The thesis entitled "SYNTHETIC INVESTIGATIONS IN TERPENOIDS AND STEROIDS" consists of 3 Chapters Chapter-I deals with the synthetic studies on the hexacyclic nortriterpene Pfaffic acid 1, and is divided into two sections. Section-I begins with a brief introduction to Pfaffic acid 1, a naturally occurring hexacyclic nortriterpene, in particular to its isolation, structural elucidation and antitumor activity. The antitumor activities of the Pfafosides A, B, C, D, E and F, the glycosides of pfaffic acid 1, isolated from the same plant is also described. The discussion presents the synthetic strategy developed to construct the AB ring system along with the results of the attempted synthesis of DEF ring of Pfaffic acid 1. The retrosynthetic analysis of 1 identified the key intermediates as AB synthon 2, and the DEF synthon 3, Regioselective hydride reduction of Wieland-Mischer ketone, followed by hydroxyl protection and Woodward methylation gave the dimethylated compound 4 Deprotection of the hydroxyl group and reduction of the carbonyl followed by acetylation resulted in the diacetate 5 Oxidation of the diacetate 5 with PDC-/BuOOH-celite system followed by lithium-liquid ammonia reduction yielded the saturated keto diol 6, which on dehydration and subsequent acetylation afforded the enone acetate 2, which formed the AB ring of Pfaffic acid 1 The synthetic studies towards the construction of DEF rings of Pfaffic acid commenced with the preparation of the indane methanol 7 The alcohol 7 was synthesized starting from 5-methoxyindan-l-one Thus 5-methoxyindanone was converted into the hydroxymethyl compound 8 by Wittig reaction and subsequent hydroboration Swern oxidation of 7, followed by methylation and reduction resulted in the indane methanol 7 Lithium-ammonia reduction of 7 gave a dihydrocompound, which on hydrolysis with oxalic acid gave the isomeric enones 9 and 10 in 1 1 ratio On the other hand, hydrolysis of the dihydrocompound with 5N HC1 in methanol afforded the isomers 9 and 10 in 85 15 ratio Addition of KCN to the isomeric enone mixture (85 15) resulted in the lactone 11 in 60% yield.The formation of the lactone 11 clearly established that the major isomer of the mixture has the angular hydrogen and hydroxymethyl group in as orientation as represented in 9, but unfortunately this geometry is unfavorable for the construction of the DEF ring of Pfaffic acid Similar Birch reduction of the alcohol 8 gave the corresponding dihydrocompound, which on hydrolysis with 5N HC1 in methanol afforded the isomeric alcohols 12 and 13 in 92 8 ratio Hydrogenation of the mixture followed by tosylation yielded the tosylates 14 and 15 in the same ratio Attempted intramolecular cyclisation of the tosylate mixture with different bases failed to yield any tricyclic compound, indicating that the major isomer has the unfavorable geometry for intramolecular alkylation. The origin of stereoselectivity during the hydrolysis of the enol-ether leading to the formation of the isomers 9 and 12 in major amount, was found to be due to a novel hydroxyl directed protonataon as represented in 16 Section-ll describes a novel oxidative C-C bond cleavage reaction with chromium reagents The alcohol 8 when oxidized with a variety of chromium reagents gave 5-methoxyindan-1-one in good yields. The mechanism of this reaction seems to go via the enol 17, which undergoes C-C bond cleavage to afford 5-methoxyindan-l-one. A number of 1-hydroxymethyl indanes 18 and 1-hydroxymethyl tetralins 19 were synthesized and their oxidation with PCC and PDC was examined In all these cases a smooth C-C cleavage was observed resulting in the respective aryl ketones Chapter-II deals with the synthetic investigations on the construction of the tricyclic ACE synthon 20, a potential intermediate for the synthesis of A-ring aromatic steroids, and is divided into two sections. Section-] describes the literature pertaining to the synthetic approaches towards A-ring aromatic steroids, with the emphasis being a critical analysis of the methodologies developed for estrone. Section-ll is divided into two parts Part-I presents the results of the synthetic studies on the construction of the tricyclic ACE synthon 20 The section starts with a need to develop a convenient methodology for the synthesis of aryltetralin 21 The new process developed for the synthesis of 21 involved a one pot Friedel-Crafts arylation of the 7-methoxy-l-tetralol 22 with the phenol to afford the aryltetralin 21 in high yield This methodology was extended to the synthesis of a number of aryl tetralins 22 to show the generality of this reaction Benzylic oxidation of the acetate of 21, afforded the aryl ketone, which on hydrolysis followed by benzylation with yielded the tetralone 24 Wittig olefination of the tetralone 24, followed by hydroboration afforded the hydroxymethyl compound 25 Swern oxidation of the hydroxymethyl compound 25 and subsequent methylation and sodium borohydride reduction gave the aryltetralin 26 along with its isomer 27 Both these isomers were separated by column chromatography over silica gel and subjected to hydrogenation to afford isomeric diols 28 and 29 Birch reduction of 28 afforded the dihydrocompound, which on acid hydrolysis resulted in a mixture of compounds consisting of 30, 31, 32, and 33 The diastereomeric isomers 30 and 31 were separated together from the other set of diastereomeric isomers 32 and 33 by column chromatography over silicagel, but the individual diastereomers could not be separated On the other hand hydrolysis of the dihydrocompound for a longer period (24 h) yielded the compound 32 as a single isomer along with the mixture 30 and 31 Part-II describes a new synthetic methodology for the construction of bicyclo[3 2 2]nonanes, During the preparation of the aryltetralin derivative 28, a hitherto unknown double Friedel-Crafts reaction, leading to the formation of bicyclo[3.2 2]nonane derivative was observed The diol 35 on treatment with phenol and A1C1, unexpectedly underwent a novel double Friedel-Crafts reaction to afford the bicyclo[3 2 2]nonane derivative 36 The mechanism of this reaction was found to go via the aryl tetralin 28 and the generality of this reaction was demonstrated by the synthesis of different aryltetralin derivatives 37, by reacting the diol with various arylating agents Chapter-III deals with the direct conversion of 130-alkylgona tetraenes into 19-nortestosterone derivatives Birch reduction of 8-dehydroestradiol-3-methyl ether 38 and 9(11)-dehydroestradiol-3-methyl ether 39 followed by acid hydrolysis results in a mixture of 19-nortestosterone 40 and retro-19- nortestosterone 41 in varying amounts However, reduction of the acetates of 38 and 39 with sodium or lithium, in the presence of aniline affords exclusively 19-nortestosterone 40 Similarly the acetate of 42 was converted to 18-homo-19-nortestosterone 43

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work describes the synthesis of 4,5-dihydropirazoles through a sonochemical methodology, from the reaction of cyclocondensation of 1,3-diaryl-2-propen-1-ones with aminoguanidine hydrochloride and thiosemicarbazide. These reactions were carried out in ethanol in periods of reduced time concerning to the methods described in the literature. Then, it presents the use of methyl 7,7,7-trichloro-4-methoxy-6-oxo-4-heptenoate for the preparation of a series of ten 1-alkyl(aryl)-5-(3,3,3-trichloro-2-oxopropylidene)pyrrolidin-2-ones, like at a Paal-Knorr synthesis. This transformation can occur with or without isolation of intermediates methyl 4-alkyl(aryl)amino-7,7,7-trichloro-6-oxo-4-heptenoates without significant change in the yields. Subsequently, it was studied the synthetic potential of the previously synthesized pyrrolidin-2-ones front to bromination for getting eight new 1-alkyl(aryl)- 4-bromo-5-(3,3,3-trihalo-2-oxopropylidene)pyrrolidin-2-ones. Bromination occurred in a regiospecific way at 4-position with good yields. Finally, 1-alkyl(aryl)-5-(3,3,3- trihalo-2-oxopropylidene)-1H-pyrrol-2(5H)-ones were obtained from the elimination of the HBr, in alkaline medium, of the brominated pyrrolidin-2-ones. / Este trabalho descreve a síntese de 4,5-diidropirazóis via metodologia sonoquímica a partir da reação de ciclocondensação de 1,3-diaril-2-propen-1-onas com cloridrato de aminoguanidina e tiosemicarbazida. Estas reações foram realizadas em etanol em períodos de tempo reduzidos em relação aos métodos descritos na literatura. Em seguida, apresenta a utilização do 7,7,7-tricloro-4-metoxi-6-oxo-4-heptenoato de metila na síntese de uma série de dez 1-alquil(aril)-5-(3,3,3-trialo-2-oxopropilideno)pirrolidin-2-onas, semelhante a síntese de Paal-Knorr. Esta transformação pode ocorrer com ou sem o isolamento dos intermediários 7,7,7- tricloro-4-amino-6-oxo-4-heptenoatos de metila sem mudança significativa nos rendimentos. Posteriormente, foi verificado o potencial sintético das pirrolindin-2-onas triclorometilsubstituídas e trifluormetilsubstituídas previamente sintetizadas frente a reações de bromação, para a obtenção de oito 1-alquil(aril)-4-bromo-5-(3,3,3-trialo-2-oxopropilideno)pirrolidin-2-onas. Esta reação ocorreu de maneira regioespecífica e com bons rendimentos. Finalmente, foram preparadas oito 1-alquil(aril)-5-(3,3,3-trialo-2-oxopropilideno)-1H-pirrol-2(5H)-onas a partir da eliminação de HBr das pirrolidin-2-onas bromadas.

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Este estudo propõe uma ligação decisiva entre o capitalismo e os assim chamados direitos humanos e sociais. O objetivo é provar que o desenvolvimento histórico dos direitos humanos, considerando sua primeira dimensão e sua segunda dimensão, não é baseado no desenvolvimento do espírito humano e da consciência universal, mas sim no processo capitalista de produção e reprodução social. Ao se seguir um caminho teórico marxista, é possível perceber que toda a forma jurídica, até mesmo os direitos humanos, está profundamente comprometida com uma estrutura capitalista de sociedade. Em adendo, este fato implica consequências importantes para todos os programas políticos e perspectivas reformistas. Os direitos civis e políticos, tanto quanto os direitos sociais, são parte de um maquinário burguês que faz do direito um instrumento de exploração e preservação do status quo, apesar do progresso relativo que eles podem trazer com eles. O Estado de Direito é apenas uma maneira particular pela qual o Estado burguês, em tempos de normalidade, emprega sua violência. E as políticas de bem-estar social não são nada além de uma intervenção estatal para apoiar o ciclo de acumulação do capital conforme necessidades concretas (e políticas). Não há nenhum tipo de esclarecimento, bondade ou senso de decência humana nos direitos relacionados à democracia liberal e às instituições de bem-estar social, mas sim contingências de determinados momentos da luta de classes e da dinâmica econômica de reprodução sob o sistema capitalista. A verdadeira emancipação só é viável pelo fim das classes sociais, um difícil horizonte que começa com uma estratégia socialista. E quanto mais a revolução socialista modifica as relações de produção para estabelecer o controle social pela classe trabalhadora, tanto menor é a hegemonia da forma jurídica sobre a vida, porque o direito perece junto com o fim da produção e da circulação de mercadorias. A luta pelo socialismo como a luta por um novo e superior tipo de vida civilizada que nenhum dos direitos humanos poderia prover à humanidade. / This study proposes a critical link between capitalism and the so-called human and social rights. The objective is to prove that the historical development of human rights, considering their first dimension and their second dimension, is not based on the development of the human spirit or of a universal consciousness, but on capitalist process of social production and reproduction. By following a marxist theoretical path, it is possible to realize that all juridical form, even human rights, is deeply compromised with a capitalist structure of society. In addition, this fact implicates important consequences for all reformist political programs and perspectives. Civil and political rights, as much as social rights, are part of a bourgeois machinery which turn law into an instrument of exploitation and preservation of status quo, despite the relative progress they may bring with themselves. The rule of Law is only a particular manner by which bourgeois state, in times of normality, employs its violence. And the policies of welfare are nothing but a state intervention to support the cycle of accumulation of capital according concrete (and political) necessities. There is not any sort of enlightenment, kindness or sense of human decency in the rights related to liberal democracy and the institutions of welfare state, but only contingences from a determined moment of struggle of class and economical dynamics of reproduction under capitalist system. A true emancipation is only viable by the end of social classes, a difficult horizon that begins with a socialist strategy. And the more a socialist revolution changes the relations of production in order to establish a social control by working class, the lesser is the hegemony of the juridical form over life, because law perishes tied to the end of production and circulation of commodities. The struggle for socialism reveals itself as a struggle for a new and superior kind of civilized life which none of the human rights could provide to mankind.

1) MOTIVOS Y JUSTIFICACIONESDos han sido los motivos que nos han impulsado a rea1izar la presente tesis; por una parte la evidencia de la enfermedad litiásica que abarca la tercera parte de los enfermos urológicos, siendo el 94% de ellos subsidiarios de tratamiento de litotricia extracorpórea por ondas de choque, ya sea como monoterapia o como tratamiento combinado. El segundo motivo es la laguna de conocimientos que existe en la literatura respecto de los efectos adversos de las ondas de choque y especialmente en lo concerniente a los modelos piezoeléctrico y electromagnético.2) FUNDAMENTOS TÉCNICOSEn este capitulo se realiza un estudio de los aspectos técnicos de los distintos litotriptores especialmente en los aspectos que puedan incidir en la Clínica Humana. Se realiza asimismo un estudio comparativo de los tres modelos: electrohidráulico, piezoeléctrico y electromagnético.3) FUNDAMENTOS BIOLÓGICOSSe revisan los conocimientos actuales acerca de la interacción de las ondas de choque con los tejidos vivos. Se revisan las series clínicas publicadas y los trabajos experimentales realizados, cuyas conc1usiones son:1. Los litotriptores electrohidráulicos resultan más lesivos que los piezoeléctricos y los electromagnéticos.2. Las lesiones son, por lo general, dosis dependientes.3. Un mismo número de ondas de choque resulta más lesivo ap1icado en un solo tratamiento que repetido en varios.4. Resulta más lesivo aumentar el kilovoltaje que el número total de ondas aplicadas.5. El tamaño de 1as lesiones observadas es por lo general pequeño.6. Las lesiones pueden conllevar riesgo de hipertensión arterial.7. Resultan especialmente vulnerables los órganos conteniendo gas: pulmón e intestino.8. El tipo de 1esión observado por los distintos autores es similar y sólo se apuntan diferencias cuantitativas: fenómenos hemorrágicos y de necrosis, infiltrados ce1ulares (po1imorfonucleares y mononucleares), destrucción glomerular y tubular, lesiones vasculares y curación por cicactrización fibrosa.4) OBJETIVOS1. Diseñar un modelo que permita reproducir los tratamientos realizados en el humano sobre un animal de experimentación.2. Describir 1as lesiones que puedan aparecer en el riñón y órganos adyacentes, desde un punto de vista macroscópico, microscópico y ultraestructural.3. Estudiar, en su caso, la evolutividad de las lesiones.4. Determinar y cuantificar, mediante estudios biológicos en sangre y orina, las posibles alteraciones de la hemostasis producida por afectación renal, de órganos vecinos u otros.5. Efectuar un estudio comparativo entre los efectos producidos por las ondas de choque piezoeléctricas y las que utilizan otras fuentes de energía (electrohidráulicas o electromagnéticas).5) MATERIAL Y MÉTODOSNuestro modelo experimental está formado por 41 conejos distribuidos en grupos: un grupo general integrado por 30 conejos birrenos subdividido en grupos de cinco animales sacrificados respectivamente a las 2 horas, 24 h., 14 días, 21 d. y 31 d. después del tratamiento con O. de C; un segundo grupo formado por 5 conejos a los que previamente se había extirpado el riñón derecho y un tercer grupo formado por 6 conejos que constituye el grupo control.Todos los conejos han sido bombardeados con 5.000 ondas de choque piezoeléctricas en un litotriptor "Piezolith 2.300" rea1izadas a intensidad máxima (4).Los estudios realizados han sido:1. Estudio macroscópico de orina, piel, tejido celular subcutáneo, masa muscular lumbar, riñón. retroperitoneo y contenido peritoneal.2. Determinaciones analíticas en sangre y orina: Hto, Hb, Htíes, leucocitos, plaquetas, creatinina, creatinfosfoquinasa, láctico-deshidrogenasa y gamma-glutamiltranspeptidasa, excreción urinaria de creatinina, beta-2 microglobu1ina y N. acetilglucosaminidasa.3. Estudio histológico renal de todos los conejos.4. Estudio ultraestructural mediante M/E de transmisión.5. Estudio ultraestructural mediante M/E de barrido.6) RESULTADOS- Aspectos macroscópicos: hematuria en todos los animales, lesiones equimóticas en piel en el 54% de los animales, un 5.7% de hematomas retroperitoneales y colecciones hemáticas perirrenales, un 45.7% de lesiones parenquimatosas.- Aspectos analíticos: descenso moderado de HTO, aumentos de leucocitos, ASAT, amilasa, CPK y LDH, en general normalizada a las 72 horas. No presentan cambios significativos la creatinina, ALAT, gammaglutamiltranspeptidasa, bilirrubina y fosfatasas alca1inas.- En las determinaciones urinarias destaca la proteinuria y el aumento de excreción urinaria de NAG.Se describen igualmente las alteraciones histológicas y ultraestructurales (transmisión y barrido).7) CONCLUSJONES1. El modelo elegido ha resultado valido por su manejabilidad, homogeneidad y capacidad para reproducir el experimento.2. En ningún caso, el tratamiento con ondas de choque piezoeléctricas ha resultado letal para los conejos.3. La acción de las ondas de choque piezoeléctricas, a dosis "standard", sobre el riñón alitiásico de conejo, ha comportado lesiones parenquimatosas macroscópicamente detectables en el 45.7% de los casos.4. La hematuria detectada en todos los animales del experimento traduce la existencia de lesión renal por haberse descartado todos los fenómenos relacionados con la litiasis. 5. No se ha observado lesión o alteración en ningún órgano intraperitoneal.6. Los descensos importantes de los valores de hematocrito y hemoglobina traducen la existencia de colecciones hemáticas significativas.7. Existe en todos los casos una afectación del tejido muscular interpuesto entre el riñón y aparato, cuantificable a través de la elevación de la creatinfosfoquinasa (CPK).8. No se han producido déficits de función renal significativos en los animales de nuestro experimento.9. Las lesiones histológicas observadas han demostrado una gran expresividad en la fase aguda y una práctica "restitutio ad integrum" a los 31 días.10. El número y tamaño de las colecciones hemáticas subcapsulares y perirrenales, son suficientes para preveer la aparición, en algún caso, de hipertensión arterial por el "mecanismo de Page".11. La cantidad de tejido renal lesionado, con la dosis "standard" de ondas de choque piezoeléctricas, es insuficiente para producir déficits funcionales significativos.12. En todos los casos de tratamiento con ondas de choque piezoeléctricas se produce una proteinuria significativa, máxima en las primeras 72 h. y todavía detectable a los 31 días.13. El modelo experimental elegido ha sido valido para dar respuesta a los objetivos propuestos. / Extracorporeal Shock Wave Lithotripsy is an accepted procedure for the treatment of renal lithiasis, and there are currently over a million patients who have been treated. Although we have some information about its side effects, there is unanimous acceptance of the need to perform more studies and in particular with regard to piezoelectric and electromagnetic models.We designed an experimental model with 41 rabbits divided into three groups: 30 birenal rabbits, 5 monorenal rabbits and 6 rabbits as a control group. All except the control group received 5000 impulses on their 1eft kidney. Prior to treatment, blood and urine tests were performed on all rabbits. Subsequent tests were performed 2 hours, 24 h., 72 h., 14 days, 21 d. and 31 days after treatment. Macroscopic, microscopic and ultrastructural (M/E and S.E.M.) studies were also made of the treated kidneys.The results include: 45.7% of blood collections, of which 12.5% are perirenal and 87.5% subcapsular; 45.7% of parenchymatous lesions of between 13 x 10 mm and 3 x 2 mm in size.As regards the analytical tests, the most notable are rises in the number of leucocytes, CPK and creatinine in b1ood, and proteinuria. All figures appear to have returned to normal 14 days after treatment.Morphological analysis showed the presence of very expressive and variable phenomena of haemorrhage, vascular lesions, lesions of tubular necrosis and in advanced stages, the presence of focal fibrosis. The M/E study made it possible to assess accurately the lesions of the tubular cell and the S.E.M. was particularly valid for examining glomerular impairment.

En esta tesis se reformulan de manera detallada la primera aproximación de Born relativista con ondas planas (PWBA), para colisiones inelásticas de electrones, positrones y partículas pesadas con átomos o iones, suponiendo que la función de onda atómica puede describirse mediante un modelo de partículas independientes. Además, se deducen expresiones cerradas de las intensidades de oscilador generalizadas longitudinal (GOS) y transversal (TGOS), y para la intensidad de oscilador óptica (OOS). Un aspecto básico de nuestra formulación es que hemos evitado la aproximación de pequeñas transferencias de momento utilizada por Fano (1963), que altera significativamente las secciones eficaces integradas para energías cercanas al umbral de ionización. Liberada de esta aproximación, la PWBA es idéntica a la DWBA (la aproximación de Born con ondas distorsionadas) en el límite de potencial distorsionador nulo.En la tesis también se describen métodos numéricos robustos para el cálculo de las GOSs longitudinal y transversal, así como esquemas de interpolación y de extrapolación para obtener la la sección eficaz doblemente diferencial (SEDD) a partir de las GOSs tabuladas, que hemos implementado en un conjunto de programas de cálculo. Utilizando el potencial autoconsistente de DHFS, hemos generado una base de datos completa de GOSs, TGOSs, OOSs, y perfiles --Born-Compton' para todas las capas de la configuración del estado fundamental de átomos neutros de los elementos desde el hidrógeno hasta el einstenio. Las GOSs calculadas presentan desviaciones sistemáticas de la regla de suma de Bethe, que son consecuencia de efectos relativistas. A partir de nuestra base de datos de GOSs, hemos calculado secciones eficaces totales, secciones eficaces de frenado, y secciones eficaces de dispersión de energía para colisiones inelásticas de electrones, positrones y protones con átomos libres, integrando numéricamente la SEDD.Teniendo en cuenta las desviaciones de la regla de suma, en esta memoria también se deducen fórmulas asintóticas para las secciones eficaces integradas. Además, a partir de ellas hemos obtenido correcciones de capas directamente, como las diferencias entre estas fórmulas y los valores numéricos de las secciones eficaces. Tanto las desviaciones de la regla de suma como las correcciones de capas se originan principalmente en las capas internas, que son poco sensibles al estado de agregación, por lo que los valores obtenidos son también aproximadamente válidos para colisiones con moléculas y con medios densos.Combinando la PWBA y la DWBA, finalmente en esta tesis se detalla un procedimiento robusto para el cálculo de secciones eficaces de ionización de capas internas por impacto de electrones y positrones, para energías arbitrariamente grandes. Para energías por debajo de 16 veces la energía de ionización, utilizamos la DWBA para determinar las correcciones de distorsión e intercambio a la PWBA. Por encima de esta energía, la PWBA escalada con el factor empírico E/(E+bEa) reproduce fielmente los valores DWBA. Utilizando este esquema, hemos generado una base de datos de secciones eficaces de ionización para las capas K, L y M de todos los elementos desde Z=1 hasta Z=99, por impacto de electrones y positrones con energías entre 50 eV y un 1 GeV. Esta base de datos es útil para el análisis cuantitativo en EPMA y AES, y para la simulación MC del transporte acoplado de electrones y fotones. Hemos implementado esta base de datos en el código PENELOPE, y simulado la generación de rayos x en muestras irradiadas por haces de electrones. La comparación con medidas experimentales confirma que al utilizar DWBA en vez de la PWBA mejora la fiabilidad de las simulaciones. Para facilitar el uso de nuestras secciones eficaces de ionización, hemos parametrizado los valores numéricos mediante expresiones analíticas simples. / We present a detailed formulation of the relativistic plane-wave Born approximation (PWBA) for inelastic collisions of charged particles with free atoms and positive ions. The wave functions of the target atom or ion are calculated from a central-¯eld independent-electron model with the Dirac-Hartree-Fock-Slater self-consistent potential. The double-differential cross section, depending on the energy loss and the recoil energy, is expressed as a sum of two terms which are products of purely kinematical factors and the generalized oscillator strengths (GOSs). Transitions induced by the instantaneous Coulomb interaction between the projectile and the active target electron are described by the longitudinal GOS. Transitions caused by the transverse interaction (exchange of virtual photons) are accounted for by a transverse GOS. We derive closed expressions for the longitudinal and transverse GOSs in terms of vector coupling coefficients and radial integrals. A set of Fortran programs have been written to compute the GOSs, the energy-loss differential cross section and integrals of the latter. We also present systematic derivations of asymptotic formulas for the total cross section, the stopping cross section and the energy-straggling cross section. Shell corrections for these quantities are obtained from the differences between computed numerical values and the predictions of the asymptotic formulas.A method is also described for computing total cross sections for the ionization of inner shells of atoms and positive ions by impact of electrons and positrons with arbitrary energies. The method combines the relativistic PWBA with a semirelativistic version of the distorted-wave Born approximation (DWBA). The difference between the total ionization cross sections that result from the DWBA and the PWBA (considering the longitudinal interaction only) has been calculated numerically for projectiles with kinetic energies up to 16 times the ionization energy of the active shell. In this energy range, ionization cross sections with the accuracy of a distorted-wave calculation are obtained by simply adding this difference to the cross section resulting from the conventional PWBA. For higher energies, the cross section is obtained by multiplying the PWBA cross section by an energy-dependent scaling factor that is determined by a single fitted parameter. Numerical results are shown to agree with experimental data, when these are available.

Molts sistemes físics tenen la propietat que la seva dinàmica ve definida per algun tipus de difussió espaial en competició amb un fenòmen de reacció, com per exemple en el cas de dos components químics que reaccionen al mateix temps que es difon l'un en el si de l'altre. La presència d'aquests dos fenòmens, la difusió i la reacció, sovint dóna lloc a patrons no homogenis de gran riquesa. Els models matemàtics que descriuen aquest tipus de comportament són normalment equacions en derivades parcials les solucions de les quals representen aquests patrons. En aquesta tesi s'analitza l'equació de Ginzburg-Landau complexa general, que és una equació en derivades parcials de reacció-difusió que s'utilitza sovint com a model matemàtic per a descriure sistemes oscil·latoris en dominis extensos. En particular estudiem els patrons que sorgeixen en el pla quan s'imposa que el grau de Brouwer de la solució no sigui nul. Aquests patrons estan formats per ones de rotació en forma d'espirals, és a dir, les corbes de nivell de la solució formen espirals que emanen dels punts on la funció s'anul·la. Quan la solució s'anul·la només en un punt i per tant només hi ha una espiral, tota la dependència temporal apareix en el terme de freqüència. Així doncs, la funció solució es pot expressar com a funció del radi polar i en termes del seu grau topològic i la freqüència de l'ona. Per tant, aquestes solucions es poden expressar en termes d'un sistema d'equacions diferencials ordinàries. Aquestes solucions només existeixen per una certa freqüència que depèn unívocament dels paràmetres de l'equació i, com a conseqüència i degut a la relació de dispersió entre el nombre d'ones i la freqüència, el nombre d'ones a l'infinit, l'anomenat nombre d'ones asimptòtic, ve també determinat unívocament pels paràmetres. Quan les solucions tenen més d'un zero aïllat la condició sobre el grau de la funció fa que de cada zero sorgeixi una espiral diferent i aquestes es mouen en el pla mantenint la seva estructura local. En aquest treball s'usen tècniques d'anàlisi asimptòtica per trobar equacions del moviment per als centres de les espirals i es troba que aquesta evolució temporal és lenta. En concret, per la distàncies relatives grans entre els centres de les espirals, l'escala de temps per a la seva dinàmica ve donada pel logaritme de l'invers d'aquesta distància. Es demostra que aquestes equacions del moviment són diferents en funció de la relació entre els paràmetres de l'equació de Ginzburg-Landau complexa i la separació entre els centres de les espirals, i que la forma com es passa d'unes equacions a les altres és molt singular. També es demostra que el nombre d'ones asimptòtic per al cas de sistemes amb diverses espirals també està unívocament determinat pels paràmetres però no obstant, el cas de sistemes amb diverses espirals es diferencia del cas d'una única ona en què deixa de ser constant i evoluciona al mateix ritme que la velocitat dels centres de les espirals. / Many physical systems have the property that its dynamics is driven by some kind of spatical diffusion that is in competition with a reaction, like for instance two chemical species that react at the same time that there is a diffusion of each of them into the other. This interplay between reaction and diffusion produce non-homogeneous patterns that can sometimes be very rich. The mathematical models that describe this kind of behaviours are usually nonlinear partial differential equations whose solutions represent these patterns. In this thesis we focus on an especific reaction-diffusion equation that is the so-called general complex Ginzburg-Landau equation that is used as a model for oscillatory systems in extended domains. In particular we are interested in the type of patterns in the plane that arise when the solutions have a non-vanishing Brouwer degree. These patterns have the property that they exhibit rotating waves in the shape of spirals, which means that the contour lines arrange in the shape of spirals that emerge from the points where the solution vanishes. When the solution vanishes only at one point all the time dependence appears as a frequency term so the solutions can be expressed as a function of the polar radius and in terms of the topological degree of the solution and the frequency of the wave. Therefore, these solutions can be expressed in terms of a system of ordinary differential equations. These solutions do only exist with a given frequency, and as a consequence and due to the existence of a dispresion relation, the wavenumber far from the origin, the so-called asymptotic wavenumber, is also unique. When the solutions have more than one isolated zero, the condition on the degree of the function has the effect of producing several spirals that emerge from the different zeros of the solution. These spirals evolve in time keeping their structure but moving around on the plane. In this work we use asymptotic analysis techniques to derive laws of motion for the centres of the spirals and we show that the time evolution of these patterns is slow and, for large relative separations of the centres of the spirals, the time scale for the their dynamics is logarithmic in the inverse of this distance. These laws of motion are different depending on the relation between the parameters of the complex Ginzburg-Landau equation and the relative separation of the spirals. We show that the way these laws change as the spirals separate or approach is highly singular. We also show that the asymptotic wavenumber in the case of multiple spirals is as well unique and that it evolves in time at the same rate as the velocity of the centres.

Gold catalysts have the characteristic of promoting nucleophilic reaction. The cyclization reaction of enediynes catalyzed by gold activated by silver in toluene at 100oC to give 6H-dibenzo[c,h]chromen-6-ones (63), 6H-benzo[c]chromen-6-one (66) and Arnottin I (10) is described. Treatment of enediynes (61¡B65) with 5 mol% of Ph3PAuCl and 10 mol% of AgSbF6 in toluene at 100oC gave 6H-dibenzo[c,h]chromen-6-ones (63) and 6H-benzo[c]chromen-6-one (66) in good yield. In addition to using gold catalyst, electrophilic reagents employed in the reaction caused one cyclization instead of two cyclization. Furthemore, a mechanistic study and GC-MS data showed that the toluene could participate in the reaction. Enediynes (73) can be synthesized by a series of organic synthesis with few steps. Treatment of enediynes (73) with 5 mol% of Ph3PAuCl and 10 mol% of AgSbF6 in toluene at 100oC gave natural product-Arnottin I (10).

SANTOS, Juliana de Brito Marques dos. Era uma vez... um chapeuzinho, seis surdos, seis histórias. 2006. 122f. – Dissertação (Mestrado) – Universidade Federal do Ceará, Departamento de Letras Vernáculas, Programa de Pós-graduação em Linguística, Fortaleza (CE), 2006. / Submitted by Márcia Araújo (marcia_m_bezerra@yahoo.com.br) on 2014-08-20T12:13:40Z No. of bitstreams: 1 2006_dis_jbmsantos.pdf: 8938210 bytes, checksum: 4dfd50031bbd3df4ba6f7ef45c885d3c (MD5) / Approved for entry into archive by Márcia Araújo(marcia_m_bezerra@yahoo.com.br) on 2014-08-20T16:35:30Z (GMT) No. of bitstreams: 1 2006_dis_jbmsantos.pdf: 8938210 bytes, checksum: 4dfd50031bbd3df4ba6f7ef45c885d3c (MD5) / Made available in DSpace on 2014-08-20T16:35:30Z (GMT). No. of bitstreams: 1 2006_dis_jbmsantos.pdf: 8938210 bytes, checksum: 4dfd50031bbd3df4ba6f7ef45c885d3c (MD5) Previous issue date: 2006 / The objective of this paper is to investigate the singularity of deaf student’s writing, observing and analyzing on how their life story influences on their written Portuguese. The research was based on the analysis of the texts that were written an rewritten about the fairytale of Little Red Riding Hood, written by six deaf students, of the 7th grade, that study at the Instituto Cearense de Educação de Surdos (ICES), with the objective of observing the individual characteristics present in each texts of written by the six students. Besides the collection of the texts, in May and November 2005, there were carried out three interviews, all of them made with the help of an interpreter. The first interview was made through a questionnaire, in May 2005; the second one was structured, and the other was semi-structured, both were made in November 2005. The objective of the interviews sere to collect data on the life story of the six students subjects, and also on their experiences in the school and with their families, and their opinion on the importance of the use of Portuguese language and of LIBRAS (Brazilian Sign Language). The data collected in the interviews, was compared with the analysis of the characteristics of the student’s text, trying to observe how their life story could be present in their writing, as we believed that the act of writing is a reflex of our discursive formation. This research, was carried out based on the social-interactive of the language, agree with the studies of Vygotsky and Bakhtin. Besides the review of great researchers Vygotsky and Bakhtin, I also present in this study a brief history deaf education and some characteristics of the LIBRAS (Brazilian Sign Language), as I agree these are some of the factors that influence the writing of the deaf. / Este trabalho tem como objetivo a investigação da singularidade da escrita dos surdos, observando e analisando como a história de vida de cada um influencia no português escrito. Para a realização da pesquisa, foram analisados os textos escritos e reescritos da história Chapeuzinho Vermelho, produzidos por seis alunos surdos, da 7ª. série, do Instituto Cearense de Educação de Surdos, com o intuito de observar as características individuais presentes nos textos de cada um dos sujeitos. Além da coleta dos textos, que ocorreu, respectivamente, em maio e novembro de 2005, foram realizadas três entrevistas, todas com o auxílio de um intérprete. A primeira, direcionada por meio de um questionário, ocorreu em maio de 2005; e as duas últimas, uma não estruturada e outra semi-estruturada, ocorreram em novembro de 2005. As entrevistas tiveram como objetivo coletar dados sobre a história de vida dos sujeitos, suas vivências na escola e na família, suas opiniões sobre a importância e o uso da língua portuguesa e da LIBRAS etc. As informações, obtidas nas entrevistas, foram comparadas com a análise das características dos textos dos sujeitos, procurando observar como a história de cada um pode estar presente em seus discursos, posto que acreditamos ser o desempenho na escrita um reflexo de sua formação discursiva. Para a realização desta pesquisa, foi assumida a concepção sócio-interacionista da linguagem, corroborando com Vygotsky e de Bakhtin. Além de revisitar os preceitos destes célebres autores, também apresento neste estudo um breve histórico da educação dos surdos e algumas características da LIBRAS, por compreender serem estes alguns dos fatores que influenciam a escrita dos surdos.

Este estudo propõe uma ligação decisiva entre o capitalismo e os assim chamados direitos humanos e sociais. O objetivo é provar que o desenvolvimento histórico dos direitos humanos, considerando sua primeira dimensão e sua segunda dimensão, não é baseado no desenvolvimento do espírito humano e da consciência universal, mas sim no processo capitalista de produção e reprodução social. Ao se seguir um caminho teórico marxista, é possível perceber que toda a forma jurídica, até mesmo os direitos humanos, está profundamente comprometida com uma estrutura capitalista de sociedade. Em adendo, este fato implica consequências importantes para todos os programas políticos e perspectivas reformistas. Os direitos civis e políticos, tanto quanto os direitos sociais, são parte de um maquinário burguês que faz do direito um instrumento de exploração e preservação do status quo, apesar do progresso relativo que eles podem trazer com eles. O Estado de Direito é apenas uma maneira particular pela qual o Estado burguês, em tempos de normalidade, emprega sua violência. E as políticas de bem-estar social não são nada além de uma intervenção estatal para apoiar o ciclo de acumulação do capital conforme necessidades concretas (e políticas). Não há nenhum tipo de esclarecimento, bondade ou senso de decência humana nos direitos relacionados à democracia liberal e às instituições de bem-estar social, mas sim contingências de determinados momentos da luta de classes e da dinâmica econômica de reprodução sob o sistema capitalista. A verdadeira emancipação só é viável pelo fim das classes sociais, um difícil horizonte que começa com uma estratégia socialista. E quanto mais a revolução socialista modifica as relações de produção para estabelecer o controle social pela classe trabalhadora, tanto menor é a hegemonia da forma jurídica sobre a vida, porque o direito perece junto com o fim da produção e da circulação de mercadorias. A luta pelo socialismo como a luta por um novo e superior tipo de vida civilizada que nenhum dos direitos humanos poderia prover à humanidade. / This study proposes a critical link between capitalism and the so-called human and social rights. The objective is to prove that the historical development of human rights, considering their first dimension and their second dimension, is not based on the development of the human spirit or of a universal consciousness, but on capitalist process of social production and reproduction. By following a marxist theoretical path, it is possible to realize that all juridical form, even human rights, is deeply compromised with a capitalist structure of society. In addition, this fact implicates important consequences for all reformist political programs and perspectives. Civil and political rights, as much as social rights, are part of a bourgeois machinery which turn law into an instrument of exploitation and preservation of status quo, despite the relative progress they may bring with themselves. The rule of Law is only a particular manner by which bourgeois state, in times of normality, employs its violence. And the policies of welfare are nothing but a state intervention to support the cycle of accumulation of capital according concrete (and political) necessities. There is not any sort of enlightenment, kindness or sense of human decency in the rights related to liberal democracy and the institutions of welfare state, but only contingences from a determined moment of struggle of class and economical dynamics of reproduction under capitalist system. A true emancipation is only viable by the end of social classes, a difficult horizon that begins with a socialist strategy. And the more a socialist revolution changes the relations of production in order to establish a social control by working class, the lesser is the hegemony of the juridical form over life, because law perishes tied to the end of production and circulation of commodities. The struggle for socialism reveals itself as a struggle for a new and superior kind of civilized life which none of the human rights could provide to mankind.