tailor the program to this particular high school. Pre- and post survey data were obtained from 10 students 15-17 years of age enrolled in the N-O-T program for violating the campus' tobacco-free policy. A secondary data analysis using paired samples t test did not determine a statistically significant effect on smoking cessation in this small population of students. The findings did show a significant positive correlation between those who found the program 'very helpful' and a decrease in the number of cigarettes smoked pre- and post program. Content analysis of student data resulted in recommendations to modify the program to make it more effective for this school. Awareness of interactions and relationships with others and successfully dealing with social changes through a program like the N-O-T program will lead to increased life-long health benefits, decreased medical costs, and lost productivity associated with tobacco use. School nurses are in an ideal position to implement a successful smoking cessation program.

A parte de los artículos, esta memoria consta de cinco partes más: una introducción bibliográfica, unos objetivos, un capítulo de resultados y discusión, unas conclusiones y, por último, un compendio de todas las referencias bibliográficas consultadas para la elaboración de este trabajo. El grupo de investigación al que pertenezco comenzó los estudios de ligandos derivados del pirazol a principios de los años 90. Desde entonces, no se han parado las investigaciones, dando lugar a la síntesis de nuevos ligandos pirazólicos 3,5- disubstituidos potencialmente di-, tri- y tetradentados. En un principio se ensayó la reactividad de estos ligandos con metales de la primera serie de transición [Mn(II), Fe(III), Co(II), Ni(II), Cu(II)], obteniendo una gran diversidad estructural. En los últimos años se ha ampliado el número de ligandos y el número de complejos, utilizando metales de la segunda y tercera serie de transición [Pd(II) y Pt(II)]. Siguiendo con el estudio de ligandos derivados del pirazol, se abre una nueva línea de investigación dentro del grupo, basada en la síntesis y estudio de la química de coordinación de los ligandos pirazólicos substituidos en la posición 1 por grupos amina, fosfina, fosfinito, alcohol, éter, tiol, tioéter y tioéter-alcohol. Los metáles utilizados son básicamente de la segunda y tercera serie de transición [Ru(II), Rh(I), Pd(II) y Pt(II)]. Dentro de esta línea de investigación es donde está enmarcada esta Tesis que lleva por título: "Síntesis y caracterización de compuestos de coordinación con ligandos híbridos N,O¬pirazol. Aplicaciones en Catálisis y Síntesis de Nanopartículas."

Novel bis(tetrahydroisoquinoline) N,N'-dioxides 1,2 belong to the group of compounds with axial chirality that act as a Lewis base. These properties make them useful chiral catalysts in reactions such as allylation, opening of epoxides, etc. that exhibit high enantioselectivity. The prepared chiral bis(tetrahydroisoquinoline) N,N'-dioxides (R,Rax,R)-1, (R,Sax,R)-1, (Rax,R)-2 a (Sax,R)-2 were tested as catalysts in enantioselective allylation of variously substituted α,β−unsaturated aldehydes and dienals with allyltrichlorosilane (Scheme 1). All the catalysts exhibited high catalytic activity as well as high asymmetric induction (up to 96% for α,β- unsaturated aldehydes;1 up to 98 % for dienals). Appropriate choice of solvent as a reaction medium3,4 and substitution in α-position in aldehydes were the crucial factors for the successful course of the reaction. The catalytic activity of (R,Rax,R)-1 and (R,Sax,R)-1 was also tested in asymmetric opening of meso-epoxides with tetrachlorosilane (ee up to 69 %) (Scheme 2). N N O O O O 1 N N O O O 2 Scheme 1 Scheme 2 1) Vlašaná, K.; Hrdina, R.; Valterová, I.; Kotora, M. Eur. J. Org. Chem. 2010, 7040. 2) Kadlčíková, A.; Hrdina, R.; Valterová, I.; Kotora, M. Adv. Synth. Catal. 2009, 351,1279. 3) Hrdina, R.; Opekar, F.; Roithová, J.; Kotora, M. Chem. Commun....

Dados do Instituto Nacional do C&acirc;ncer revelam 14,1 milh&otilde;es de casos novos de c&acirc;ncer em 2012 em todo o mundo, e a estimativa para 2014/2015 no Brasil aponta para mais 500 mil novos casos. Assim, pesquisas voltadas &agrave; produ&ccedil;&atilde;o de nanopart&iacute;culas e hidrog&eacute;is, constitu&iacute;dos de pol&iacute;meros naturais ou sint&eacute;ticos, s&atilde;o importantes para o desenvolvimento de sistemas destinados &agrave; libera&ccedil;&atilde;o controlada de f&aacute;rmacos antitumorais. Nesse sentido, este estudo visou produzir derivados hidrof&iacute;licos de quitosanas, N,O-metoxi(polietilenoglicol)-g-quitosana, destinados ao encapsulamento e &agrave; libera&ccedil;&atilde;o de f&aacute;rmacos antitumorais. As caracter&iacute;sticas estruturais e f&iacute;sico-qu&iacute;micas dos pol&iacute;meros foram avaliadas por FTIR, RMN 1H, solubilidade em fun&ccedil;&atilde;o do pH, viscosimetria, DRX e TGA. As quitosanas de partida, com diferentes graus m&eacute;dios de desacetila&ccedil;&atilde;o e massas molares m&eacute;dias viscosim&eacute;tricas, QD1x ( = 64,0 &plusmn; 1,1 % e = 495,6 &plusmn; 6,3.103 g mol-1), QD2x ( = 75,8 &plusmn; 0,8 % e = 346,8 &plusmn; 5,8.103 g mol-1) e QD3x ( = 92,3 &plusmn; 0,9 % e = 501,9 &plusmn; 5,9.103 g mol-1), produzidas pela aplica&ccedil;&atilde;o do processo DAIUS &agrave; &#946;-quitina, e quitosana comercial, Q ( = 94,7 &plusmn; 0,7 % e = 82,9 &plusmn; 2,0.103 g mol-1), foram avaliadas quanto aos teores de metais pesados por ICP OES e os resultados comparados aos limites permitidos pela ANVISA e Farmacopeia norte-americana. Teores significativos de metais foram detectados nas quitosanas QD1x, QD2x e QD3x (Ti e Al) e na quitosana comercial (Ni). O emprego de &#945;-metoxipoli(etilenoglicol)-&#969;-carboxi possibilitou a s&iacute;ntese dos derivados PgQD1x, PgQD2x, PgQD3x e PgQ, que apresentaram graus m&eacute;dios de substitui&ccedil;&atilde;o semelhantes ( &#8776; 40%). Os derivados foram hidrossol&uacute;veis em amplo intervalo de pH (1 &ndash; 11) e apresentaram viscosidades intr&iacute;nsecas significativamente inferiores quando comparados &agrave;s quitosanas. Foi observado que a estabilidade t&eacute;rmica e a cristalinidade das quitosanas s&atilde;o inferiores &agrave;s de beta-quitina, enquanto os derivados exibiram maior cristalinidade e s&atilde;o termicamente mais est&aacute;veis quando comparados &agrave;s quitosanas. Em geral, o aumento da raz&atilde;o molar &ndash;NH3+/TPP empregada na prepara&ccedil;&atilde;o das nano e microsuspens&otilde;es de pol&iacute;mero/TPP pelo m&eacute;todo de gelifica&ccedil;&atilde;o i&ocirc;nica resultou no aumento da densidade de cargas positivas nas superf&iacute;cies das part&iacute;culas. Entretanto, a ocorr&ecirc;ncia de numerosas cadeias de mPEG nos pol&iacute;meros N,O-mPEG-g-quitosana levou &agrave; predomin&acirc;ncia das cadeias laterais hidrof&iacute;licas nas superf&iacute;cies das part&iacute;culas, blindando as cargas positivas, favorecendo a hidrata&ccedil;&atilde;o das part&iacute;culas e o aumento dos di&acirc;metros hidrodin&acirc;micos m&eacute;dios. A influ&ecirc;ncia das viscosidades intr&iacute;nsecas dos pol&iacute;meros e das concentra&ccedil;&otilde;es polim&eacute;ricas foi avaliada atrav&eacute;s do par&acirc;metro de recobrimento (c[&#951;]). Essa avalia&ccedil;&atilde;o revelou que os di&acirc;metros hidrodin&acirc;micos m&eacute;dios das part&iacute;culas s&atilde;o diretamente afetados por c[&#951;] nos casos dos sistemas quitosana/TPP, enquanto as viscosidades intr&iacute;nsecas dos derivados N,O-mPEG-g-quitosana s&atilde;o determinantes nos sistemas N,O-mPEG-g-quitosana/TPP. O estudo do comportamento reol&oacute;gico dos hidrog&eacute;is de N,O-mPEG-g-quitosana revelou que G&rsquo; > G&rsquo;&rsquo; nos casos de PgQD3x, PgQD1x e PgQ, o que &eacute; caracter&iacute;stico de gel r&iacute;gido, enquanto que no caso de PgQD2x foi observado G&rsquo;&rsquo; > G&rsquo;, indicando a predomin&acirc;ncia do comportamento viscoso sobre o el&aacute;stico. O ponto de crossover foi observado acima de 38,2 &ordm;C, indicando a forma&ccedil;&atilde;o de hidrogel estruturado termosens&iacute;vel. Assim, pesquisas futuras poder&atilde;o investigar a influ&ecirc;ncia das caracter&iacute;sticas estruturais e f&iacute;sico-qu&iacute;micas destes carreadores polim&eacute;ricos, visando melhor efici&ecirc;ncia de incorpora&ccedil;&atilde;o e libera&ccedil;&atilde;o in vitro de f&aacute;rmacos antitumorais. / Data from National Institute of Cancer show an increase of 14.1 million new cases of cancer over the world in 2012, and the estimate for 2014/2015 in Brazil points to over 500,00 new cases. Thus, research focused on the production of nanoparticles and hydrogels, consisting by natural or synthetic polymers, are important for the development of systems for controlled release of antitumoral drugs. Therefore, this study aimed to produce systems based on hydrophilic derivative of chitosan, N,O-methoxy(polyethyleneglycol)-g-chitosan, for the encapsulation and release of antitumor drugs. The structural and physicochemical characteristics of the chitosan and the polymers were analyzed by FTIR, 1H NMR, solubility as function of pH, viscosimetry, XRD and TGA. The parent chitosan with different average degrees of deacetylation and viscosimetric average molecular weight, QD1x ( = 64,0 &plusmn; 1,1 % e = 495,6 &plusmn; 6,3.103 g mol-1), QD2x ( = 75,8 &plusmn; 0,8 % e = 346,8 &plusmn; 5,8.103 g mol-1) e QD3x ( = 92,3 &plusmn; 0,9 % e = 501,9 &plusmn; 5,9.103 g mol-1), produced applying the USAD to &#946;-chitin, and the comercial chitosan, Q ( = 94,7 &plusmn; 0,7 % e = 82,9 &plusmn; 2,0.103 g mol-1) were analyzed for heavy metal content by ICP OES and the results compared to the limits allowed by ANVISA and US Pharmacopoeial. Significant levels of metals were detected in chitosan QD1x, QD2x and QD3x (Ti and Al) and commercial chitosan (Ni). The use of &#945;-methoxypoly(ethyleneglycol)-&#969;-carboxy enabled the synthesis of derivatives PgQD1x, PgQD2x, PgQD3x and PgQ, which had similar average degree of substitution ( &#8776; 40%). The derivatives were soluble in a broad pH range (1-11) and presented significantly lower intrinsic viscosities as compared to chitosan. It was observed that the thermal stability and crystallinity of chitosan are inferior to &#946;-chitin, while the derivatives exhibit higher crystallinity and are more thermally stable as compared to chitosan. In general, increasing molar ratio of &ndash;NH3+/TPP in the preparation of nano- and microsuspensions of polymer/TPP by ionic gelation method, resulted in an increased positive charge density on the surfaces of the particles. However, the occurrence of a great number of chains of mPEG along the N,O-mPEG-g-chitosan chains led to the predominance of hydrophilic side chains on the surfaces of the particles, shielding the positive charges, favoring the hydration of the particles and the increasing the average hydrodynamic diameter. The influence of the intrinsic viscosities of the polymers and polymer concentrations were evaluated by the overlapping parameter (c[&#951;]). This assessment revealed that the average hydrodynamic diameter of the particles are directly affected by c[&#951;] in the case of chitosan/TPP systems, while the intrinsic viscosities of the derivates N,O-mPEG-g-chitosan are essential for N,O-mPEG-g-chitosan/TPP systems. The study of the rheological behavior of the hydrogels of N,O-mPEG-g-chitosan revealed that G&rsquo; > G&rsquo;&rsquo; in the case of PgQD3x, PgQD1x and PGQ which is characteristic of structured gel, whereas in the case of PgQD2x it was observed G&rsquo;&rsquo; > G&rsquo; indicating the predominance of the viscous behavior over the elastic. The crossover point was observed above 38.2 &deg;C, indicating the formation of structured thermosensitive hydrogel. Thus, future research will investigate the influence of structural and physicochemical characteristics of polymeric carriers, aiming a better incorporation and release in vitro efficiency of antitumor drugs.

Dados do Instituto Nacional do C&acirc;ncer revelam 14,1 milh&otilde;es de casos novos de c&acirc;ncer em 2012 em todo o mundo, e a estimativa para 2014/2015 no Brasil aponta para mais 500 mil novos casos. Assim, pesquisas voltadas &agrave; produ&ccedil;&atilde;o de nanopart&iacute;culas e hidrog&eacute;is, constitu&iacute;dos de pol&iacute;meros naturais ou sint&eacute;ticos, s&atilde;o importantes para o desenvolvimento de sistemas destinados &agrave; libera&ccedil;&atilde;o controlada de f&aacute;rmacos antitumorais. Nesse sentido, este estudo visou produzir derivados hidrof&iacute;licos de quitosanas, N,O-metoxi(polietilenoglicol)-g-quitosana, destinados ao encapsulamento e &agrave; libera&ccedil;&atilde;o de f&aacute;rmacos antitumorais. As caracter&iacute;sticas estruturais e f&iacute;sico-qu&iacute;micas dos pol&iacute;meros foram avaliadas por FTIR, RMN 1H, solubilidade em fun&ccedil;&atilde;o do pH, viscosimetria, DRX e TGA. As quitosanas de partida, com diferentes graus m&eacute;dios de desacetila&ccedil;&atilde;o e massas molares m&eacute;dias viscosim&eacute;tricas, QD1x ( = 64,0 &plusmn; 1,1 % e = 495,6 &plusmn; 6,3.103 g mol-1), QD2x ( = 75,8 &plusmn; 0,8 % e = 346,8 &plusmn; 5,8.103 g mol-1) e QD3x ( = 92,3 &plusmn; 0,9 % e = 501,9 &plusmn; 5,9.103 g mol-1), produzidas pela aplica&ccedil;&atilde;o do processo DAIUS &agrave; &#946;-quitina, e quitosana comercial, Q ( = 94,7 &plusmn; 0,7 % e = 82,9 &plusmn; 2,0.103 g mol-1), foram avaliadas quanto aos teores de metais pesados por ICP OES e os resultados comparados aos limites permitidos pela ANVISA e Farmacopeia norte-americana. Teores significativos de metais foram detectados nas quitosanas QD1x, QD2x e QD3x (Ti e Al) e na quitosana comercial (Ni). O emprego de &#945;-metoxipoli(etilenoglicol)-&#969;-carboxi possibilitou a s&iacute;ntese dos derivados PgQD1x, PgQD2x, PgQD3x e PgQ, que apresentaram graus m&eacute;dios de substitui&ccedil;&atilde;o semelhantes ( &#8776; 40%). Os derivados foram hidrossol&uacute;veis em amplo intervalo de pH (1 &ndash; 11) e apresentaram viscosidades intr&iacute;nsecas significativamente inferiores quando comparados &agrave;s quitosanas. Foi observado que a estabilidade t&eacute;rmica e a cristalinidade das quitosanas s&atilde;o inferiores &agrave;s de beta-quitina, enquanto os derivados exibiram maior cristalinidade e s&atilde;o termicamente mais est&aacute;veis quando comparados &agrave;s quitosanas. Em geral, o aumento da raz&atilde;o molar &ndash;NH3+/TPP empregada na prepara&ccedil;&atilde;o das nano e microsuspens&otilde;es de pol&iacute;mero/TPP pelo m&eacute;todo de gelifica&ccedil;&atilde;o i&ocirc;nica resultou no aumento da densidade de cargas positivas nas superf&iacute;cies das part&iacute;culas. Entretanto, a ocorr&ecirc;ncia de numerosas cadeias de mPEG nos pol&iacute;meros N,O-mPEG-g-quitosana levou &agrave; predomin&acirc;ncia das cadeias laterais hidrof&iacute;licas nas superf&iacute;cies das part&iacute;culas, blindando as cargas positivas, favorecendo a hidrata&ccedil;&atilde;o das part&iacute;culas e o aumento dos di&acirc;metros hidrodin&acirc;micos m&eacute;dios. A influ&ecirc;ncia das viscosidades intr&iacute;nsecas dos pol&iacute;meros e das concentra&ccedil;&otilde;es polim&eacute;ricas foi avaliada atrav&eacute;s do par&acirc;metro de recobrimento (c[&#951;]). Essa avalia&ccedil;&atilde;o revelou que os di&acirc;metros hidrodin&acirc;micos m&eacute;dios das part&iacute;culas s&atilde;o diretamente afetados por c[&#951;] nos casos dos sistemas quitosana/TPP, enquanto as viscosidades intr&iacute;nsecas dos derivados N,O-mPEG-g-quitosana s&atilde;o determinantes nos sistemas N,O-mPEG-g-quitosana/TPP. O estudo do comportamento reol&oacute;gico dos hidrog&eacute;is de N,O-mPEG-g-quitosana revelou que G&rsquo; > G&rsquo;&rsquo; nos casos de PgQD3x, PgQD1x e PgQ, o que &eacute; caracter&iacute;stico de gel r&iacute;gido, enquanto que no caso de PgQD2x foi observado G&rsquo;&rsquo; > G&rsquo;, indicando a predomin&acirc;ncia do comportamento viscoso sobre o el&aacute;stico. O ponto de crossover foi observado acima de 38,2 &ordm;C, indicando a forma&ccedil;&atilde;o de hidrogel estruturado termosens&iacute;vel. Assim, pesquisas futuras poder&atilde;o investigar a influ&ecirc;ncia das caracter&iacute;sticas estruturais e f&iacute;sico-qu&iacute;micas destes carreadores polim&eacute;ricos, visando melhor efici&ecirc;ncia de incorpora&ccedil;&atilde;o e libera&ccedil;&atilde;o in vitro de f&aacute;rmacos antitumorais. / Data from National Institute of Cancer show an increase of 14.1 million new cases of cancer over the world in 2012, and the estimate for 2014/2015 in Brazil points to over 500,00 new cases. Thus, research focused on the production of nanoparticles and hydrogels, consisting by natural or synthetic polymers, are important for the development of systems for controlled release of antitumoral drugs. Therefore, this study aimed to produce systems based on hydrophilic derivative of chitosan, N,O-methoxy(polyethyleneglycol)-g-chitosan, for the encapsulation and release of antitumor drugs. The structural and physicochemical characteristics of the chitosan and the polymers were analyzed by FTIR, 1H NMR, solubility as function of pH, viscosimetry, XRD and TGA. The parent chitosan with different average degrees of deacetylation and viscosimetric average molecular weight, QD1x ( = 64,0 &plusmn; 1,1 % e = 495,6 &plusmn; 6,3.103 g mol-1), QD2x ( = 75,8 &plusmn; 0,8 % e = 346,8 &plusmn; 5,8.103 g mol-1) e QD3x ( = 92,3 &plusmn; 0,9 % e = 501,9 &plusmn; 5,9.103 g mol-1), produced applying the USAD to &#946;-chitin, and the comercial chitosan, Q ( = 94,7 &plusmn; 0,7 % e = 82,9 &plusmn; 2,0.103 g mol-1) were analyzed for heavy metal content by ICP OES and the results compared to the limits allowed by ANVISA and US Pharmacopoeial. Significant levels of metals were detected in chitosan QD1x, QD2x and QD3x (Ti and Al) and commercial chitosan (Ni). The use of &#945;-methoxypoly(ethyleneglycol)-&#969;-carboxy enabled the synthesis of derivatives PgQD1x, PgQD2x, PgQD3x and PgQ, which had similar average degree of substitution ( &#8776; 40%). The derivatives were soluble in a broad pH range (1-11) and presented significantly lower intrinsic viscosities as compared to chitosan. It was observed that the thermal stability and crystallinity of chitosan are inferior to &#946;-chitin, while the derivatives exhibit higher crystallinity and are more thermally stable as compared to chitosan. In general, increasing molar ratio of &ndash;NH3+/TPP in the preparation of nano- and microsuspensions of polymer/TPP by ionic gelation method, resulted in an increased positive charge density on the surfaces of the particles. However, the occurrence of a great number of chains of mPEG along the N,O-mPEG-g-chitosan chains led to the predominance of hydrophilic side chains on the surfaces of the particles, shielding the positive charges, favoring the hydration of the particles and the increasing the average hydrodynamic diameter. The influence of the intrinsic viscosities of the polymers and polymer concentrations were evaluated by the overlapping parameter (c[&#951;]). This assessment revealed that the average hydrodynamic diameter of the particles are directly affected by c[&#951;] in the case of chitosan/TPP systems, while the intrinsic viscosities of the derivates N,O-mPEG-g-chitosan are essential for N,O-mPEG-g-chitosan/TPP systems. The study of the rheological behavior of the hydrogels of N,O-mPEG-g-chitosan revealed that G&rsquo; > G&rsquo;&rsquo; in the case of PgQD3x, PgQD1x and PGQ which is characteristic of structured gel, whereas in the case of PgQD2x it was observed G&rsquo;&rsquo; > G&rsquo; indicating the predominance of the viscous behavior over the elastic. The crossover point was observed above 38.2 &deg;C, indicating the formation of structured thermosensitive hydrogel. Thus, future research will investigate the influence of structural and physicochemical characteristics of polymeric carriers, aiming a better incorporation and release in vitro efficiency of antitumor drugs.

Made available in DSpace on 2015-04-14T13:56:32Z (GMT). No. of bitstreams: 1 462536.pdf: 1936978 bytes, checksum: 551a99d3e7495bc45e9ce1dea5d91aea (MD5) Previous issue date: 2014-08-20 / With the popularization of the use of Unmanned Aerial Vehicles (UAV s) grows the need to use more sophisticated, robust and effective controllers in order to enhance its flight performance. This work aims the development of a non-linear control to be applied on a quadrotor aircraft, reducing flight time and improving system stability. The most commonly control technique used consist of a linear control law known as Proportional Integrate Derivative (PID), which provides stability and displacement for this class of system. However, this technique has certain limitations in performance by not considering construction parameters such as actuator s saturation and inertial moments, associated with the mass distribution of the system. Given this scenario, it is proposed the implementation of a control law, based on a formulation of optimal response time named Proximate Time Optimal Servomechanism (PTOS) to be applied on the degrees of freedom for rotation and translation of the vehicle. Furthermore, it is proposed a new approach to operate on a bidirectional displacement of a geo-referenced trajectory control system, based on the concept of optimal time, such as PTOS. Firstly it is presented the system dynamics, then a linearization, for purpose of control design, is achieved so that the proposed controllers are developed. / Com a populariza??o do uso de Ve?culos A?reos N?o Tripulados (VANT s) cresce a necessidade do uso de controladores mais sofisticados, mais robustos e mais eficazes, de forma a aprimorar sua performance de voo. Este trabalho tem como objetivo a implementa??o de uma t?cnica de controle n?o linear para ser aplicada em VANT s do tipo quadc?ptero, reduzindo o tempo de voo e aprimorando a estabilidade do sistema. A t?cnica de controle comumente usada consiste em uma lei de controle linear conhecida como PID (Proporcional Integrador Derivador) que, embora proporcione estabilidade e deslocamento para essa classe de sistema, esta t?cnica apresenta certas limita??es de desempenho e performance por n?o considerar par?metros construtivos, tais como a satura??o do pr?prio atuador e momentos inerciais associados ? distribui??o de massa no sistema. Neste cen?rio, ? proposto a implementa??o de uma lei de controle, baseada em uma formula??o de tempo de resposta quase ?timo denominada Proximate Time Optimal Servomechanism (PTOS), a ser aplicada nos graus de liberdade relativos a rota??o e transla??o do ve?culo. N?o obstante, ? proposta uma t?cnica de controle bidirecional para atuar no controle da trajet?ria georreferenciada do sistema, alicer?ada no conceito de tempo ?timo, tal como PTOS. Como metodologia, primeiramente ? apresentado o modelo da din?mica do sistema, tal como uma representa??o linear para fins de projeto de controle, para que ent?o sejam desenvolvidos os controladores propostos. O desenvolvimento ? validado offline, via simula??es dos algor?timos.

Made available in DSpace on 2016-04-04T18:33:02Z (GMT). No. of bitstreams: 1 Juliana Daros Carneiro.pdf: 952616 bytes, checksum: eaf6399e6fbadcf49a1027d178dccfbd (MD5) Previous issue date: 2011-02-18 / This is a study of a partnership between the Municipal Secretariat of Citizenship, Welfare and Social Inclusion (SMCAIS), a nongovernmental organization (NGO) and a public school in a town in the state of S?o Paulo (SP) . This partnership is developed through socio-educational activities for children and male adolescents, aged between 6 and 14 years, against the school schedule. The overall objective is to identify as non-formal education has been conceived and proposed within this partnership. Specifically, it aims to examine what they are and who should receive these socio-educational; discuss the presence of instruments and valuation models, both of public policy interest in the field of non-formal education and, finally, to identify the ( s) form (s) of existence of dialogue between the various bodies that compose this public assistance policy. The research methodology consists of: (i) review of key concepts such as non-formal education, evaluation, non-governmental organization, public and social policies, (ii) research on documentary material relating to the partnership, especially SMCAIS and NGOs (Resolution No. 01/2009 municipal, annual management reports, news articles, bylaws, work plans for 2009 and 2010 annual technical report of 2009 activities, organization chart) and (iii) semi-structured interviews with one representative from each of the institutions that make up this partnership (the educational coordinator of the NGO, a psychologist at the City Office and vice director of the school). We used a qualitative approach and the empirical material has been reviewed and organized according to categories constructed along the analytical process. As final results, we found that the non-formal education in our case, seems to be designed in ways contradictory, since while he assumed the defense speech of social transformation, in practice this character is not evident. These contradictions were analyzed in so-called socio-educational activities, forms of dialogue established between the institutions and instruments of evaluation. With regard to assessment procedures used were able to identify weaknesses and limitations, when it is adopted as reference the concept of formative evaluation: the tools are focused on the bureaucratic, technical, financial and quantitative development of the project, and are is centralized by a single institution, the SMCAIS. We believe that this research will bring significant contributions to advancing the discussions on educational concepts present in the forms of partnership between state public sector and private sector, from a broad view of education. / Trata-se de um estudo sobre uma parceria entre a Secretaria Municipal de Cidadania, Assist?ncia e Inclus?o Social (SMCAIS), uma organiza??o n?o-governamental (ONG) e uma escola p?blica estadual de uma cidade do interior do estado de S?o Paulo (SP). Esta parceria ? desenvolvida por meio de a??es s?cio-educativas destinadas a crian?as e adolescentes do sexo masculino, com idade entre 6 e 14 anos, no contra turno escolar. O objetivo geral da pesquisa ? identificar como a educa??o n?o-formal vem sendo concebida e proposta dentro desta parceria. Especificamente, pretendemos verificar o que s?o e a quem se destinam estas a??es s?cio-educativas; problematizar a presen?a de instrumentos e modelos de avalia??o, tanto da pol?tica p?blica como das a??es no campo da educa??o n?o-formal; e, por fim, identificar a(s) forma(s) de exist?ncia de di?logo entre as diferentes inst?ncias que comp?em essa pol?tica p?blica assistencial. A metodologia de pesquisa ? composta por: (i) a revis?o bibliogr?fica dos conceitos chaves, tais como educa??o n?o-formal, avalia??o, organiza??o n?o-governamental, pol?ticas p?blicas e sociais; (ii) pesquisa documental sobre materiais referentes ? parceria, especialmente da SMCAIS e da ONG (resolu??o municipal n?01/2009, relat?rios anuais de gest?o, reportagens, estatuto social, Planos de trabalho de 2009 e 2010, relat?rio t?cnico anual de atividades de 2009, organograma da entidade) e (iii) entrevistas semiestruturadas com um representante de cada uma das institui??es que comp?em esta parceria (a coordenadora pedag?gica da ONG, a psic?loga da secretaria municipal e o vice-diretor da escola). Utilizamos uma abordagem qualitativa e o material emp?rico foi examinado e organizado de acordo com categorias constru?das ao longo do processo anal?tico. Como resultados finais, identificamos que a educa??o n?o-formal no caso em estudo, parece ser concebida de formas contradit?rias, uma vez que ao mesmo tempo em que assume o discurso de defesa da transforma??o social, na pr?tica este car?ter n?o ? evidenciado. Estas contradi??es foram analisadas nas chamadas a??es s?cioeducativas, nas formas de di?logo estabelecidas entre as institui??es e nos instrumentos de avalia??o. No que se refere aos procedimentos de avalia??o utilizados foi poss?vel identificar fragilidades e limita??es, quando adota-se como refer?ncia o conceito de avalia??o formativa: os instrumentos est?o focalizados em aspectos burocr?ticos, t?cnicos, financeiros e quantitativos do desenvolvimento do projeto; e, encontram-se centralizados por uma ?nica institui??o, a SMCAIS. Consideramos que a presente pesquisa trar? contribui??es importantes para fazer avan?ar as reflex?es sobre concep??es educacionais presentes nas formas de parceria entre setor p?blico estatal e setor privado, a partir de uma vis?o ampla de educa??o.