Dissertations / Theses on the topic 'Carioca S.A'

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Regarding the studies about the behavior of the consumer and crisis management reflects the numerous contributions of social sciences and humanities. The connection of these two areas of understandings was possible through the observation of experiences the consumers lived through, during the recent Brazilian aviation crisis, which made it possible to understand the inconstant trust of the executives after the crisis. The dissertation contextualizes how the executives from Rio de Janeiro think and act, compounding an extremely singular vision regarding their perceptions after the Brazilian aviation crisis. To support the field work expost facto, the theoretical reference includes authors linked to the marketing of services, consumer behavior, consumption and citizenship, trust and crisis management. From the economic and business point of view, the organizations understand the relevance of the study regarding trust when confirmed that the consumers want to trust their suppliers and have the expectation that the products, goods and services be unswerving to the ideas and aspirations that are developed in their lives. The elements of trust are classified into: i) factors linked to the authors decision to trust and support the singular mixture of personality, culture and experience; ii) situational factors that have to do with the aspects of specific situations and relationships between the parties. The work demanded: i) exploratory field work, ii) data collection from secondary sources (print and electronic media), iii) official information divulged by the institutions involved, iv) interviews with time sensitive users of a hypothetical deduction character with a qualitative approach, necessary to attract the perspective subjects in the investigation ex-post facto. The Contents Analysis method allowed to understand the world of the significant of the actions and human relations in their overall situation. In exploring a critical situation such as the one faced by the Brazilian aerial blackout , the work witnessed how the aviation crisis, complex and long-lasting, weakened institutions and the consumers belief was greatly affected.
Os estudos sobre o comportamento do consumidor e o gerenciamento de crises refletem as m?ltiplas contribui??es das ci?ncias sociais e humanas. A uni?o destas duas ?reas do conhecimento foi poss?vel atrav?s da observa??o das experi?ncias vividas pelos consumidores na recente crise a?rea brasileira, que permitiu compreender a vari?vel confian?a dos executivos ap?s a mesma. A disserta??o contextualizou o modo como os executivos do Rio de Janeiro pensam e agem, compondo uma vis?o muito singular sobre as suas percep??es ap?s a crise a?rea brasileira. Para ancorar a pesquisa de campo ex-post facto, o referencial te?rico conta com autores ligados ao marketing de servi?os, comportamento do consumidor, consumo e cidadania, confian?a e gerenciamento de crise. Do ponto de vista econ?mico e empresarial, as organiza??es compreendem a relev?ncia do estudo sobre confian?a quando afirmam que os consumidores querem confiar em seus fornecedores, e t?m a expectativa de que os produtos, bens e servi?os sejam fi?is aos ideais e aspira??es que desenvolvem em suas vidas (Roberts, 2005). Os elementos da confian?a se distribuem em: i) fatores ligados ao autor da decis?o de confiar e se ancoram na mistura singular de personalidade, cultura e experi?ncia; ii) fatores situacionais que tem a ver com os aspectos da situa??o espec?fica e do relacionamento entre as partes (Hurley, 2006). O trabalho demandou: i) pesquisa de campo explorat?ria, ii) coleta de dados em fonte secund?ria (m?dia impressa e eletr?nica), iii) informa??es oficiais divulgadas pelas institui??es envolvidas, iv) entrevistas com usu?rios time sensitive de car?ter hipot?ticodedutivo (Foddy, 1993), com abordagem qualitativa, necess?ria para captar a perspectiva dos sujeitos em uma investiga??o ex-post facto (Gil, 1996). O m?todo de An?lise de Conte?do (Bardin, 1977) possibilitou compreender o mundo de significados das a??es e rela??es humanas no seu contexto. Ao explorar uma situa??o cr?tica como a enfrentada pelo apag?o a?reo brasileiro, o trabalho evidenciou como a crise a?rea, complexa e de longa dura??o, fragilizou institui??es e afetou a credibilidade de consumidores intensivos.

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This dissertation seeks to analyze the reports about the homicides perpetrated in the city of Rio de Janeiro in the first decade of the twentieth century. With this aim, we will research the main newspapers of the federal capital of the period. In addition, we will collate the newspaper reports with the documents produced by the police and judicial authorities. In this sense, we intend to observe the similarities and disparities among our main sources of research, that is, Rio?s newspapers and criminal processes. To do so, we will analyze the murder of a police soldier in Morro da Favela. In the first place, we will see how the different newspapers reported the conflict involving several public security agents. Next, we will analyze the testimonies of the witnesses and protagonists of his murder.
A presente disserta??o busca analisar as reportagens sobre os homic?dios perpetrados na cidade do Rio de Janeiro na primeira d?cada do s?culo XX. Com este fito, pesquisaremos os principais jornais da capital federal do per?odo. Al?m disso, iremos cotejar os relatos dos impressos com os documentos produzidos pelas autoridades policiais e judici?rias. Nesse sentido, pretendemos observar as similaridades e disparidades entre as nossas principais fonte de pesquisa, ou seja, os jornais cariocas e os processos criminais. Para tanto, analisaremos o homic?dio de um soldado policial no Morro da Favela. Em primeiro lugar, veremos como os diferentes jornais relataram o conflito envolvendo diversos agentes de seguran?a p?blica. Em seguida, analisaremos os depoimentos das testemunhas e protagonistas deste assassinato.

Submitted by PPG Hist?ria (historia-pg@pucrs.br) on 2018-09-26T18:02:59Z No. of bitstreams: 1 VERS?O FINAL Disserta??o Imagens p?blicas em disputa - Cristiane Mitsue Corr?a.pdf: 3854910 bytes, checksum: 54fa8bbbcbc134290057a5feecdce605 (MD5)
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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES
Conselho Nacional de Pesquisa e Desenvolvimento Cient?fico e Tecnol?gico - CNPq
The research aims to analyze the construction of the public image of President Jo?o Goulart and his government (1961-1964) through the press in Rio de Janeiro - Correio da Manh?, Jornal do Brasil and ?ltima Hora. Three political moments are analyzed that marked different phases and moments of the government: inauguration of Goulart, in 1961; referendum for return of presidentialist regime or maintenance of parliamentary system, in 1963; and reform meeting, in 1964. The aim is to analyze and understand how newspapers elaborated president's public image on political events that had in common the discussion of categories such as democracy, citizenship and popular participation, located in periods of political, economic and military crisis. In this study, when analyzing the journalistic discourses and the changes of opinion of press according to the political events, the importance of production of press in our perception of the social, political and historical reality is considered, determining a look on the past.
A pesquisa tem como objetivo analisar a constru??o de imagens p?blicas do presidente Jo?o Goulart e seu governo (1961-1964) atrav?s da grande imprensa carioca ? Correio da Manh?, Jornal do Brasil e ?ltima Hora. Analisa-se tr?s momentos pol?ticos que marcaram fases diferentes do governo: a posse de Goulart, em 1961; o plebiscito pelo retorno do regime presidencialista ou a manuten??o do sistema parlamentarista, em 1963; e o com?cio das reformas de base, em 1964. Trata-se de analisar e compreender de que maneira os jornais elaboraram as imagens do presidente em eventos pol?ticos que tinham em comum a discuss?o de categorias como democracia, cidadania e participa??o popular, situados em per?odos de crises pol?tica e militar, em um contexto maior de crise econ?mica no pa?s. Neste estudo, ao analisar os discursos jornal?sticos e as mudan?as de opini?o dos jornais conforme os acontecimentos pol?ticos, considera-se a import?ncia da produ??o da grande imprensa na nossa percep??o da realidade social, pol?tica e hist?rica, determinando um olhar sobre o passado.

Through the theoretical perspective of the Political Sociology of Public Policy Instruments (Lascoumes & Le Galès 2004), the thesis explores the role of the slum upgrading instrument in the evolution of Rio de Janeiro's housing policy and governance. Specifically, it examines the significance of slum upgrading choice and use over the past two decades. The research is guided by the following question: how did the slum upgrading influence Rio de Janeiro's housing policy and governance development from 1993 to 2012? The research considers three hypotheses: 1. The slum upgrading contributed to produce the inflexion points of the evolution of Rio's housing policy. 2. The slum upgrading fostered the transformation of Rio's housing governance. 3. The slum upgrading supported the depoliticization of Rio's housing policy. On its theoretical stand, the research builds on the one hand on the Political Sociology of Public Policy Instruments (PPI) approach that argues that policy instruments contribute to structure public policy as they generate specific effects (Lascoumes & Le Galès 2004). On the other, the research builds on the Actor-Network-Theory (ANT) that understands 'the social' as an heterogeneous network of entities called 'actants' created by a specific movement of 'associations' conceptualized as 'translation' (Latour 2005; Callon 1986). Based on these perspectives, the thesis analysed the slum upgrading as a 'policy instrument', itself being an 'actant'. Subsequently, through 'detective work' (Austrin & Farnsworth 2005), the thesis delved into the unfolding of Rio's slum upgrading network of 'associations' using primary municipal archives, semi-structured interviews and policy documents. The investigation resulted in the production of a chronological 'thick description' which reveals the slum upgrading role in Rio's housing policy and governance transformation.

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Twelve heterocyclic dialkylphosphorylhydrazones compounds were synthesized in this work. Dialkylphosphorylhydrazones were obtained through 3 steps of reaction. The first step consists on the synthesis of different dialkylphosphonates obtained by reaction of triethyl phosphate (PCl3) with 3 mols of the corresponding alcohol. The second step occurs by the reaction with dialkylphosphonates synthesized and hydrazine, producing dialkylphosphorylhydrazines. The third and last step is the condensation reaction of these dialkylphosphorylhydrazines with different heterocycle substituted aromatic aldehydes. The analysis of the 1H NMR spectra allowed to observe the stereoisomers E and Z, with the formation of E diastereisomer preferencially. All the compounds were characterized by 1H, 13C and 31P NMR, IR and mass spectroscopy. Tests in vitro with, Alternaria sp., Colletotrichum sp., Fusarium sp. e Fusarium solani, known as patogenic in papaya (Carica papaya L.) were performed in order to confirm if the compounds showed fungicide activity. The substance 6 B was the one with the best performance in the inhibition of all fungal growths. Finally, tests with acetylcholinesterase enzyme indicated that all substances did not inhibit this enzyme. Figure 2 - General structures of dialkylphosphoryhidrazones synthesized. R ? Ethyl; propyl; isopropyl e isobuthyl. X = O, Y, Z e W = CH; X = S, Y, Z e W = CH; X = NH, Y, Z e W = CH; X = NH, Y= CH, Z=CH e W = N; X = CH, Y= N, Z=CH e W = N;
Neste trabalho foram sintetizadas doze (12) novas dialquilfosforilidrazonas heteroc?clicas. Esses compostos foram obtidos utilizando-se tr?s etapas de rea??o. A primeira etapa consiste na s?ntese de diferentes fosfonatos de dialquila, obtidos por meio da rea??o do tricloreto de f?sforo (PCl3) com tr?s mols do ?lcool correspondente. A segunda etapa ocorre por meio da rea??o dos fosfonatos de dialquila sintetizados com a hidrazina, formando as dialquilfosforilidrazinas. A terceira e ?ltima etapa ? a condensa??o destas dialquilfosforilidrazinas com diferentes alde?dos heteroc?clicos. A an?lise dos espectros de RMN-1H indica a forma??o de diastereois?meros, E e Z, com predomin?ncia do diastereis?meros E. Todos os compostos obtidos foram caracterizados por RMN de H1 e C13 e P31, IV, an?lises de massas. Em seguida foram realizados testes in vitro para verificar se os mesmos possuem atividade fungicida sobre os fungos Alternaria sp., Colletotrichum sp., Fusarium sp. e Fusarium solani, conhecidos por serem pat?genos da cultura de mam?o (Carica papaya L.). O composto 6 B foi o que apresentou o melhor efeito fungicida sobre o crescimento de todos os fungos. Finalmente foram realizados testes com a enzima acetilcolinesterase a fim de observar a toxicidade dos compostos sintetizados frente a esta enzima. Figura 1- Estrututa gen?rica das dialquilfosforilidrazonas heteroc?clicas sintetizadas. R ? Etil; propil; isopropil e isobutil. X = O, Y, Z e W = CH; X = S, Y, Z e W = CH; X = NH, Y, Z e W = CH; X = NH, Y= CH, Z=CH e W = N; X = CH, Y= N, Z=CH e W = N.

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES)
A ordem Tetraodontiformes se destaca por exibir caracter?sticas morfol?gicas e gen?ticas bastante singulares, representando um dos principais ramos derivados da diversifica??o dos tele?steos. Alguns dos seus grupos constituem os vertebrados com os genomas mais compactos, qualificando-os como modelo de estudo da evolu??o do genoma. Esta caracter?stica gen?mica parece ser o resultado de perdas evolutivas de DNA. Com vistas a realizar compara??es citogen?micas entre esp?cies de alguns grupos de Tetraodontiformes foram realizadas an?lises citogen?ticas nas esp?cies Cantherhines pullus e Monacanthus chinensis (Monacanthidae), Sphoeroides testudineus (Tetraodontidae) e Melichthys N?ger (Balistidae). As an?lises foram ralizadas utilizando as metodologias cl?ssicas (colora??o pelo Giemsa, bandamento C, Ag-RONs), colora??o com fluorocromos base-espec?ficos e mapeamento cromoss?mico atrav?s da hibrida??o in situ fluorescente (FISH) de sequ?ncias ribossomais 18S e 5S e telom?ricas. As esp?cies C. pullus e M. niger revelaram cari?tipos compostos de 40 cromossomos, todos acroc?ntricos. Ambas possuem apenas um par de RONs e heterocromatinas, em maior parte, pericentrom?ricas, contudo, o mapeamento de sequ?ncias telom?ricas em C. pullus mostrou marca??es telom?ricas intersticiais, resultado da din?mica de rearranjos cromoss?micos que ocorre no grupo. Compara??es citogen?ticas entre as esp?cies S. testudineus (2n=46; NF=74) e M. chinensis (2n=34; NF=34) revelaram cari?tipos d?spares em rela??o ao n?mero diploide e de bra?os cromoss?micos, bem como quanto ao diminuto tamanho dos cromossomos de S. testudineus, em rela??o ao grandes cromossomos acroc?ntricos presentes em M. chinensis. A marcante diverg?ncia no tamanho dos cromossomos, estrutura cariot?pica e distribui??o de heterocromatina evidencia a elevada din?mica cromoss?mica e as m?ltiplas tend?ncias carioevolutivas presentes em Tetraodontiformes. Em vista do interesse sobre a evolu??o gen?mica na ordem, novas contribui??es ao conhecimento dos seus genomas e cari?tipos s?o fornecidos e discutidos sob perspectivas citogen?micas e evolutivas.

In recent years, the concept of burnout has been expanded and is currently a concern in all professions and occupational groups. Nowadays it is widely acknowledged that people in almost any occupation could develop burnout. To-date, only two studies have examined students' experiences of burnout. Therefore, research regarding this phenomenon in students seems warranted. The objective of this study was to firstly investigate the psychometric properties of adapted versions of the Maslach Burnout Inventory and Utrecht Work Engagement Scale in a sample of students from a tertiary institution, and secondly to consider the role of biographical variables in relation to burnout and engagement levels. A cross-sectional survey design was used to attain the research objectives. For the purposes of this study, an availability sample of students (N=353) majoring in Organisational Behaviour was drawn at one point in time. The adapted Maslach Burnout Inventory - Student Survey (MBI-SS) and the Utrecht Work Engagement Scale - Student Survey (UWES-S) as well as a biographical questionnaire were administered. Structural equation modelling confirmed two-factor models of Burnout (consisting of Exhaustion and Cynicism) and Engagement (consisting of Vigour and Dedication). Biographical variables which appear to be predictive of differences in levels of student burnout are home language, overall health status and consideration given to quitting their studies, while engagement is related to home language, academic year of study and consideration given to quitting studies. Recommendations for future research were also made
Thesis (M.A. (Industrial Psychology))--North-West University, Potchefstroom Campus, 2006.

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Fundo Mackenzie de Pesquisa
The new Pentecostalism calls attention because of its growing here in Brazil. Between the new Pentecostal churches can be mentioned the World s Church of God s Power . Founded by apostle Valdemiro Santiago in the year 1998, have conquered place in media and in number of adepts. The World s Church of God s Power is a dissident of Universal Church of God s Kingdom . Our research verify the differences and similarities between the World s Church of God s Power and Universal Church of God s Kingdom . To understand the phenomenological process, we choose the Weberian method of the sociology of comprehension. We built through the relive, one concept of pure and ideal type in the dialectic movement between World s Church of God s Power and Universal Church of God s Kingdom . In the ideality field, the Universal represents the bureaucracy, which is the process of institutionalization, historic results of all the religious movement. The World s Church of God s Power represents the prophecy, that the characteristic is the contestation. An exam of the rational domination and charismatic domination will help us to comprehend the phenomenon. The fundamental difference between the two churches is focused in charisma. The Universal institutionalize itself trough the bureaucracy, rational domination, and the World s is the prophecy that is reaffirmed by the charismatic domination.
O neopentecostalismo chama a atenção devido ao seu crescimento aqui no Brasil. Dentre as igrejas neopentecostais destaca-se a Igreja Mundial do Poder de Deus. Fundada pelo apóstolo Valdemiro Santiago em 1998, tem conquistado lugar na mídia e em número de adeptos. A Igreja Mundial do Poder de Deus é uma dissidência da Igreja Universal do Reino de Deus. Nossa pesquisa verifica o que há de convergente e divergente entre a Mundial e a Universal. Para compreender o processo fenomenológico, optamos pelo método werberiano da sociologia da compreensão. Construímos através da revivência um conceito de tipo puro ideal no movimento dialético entre a Mundial e Universal. No campo da idealidade, a Universal passa a representar a Burocracia, que é o processo de institucionalização, resultado histórico de todo movimento religioso. A Mundial representa a Profecia, cuja característica é a contestação. Em decorrência, um exame da dominação racional e dominação carismática nos ajudará compreender o fenômeno. A diferença fundamental entre as duas igrejas se concentra no carisma. A Universal se institucionaliza através da burocracia, dominação racional, e a Mundial é a profecia que se reafirma através da dominação carismática.

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Este estudo avaliou, in vitro, a resist?ncia de uni?o ? microtra??o dos sistemas adesivos Single Bond - SB (3M/ESPE) e Clearfil SE Bond - CSE (Kuraray) ? dentina sadia e cariada, com ou sem aplica??o pr?via do laser Nd:YAG associado ou n?o a presen?a de fl?or. A superf?cie oclusal de 60 terceiros molares humanos foi removida para obten??o de uma superf?cie dentin?ria plana. Metade destes dentes foram submetidos ? ciclagem de pH para realiza??o de c?rie artificial e a outra metade permaneceu com a dentina h?gida. Os dentes foram divididos em 12 grupos, sendo que a dentina dos grupos 1-6 era cariada e dos grupos 7-12 sadia. Foram realizados 3 tratamentos distintos: irradia??o da dentina com laser Nd:YAG (60 mJ, 15 Hz e 0,9 W); irradia??o da dentina com laser Nd:YAG associado ao fl?or em gel; e sem tratamento (controle). Doze dentes, tratados como descrito acima, foram utilizados para avalia??o da microdureza, para an?lise em MEV e espectroscopia por energia dispersiva (EDS). Nos dentes dos grupos experimentais, a aplica??o dos sistemas adesivos foi realizada de acordo com as instru??es dos fabricantes e um plat? de resina composta (Z250/3M) com aproximadamente 6 mm de altura foi realizado. Ap?s, os esp?cimes foram armazenados em ?gua destilada por 24 h em uma estufa de cultura a 37?C. Decorrida esta etapa, os dentes foram seccionados nos sentidos x e y para obten??o de palitos (25 por grupo) com ?rea adesiva de 0,8 mm2. Estes palitos foram submetidos ao ensaio de microtra??o, em uma m?quina de ensaios mec?nicos (EMIC-DL), com velocidade de 0,5 mm/min. O padr?o de falha foi caracterizado pela an?lise em MEV e an?lise fractogr?fica. Segundo o modelo linear geral univariado (GLM) e Tukey (p < 0,05), as maiores m?dias foram obtidas quando os sistemas adesivos foram aplicados em dentina sadia, de acordo com as instru??es dos fabricantes (SB 34,2 MPa e CSE 40,65 MPa). Os resultados tamb?m mostraram que a presen?a de tecido cariado reduziu significativamente a resist?ncia de uni?o dos dois sistemas adesivos utilizados. A irradia??o da dentina com laser diminuiu a resist?ncia de uni?o do Clearfil SE Bond e n?o afetou os dentes tratados com o Single Bond. A irradia??o da dentina sadia com laser associado ao fl?or reduziu os valores de resist?ncia de uni?o para os dois sistemas adesivos, embora este tratamento em dentina cariada, utilizando o Clearfil SE 12 Bond tenha mostrado resultados superiores ao Single Bond. O tipo de falha predominante foi a falha do tipo mista. A an?lise em MEV da dentina sadia, ap?s aplica??o do laser, mostrou uma superf?cie com irregularidades e porosidades devido ? fus?o e recristaliza??o desta dentina, com t?bulos dentin?rios oclu?dos; a dentina cariada apresentou as mesmas caracter?sticas da dentina sadia irradiada, com t?bulos dentin?rios mais n?tidos devido ? reestrutura??o da dentina peritubular.

RESUMO: Desde 1640 até data extrema de 1834, os Irmãos Hospitaleiros de S. João de Deus foram os responsáveis, directa e indirectamente, pela administração e corpo de enfermagem dos Reais Hospitais Militares em Portugal, actividades que analisamos ao longo dos séculos, desenvolvendo pressupostos temáticos relativamente a sua actuação no tempo e no espaço. É durante o séc. XVII até ao séc. XIX, que vemos os cuidados da corte para com a assistência aos soldados enfermos e doentes, ao publicar inúmera legislação relativamente à complexidade assistencial na área militar, a qual foi por nós compilada para melhor contextualização da importância dos Hospitais Militares em Portugal. Os Regimentos, os Alvarás, os Regulamentos e as Ordens do Dia, constituem um objecto fundamental de pesquisa e análise para caracterizar o quotidiano nesses mesmos locais. Os Hospitais Militares desde a sua fundação, dos primórdios das Guerras da Aclamação em 1640, até ao advento do liberalismo em 1834, eram centros de conhecimento técnico e científico com um corpo assistencial especializado, onde um conjunto pluridisciplinar de profissionais zelava qualitativamente pelos assistidos, e onde os Irmãos Hospitaleiros de S. João de Deus desempenhavam funções de administradores, enfermeiros e capelães. Nesse sentido elaboramos uma listagem cronológica para inter relacionar os Irmãos Hospitaleiros e os Hospitais Militares, pois é impossível separar a Ordem de S. João de Deus da componente assistencial aos enfermos e doentes militares em Portugal. A importância urbana e arquitectónica, que os Reais Hospitais Militares tiveram no contexto orgânico e defensivo nas Praças de Guerra, é realçado pela forma como estes se encontravam implantados e construídos, demarcando-se esteticamente da globalidade edificada, pois constituíam parte integrante dos equipamentos militares, como era teorizado pelos técnicos militares. Assim analisamos a localização dos imóveis, para além do próprio edifício hospitalar, com o meio, ou seja com a urbanidade das Praças de guerra. A sobriedade arquitectónica dos Hospitais Militares, integrada nos grandes ciclos das correntes culturais europeia e nacional, associada à riqueza decorativa e iconoclasta desenvolvida nesses locais, dá-nos uma dimensão da importância científica que esses núcleos assistenciais tiveram, contribuindo para a difusão do culto e circulação da imaginária de S. João de Deus em Portugal e dos Santos venerados nos Hospitais Militares. Desta forma compreendemos o alicerçar devocional que o reino tinha por este Santo, como o fundador do conceito assistencial do hospital moderno. Estando intrinsecamente ligado a este facto vemos o proliferar do culto e da imaginária de S. João de Deus em Portugal, centrando-se a iconografia artística do Santo em torno das localidades onde se enraizaram os Hospitais Militares. Hoje, nos imóveis hospitalares, não é difícil analisar uma lenta evolução da funcionalidade dos seus espaços, gravitando o desenvolvimento estrutural assistencial em torno das enfermarias e salas de cirurgia, mantendo-se perene este arquétipo arquitectónico desde o séc. XVII até meados do séc. XIX, as quais foram levantadas, comparadas e analisadas. Foi com a exclaustração das Ordens Religiosas, pelo Decreto de 29 de Maio de 1834, que acabou a extraordinária e valorosa acção administrativa, tutelar e corpo de enfermagem dos Irmãos Hospitaleiros de S. João de Deus, na área específica da assistência militar em Portugal, extinguindo-se, nalguns casos, os Hospitais Militares, pois o reino não estava preparado para substituir esses profissionais de saúde. O nosso estudo desenvolve-se por cerca de 295 anos, espaço temporal em que os Hospitais Militares foram administrados e fundados pelos Irmãos de S. João de Deus em Portugal.---------ABSTRACT: Since 1640 until 1834 the Hospitaller Brothers of S. John of God were the responsibles, direct and indirectly, for the administration and nursing body of the Royal Military Hospitals in Portugal, activities that we analyse throughout the centuries, developing thematic presuppositions regarding its performance in time and in space. It is during the 17th century until the 19th century, that we see the court’s care with the assistance of the wounded and sick by the publishing of much legislation regarding the assistance complexity in the military area, which was compiled by us in order to achieve a better comprehension of the importance of the Military Hospitals in Portugal. The Regiments, Charters, Regulations and Orders of Day constitute a fundamental object of research and analysis to characterise the quotidian of these locations. The Military Hospitals, since its foundation, in the beginning of the Wars of Acclamation in 1640, until the advent of liberalism in 1834, were centres of technical and scientific knowledge with a specialized assistance body, were a multidisciplinary set of professionals took qualitatively care of the attended, and where the Hospitaller Brothers of S. John of God performed the tasks of administrators, nurses and chaplains. In this perspective, we created a chronological listing in order to relate the Hospitaller Brothers with the Military Hospitals, since it is impossible to separate the Hospitaller Order of S. John of God from the component of assistance to the military sick and wounded in Portugal. The urban and architectural importance that the Royal Military Hospitals had in the organic and defensive context of the War Fortifications is emphasized by the way these were implanted and built and by its architectural demarcation of the edified whole, since they constituted an integrant part of the military equipments, as it was theorized for the military architecture. Therefore we analyse the location of the real estate, analysing not only the hospital building itself, but also its relation with the environment, i. e. with the urbanism of the war fortifications. The architectural sobriety of Military Hospitals, integrated in the big cycles of cultural streams in Europe and Portugal, associated to the decorative and iconoclastic wealth developed in these locations, give us a dimension of the scientific importance that these hospitals had, contributing to the diffusion of the cult and circulation of sculptures and paintings of S. John of God in Portugal and of the Saints revered in the Hospitals. In this way, we understand the consolidation of the devotion that the kingdom had for this Saint, the founder of the assistance concept of the modern hospital. The proliferation of the cult and iconography of S. John of God is intrinsically connected to this fact, the artistic iconography concentrating itself around the localities were the Military Hospitals were built. Today, in the assistance buildings, it is not difficult to analyse a slow evolution of the functionality of its spaces, gravitating the structural assistance development around the infirmaries and surgery rooms, this architectural archetype being perennial from the 17th century until the middle of the 19th century. These infirmaries were pointed out, compared and analysed. It was the expulsion of the Religious Orders, by the Decree of May 29th 1834, that ended with the extraordinary and valorous administrative and tutelary action and nursing body of the Hospitaller Brothers of S. John of God, in the specific area of military assistance in Portugal, extinguishing, in some cases, the Military Hospitals, since the kingdom wasn’t prepared to substitute these health professionals. Our study is developed in a timeframe of 295 years, period in which the Military Hospitals were administrated and founded by the Brothers of S. John of God in Portugal.

L’époque hellénistique est le moment où les villes d’Ionie et de Carie changent peu à peu d’aspect. Dans chaque ville ou presque, quantité de monuments publics nouveaux façonnent progressivement un paysage urbain inédit qui se présente comme un miroir de la cité qui l’a créé. C’est cette transformation sans précédent des centres urbains durant l’époque hellénistique que cette thèse se propose d’étudier, en portant attention aux villes d’Ionie et de Carie dans toute leur diversité. Elle cherche à dégager le sens des changements dans deux régions à l’hellénisation ancienne et fortement urbanisées, caractérisées par des interactions entre cités et rois hellénistiques. Cette étude propose des pistes pour mieux comprendre les sociétés civiques au travers d’un lieu de vie : la ville. L’approche privilégie ce que la ville a de plus remarquable, ses édifices publics. Dans une première partie consacrée aux fortifications urbaines, aux lieux qui abritent les activités politiques, et aux espaces de la vie culturelle au sens large, les monuments publics sont évoqués en tant qu’espaces de la vie civique, et l’on s’interroge sur les raisons de la construction de tant de bâtiments nouveaux. Dans un second temps, une étude plus transversale de l’espace urbain décrit comment se met en place à cette époque un cadre de vie véritablement urbain, avec un paysage, des aménagements et une organisation de l’espace bien spécifique. La troisième partie consacrée aux thématiques économiques montre comment la prospérité des cités se traduit dans la pierre : la construction de bâtiments pour abriter les activités économiques témoigne autant du souci des cités de développer et d’encadrer ces activités que de la richesse de la vie économique des poleis. Ce dynamisme contribue aussi à expliquer une activité de construction soutenue, rendue possible par l’existence de ressources abondantes et variées à la disposition des cités. La réflexion porte pour finir sur la dimension politique et sociale des transformations de l’espace urbain. Cette dernière partie se place dans une perspective historique plus large, celle de l’évolution de la cité hellénistique
The Hellenistic period is the time when the aspect of the cities of Ionia and Caria is changing gradually. In almost each city, an amount of new public buildings progressively shaping a new urban landscape that looks like a mirror of the city that created it. It is this unprecedented transformation of urban centers during the Hellenistic period that this thesis studies, with attention to the cities of Ionia and Caria in all their diversity. We aim at making sense of the changes in these two regions, which experienced hellenisation and urbanisation early ; they are also characterized by interactions between cities and Hellenistic kings. This study suggests ways of understanding civic societies through the city. We are looking at t the most remarkable features of the city : its public buildings . In the first part devoted to urban fortifications, buildings housing political activities , and areas of cultural life , public monuments are mentioned as spaces of civic life , and we search for the reason why many new buildings were built. Then, the study describes how urban space becomes a place of truly urban life, with a landscape, facilities and a specific spatial organization. In a third section, we show how the cities’ economic prosperity is reflected in stone buildings – some of them housing economic activities – reflects the will of cities to develop and oversee economic activities and the wealth of the poleis. This also helps explain a sustained construction activity made possible by the existence of abundant and varied resources available to cities. Finally, the reflection deals with political and social aspects of the evolution of urban space. This last part is placed in a broader historical perspective, that of the evolution of the Hellenistic city

The population structure of fishery resources and the impact of environmental factors over its productivity are important processes to be considered in fisheries management. Environmental factors could determine both, the success of larval drift as the population spatial structure and its changes of biomass. Considering this, two key elements in the adequate, sustained exploitation of any fishery should be considered; the biological attributes of the species and how these vary over time and space. Research is needed to obtain a more thorough understanding of these effects, how they vary, and how they relate to environmental factors. However, spatial processes rarely constitute an explicit consideration in the evaluation and management of marine invertebrate populations, but this is particularly important in processes in which larval drift acts as one of the main mechanisms of population expansion. The ecological concept metapopulation is widely used and accepted for understanding low-mobility marine populations, and its implications for fishery management purposes should be considered. In this work we show the environmental effect over distribution, abundance and spatial structure of nylon shrimp population (Heterocarpus reedi) off central Chile (25°-37°S) from trawling surveys carried out between 1996 and 2011. Environmental variables considered where sea surface concentration of chlorophyll-a and dissolved organic matter. Results show a geographical separation in population around 32°S. Shrimp density is higher in the southern zone, where concentration of chlorophyll-a and dissolved organic matter are high due to presence of river tributaries and coastal upwelling zones. In this area, the bulk of the adult population is concentrated, which could act as "source" population and thereby its influence on larval drift could explain both, the preponderance of juveniles in the northern area as the smallest size of its population (“pseudo-sink” population). In the southern area, a process of spatial and bathymetric expansion had driven the increase in population size over time, where the colonization and individual somatic growth had been the main mechanisms. We found that periods of good environmental conditions explain high densities of shrimp with a delay of two years, which might be related mainly with larval survival and enhanced recruitment and somatic growth. In order to do a cross check of this proposal, and based on a complementary information source, 17 years of biological data collected from nylon shrimp fishery off central Chile were analyzed. We analyze these data using generalized linear models and determine the factors responsible for changes in carapace length, body weight, maturity, and sex ratio. better physical conditions and reproductive attributes of H. reedi south of 32°S would be related with the best environmental and food conditions at this zone. For example, individuals are larger, females are longer at first maturity (CL50%), and mature females are less prevalent. We outline a theoretical foundation that can guide future research on H. reedi. We also suggest that future conservation measures consider biological attributes within a spatial context. Finally, in order to contrast different hypotheses of population structure and spatial connectivity proposed along this work, we proposed a length-based population model and analyzed the biologic and fishery information available since 1945 under three hypotheses, based on the connectivity rate of two subpopulations located to the north and south of 32°S. The results show that, statistically, several hypotheses can be used to explain the data. The most likely hypothesis is that of a metapopulation in which the south zone acts as a source population (reproductive refuge) and determines, partially or totally, the arrival of recruits in the north zone, thereby explaining the population increase over the last decade. According to our study, empirical evidence will strengthen the hypothesis of spatial connectivity and, given the implications for managing the fishery of this resource, special attention should be paid to the biological-fishery conditions recorded south of 32°S, caution in its exploitation levels and consider this zone as reproductive refuge of nylon shrimp.
L'estructura poblacional dels recursos pesquers i l'impacte dels factors ambientals sobre la productivitat són processos importants a tenir en compte per a la gestió de les seves pesqueries. Els factors ambientals poden determinar l'èxit de la deriva larvària, l'estructura espacial de la població, així com les variacions de la biomassa. Tenint en compte aquests aspectes, s’haurien de considerar dos elements clau per a una explotació adequada i sostinguda de qualsevol pesqueria: les característiques biològiques de les espècies i com aquestes poden variar en el temps i en l’espai, essent necessària la millora de la comprensió d'aquests efectes, com varien, i com es relacionen amb els factors ambientals. No obstant això, els processos espacials rarament són considerats explícitament en la valoració i gestió de les poblacions d'invertebrats marins, més quan aquests aspectes són particularment importants en els processos de deriva larval actuant de principal mecanisme d'expansió d'una població. El concepte ecològic de metapopulations és àmpliament utilitzat i acceptat per a la comprensió de les poblacions marines de baixa mobilitat, i les seves implicacions haurien de ser considerades a la gestió pesquera. En aquest treball es demostra l'efecte del medi en la distribució, abundància i estructura espacial de la població de la espècie de crustaci decàpode Heterocarpus reedi anomenada a Xile en castellà com a “Camarón nailon”. S’ha mostrejat aquesta espècie a a la zona central de Xile (25 ° - 37 ° S) a partir de la informació obtinguda en campanyes oceanogràfiques de pesca d'arrossegament fets entre els anys 1996 i el 2011, així com de les característiques de l’aigua superficial (concentració de clorofil·la α i de la matèria orgànica dissolta). Els resultats van mostrar una separació geogràfica de la població a 32 ° S, on la densitat de gambes és més gran, així com també la concentració de clorofil·la α i la dissolució de matèria orgànica, això darrer degut segurament a la presència d'afluents dels rius i zones d'aflorament costaner. En aquesta zona es concentra la major part de la població adulta i podria actuar com a població “font” i la seva influència en la deriva larvària explicaria tant la preponderància de juvenils en la zona nord així com una població menys abundant (població “pseudo-sumider”). A la zona sud, l'augment de mida de la població s'explica per un procés d'expansió espacial i batimètric a traves del temps, on la colonització i el creixement somàtic dels individus serien els principals mecanismes. Els períodes de condicions ambientals favorables explicarien les altes densitats de individus de l’espècie niló dos anys després. Aquestes condicions ambientals favorables podrien estar principalment relacionades amb la supervivència de les larves, l'èxit dels processos de reclutament i el posterior creixement somàtic. D'altra banda, i amb l’objectiu de fer una verificació dels resultats dalt explicats, i basant-se en una font d'informació complementària, es van analitzar 17 anys de dades biològiques recollides en mostrejos pesquers del “camaron nylon” davant de la costa central de Xile. Es van analitzar aquestes dades utilitzant models lineals generalitzats (GLM) per tal de determinar els factors responsables dels canvis en la longitud del cefalotòrax, el pes del cos, la maduresa sexual i la proporció de sexes. Es va determinar una notable heterogeneïtat espacial en les característiques biològiques dels individus de H. reedi. Els individus en millor condició es van trobar al sud de la latitud de 32 ° S i aquesta millor condició es va relacionar amb les millors condicions ambientals i de menjar en aquesta zona. Per exemple, els individus són més grans, les femelles assoleixen abans el tamany de primera maduresa (CL50%), i les femelles madures són menys freqüents. Amb aquests resultats es presenta una base teòrica que pot guiar la recerca sobre les poblacions de H. reedi tenint en compte les consideracions espacials en les futures mesures de conservació. Finalment, per poder comparar diferents hipòtesis sobre l'estructura de la població i connectivitat espacial proposades al llarg d'aquest treball, es presenta un model de població basat en la talla i s’ha analitzat la informació biològica i pesquera disponible des de 1945. S’han tingut en compte tres hipòtesis en funció de la taxa de connectivitat de les dues subpoblacions, es a dir, les situades al nord i al sud de 32 ° S. Els resultats van mostrar que, estadísticament, diverses hipòtesi es poden fer servir per a explicar les dades disponibles. La hipòtesi més versemblant és la d'una metapoblació en la qual la zona sud actua com a població font o refugi reproductiu. Aquesta població determina parcialment o totalment l'arribada de reclutes a la zona nord i podria explicar l'augment d'aquesta població trobat a l'última dècada. Segons el nostre estudi, la hipòtesi de connectivitat espacial ha de ser contrastada només amb l'evidència empírica. Tenint en compte les implicacions per a la gestió pesquera, s’hauria de prestar una especial atenció a les condicions biològico-pesqueres que es registren al sud de 32 ° S, tenir especial precaució als nivells d'explotació pesquera i considerar aquesta zona (sud del 32 ° S) com a refugi reproductiu a Xile de l’espècie H. reedi.

La présente thèse vise à apporter des éclaircissements sur la réapparition du souci défensif, sa matérialisation et son évolution en Anatolie occidentale et centrale au début du premier millénaire av. J.-C. (Xe-VIe s.). Le territoire soumis à l'examen comprend la Phrygie, la boucle de l'Halys, la Carie, la Lydie, l'Ionie, l'Eolide et la Troade. Cette étude s'intéresse en premier lieu aux différentes méthodes de fortification utilisées au cours de cette période. Par l'examen des principales caractéristiques architecturales des murs de défense (techniques de construction, dispositifs défensifs), cette étude cherche à déterminer de quelle manière ces nouvelles constructions s'inscrivent dans la tradition architecturale anatolienne et dans quelle mesure leurs concepteurs contribuèrent à l'évolution de celle-ci en adoptant et en transformant les méthodes de fortification qui en sont issues. La construction d'un rempart, parce qu'elle impliquait de nombreux acteurs, était un fait de société majeur. Par leur conception, les techniques utilisées pour leur construction, leur emprise dans le paysage, les murailles sont des monuments chargés de symboles et des témoins privilégiés de l'histoire des sociétés qui les ont construites et perfectionnées. Au-delà des considérations archéologiques, cette étude s'attache donc aussi à replacer la construction de fortifications dans le contexte militaire mouvementé de l'Anatolie préclassique et tente également d'évaluer l'impact d'un tel projet de construction dans l'histoire politique et sociale des populations anatoliennes de l'âge du fer.

碩士
南台科技大學
生物科技系
96
Branched chain fatty acids (BCFAs) are fatty acids substituted with alkyl groups. Many of them are chiral and therefore occur in two enantiomeric forms. Chiral BCFAs have been recognized as important flavour components. 2-Methylalkanoic acids and their derivates of high enantiomeric purities have also served as valuable synthetic intermediates. Lipase-catalyzed enantioselective esterification between (R,S)-2-methylalkanoic acids and n-butanol in organic solvents was developed to produce (S)-butyl 2-methylalkanoate. Partilly purified Carica papaya lipase (pCPL) was uesd to study the effect of organic solvents, reaction temperature, various methods of pretreated enzyme and different alkyl chain length of the chiral center of (R,S)-2-methylalkanoic acids. Isooctane was selected to use for optimally reaction medium. The increase of enantioselectivity of the pCPL was observed with the increase of the straight alkyl chain length of the chiral center of (R,S)-2-methylalkanoic acids from ethyl to pentyl in the esterification reaction. The enantioselectivity for pCPL was exceeded 100 for the kinetic resolution of (R,S)-2-methylheptanoic acid in isooctane, but for the the kinetic resolution of (R,S)-2-methylbutyric acid was only reached about 2 in isooctane. An effect of water activity (aw) on reaction rate and enatioselectivity was observed. The pCPL exhibited an optimal water activity for maximum esterrification rate VS,Q and enantioselectivity E at 0.06 and 0.33, resprctively. Measurements of the temperature dependence of E allows for separation of the enthalpic and entropic components of enantioselectivity. Changes in E with alkyl chain length of the chiral center of (R,S)-2-methylalkanoic acids were mainly caused by changes in the enthalpic component.

博士
國立中興大學
園藝學系所
101
Studies on effects of natural type S-ABA on seed germination and seedling growth of papaya (Carica papaya L. cv. Tainung No. 2) were evaluated for clarify function of S-ABA. Seed germination was investigated by soaking seeds into distilled water and various concentrations of S-ABA. Percentage of seed germination in filter paper and growth medium experiments were increased by S-ABA treatments. These treatments significantly increased germination percentages (88 and 91 %, respectively) compared to control (70 and 76 %, respectively). Enhancement of germination velocity index (GVI) and seedling vigor index (VI) were obtained from treatment of S-ABA 0.01 and 0.1 ppm. While, high concentration of S-ABA (10 ppm) reduced seed germination, and resulted in abnormal germinants. However, S-ABA 1 ppm had no effect on seed germination. Young seedling stage, seedlings were treated by 2 methods of S-ABA application, foliar spray and medium supply. Results showed that S-ABA treatments increased seedling growth, especially number of leaves and roots, and fresh weight of shoot in both two application methods. Fresh weight of roots was increased by S-ABA only in foliar spray method while medium supply of S-ABA resulted in roots were small and fine. The investigation of anatomical characteristics in leaf, stem and root was supported this study. Number of palisade cell in leaf of treated seedlings was significantly increased compared to control ones. In addition, length of these cells in treated seedlings was increased but width of cell was reduced, led to leaves were dark green compared to untreated seedlings. S-ABA treatments could improve number of cell in stem and root and also increase vascular system in stem and root. Moreover, increasing in layer number of pith in stem was found from S-ABA treatments as well. Further, arrangement of cell in all three parts was more compact compared to untreated seedlings. Effects of S-ABA on nutrient and total sugar content were evaluated. S-ABA could significantly improve N and K content in all parts of seedlings, P and total soluble sugar content was increased trendily in some part of seedling. For dry weight of nutrients in whole plant, S-ABA could improve N, P, K and total soluble sugar in both two treatments of foliar spray and medium supply. Further, in 6 weeks after treatment, medium supply of S-ABA became to be more positive effect than foliar spray plants. It was found in this study that S-ABA belongs to growth promoter in tropical fruit tree, papaya. The concentration in 0.1 ppm was more effect on seedling growth and nutrient accumulation. The foliar spray of S-ABA had positive effect on leaf growth, thereafter indirectly improved stem and root growth. Moreover, the introducing of medium supply method directly enhanced root growth.

博士
國立成功大學
化學工程學系碩博士班
93
For the first time, the crude papain as the spary-dried latex from Carica papaya (EC 3.4.22.2) is discovered as a versatile enantioselective biocatalyst for obtaining chiral acids from their racemic thioesters. The dogma of this thesis is to develop the lipase-catalyzed kinetic resolution and dynamic kinetic resolution processes for obtaining the chiral profen from the corresponding (R,S)-profen thioesters. 　The hydrolytic resolution of (R,S)-naproxen 2,2,2-trifluoroethyl thioester via a crude Carica papaya lipase in water-saturated organic solvents is first employed as the model system, in which effects of temperature and solvents on the lipase activity and enantioselectivity are first investigated. An optimal temperature of 60oC for the initial rate of (S)-thioester and a high enantiomeric ratio greater than 100 at 45oC in isooctane are obtained. A kinetic analysis by considering product inhibition and lipase deactivation is furthermore performed in water-saturated isooctane at 45oC, leading agreements of experimental and best-fit time-course conversions. A detailed comparison of the kinetic and thermodynamic behaviors of Carica papaya and Candida rugosa lipases in isooctane and cyclohexane indicates that both lipases are very similar in terms of the thermodynamic parameters of ΔΔH and ΔΔS, E value and initial rate for the (S)-substrate when either (R,S)-naproxen thioester or ester is the substrate. 　With the hydrolytic resolution of (R,S)-naproxen 2,2,2-trifluoroethyl thioesters in water-saturated isooctane as a model system, improvements of the specific lipase activity and thermal stability were found when a crude Carica papaya lipase was partially purified and employed as the biocatalyst. Improvements of lipase activity and enantioselectivity were obtained when polar organic solvents, pH 8 buffer or aqueous solution containing methyl-b-cyclodextrin, but not NaCl or 18-crown-6, were employed in the pretreatment. The lipase pretreated with isopropyl ether was selected as the best lipase and employed for the resolution of (R,S)-profen 2,2,2-trifluoroethyl thioesters. The partially purified Carica papaya lipase (pCPL) was furthermore explored as an effective enantioselective biocatalyst for the hydrolytic resolution of (R,S)-profen thioesters in water-saturated organic solvents. The kinetic analysis in water-saturated isooctane indicated that both acyl donor and acyl acceptor have profound influences on the lipase activity, E value and enantioselectivity. Inversion of the enantioselectivity from (S)- to (R)-thioester was found for (R,S)-fenoprofen and (R,S)-ketoprofen thioesters that contained a bulky substituent at the meta position of 2-phenyl moiety of the acyl part. Kinetic constants for the acylation step were furthermore estimated for elucidating the kinetic data and postulating an active site model. The thermodynamic analysis indicated that the enantiomer discrimination was driven by the difference of activation enthalpy (ΔΔH) and that of activation entropy (ΔΔS), yet the former was dominated for most of the reacting systems. The postulated active site model was supported from the variation of ΔΔH and ΔΔS with the acyl moiety, in which a good linear enthalpy-entropy compensation relationship was also illustrated. A comparison of the performances between Candida rugosa lipase (CRL) and pCPL indicated that pCPL was superior to CRL in terms of the better thermal stability, similar or better lipase activity for the fast-reacting substrate, time-course-stability and lower enzyme cost. Both racemization and non-enzymatic hydrolysis of (R,S)-profen thioesters with trioctylamine as the catalyst follow the Hammett relationships. The dynamic kinetic resolution of the substrate by adding trioctylamine as the racemization catalyst and enzyme activator was furthermore performed, giving improvements on the yield and stereo-purity for the (S)-naproxen product. Similar enzyme behaviors for pCPL were demonstrated when 2,2,2-trifluoroethyl thioesters of (R,S)-fenoprofen and (R,S)-flurbiprofen were replaced as the substrate. With hydrolysis of olive oil in aqueous solutions and hydrolytic resolution of (R,S)-profen 2,2,2-trifluoroethyl thioesters in water-saturated isooctane as the model systems, the lipolysis and enantioselective hydrolysis activities of four partially purified Carica papaya lipases of different plant variety and geography location of cultures were compared and selected pCPL-Indo from 　Indonesia as the best lipase preparation. For lipolysis, an optimal pH of 8.5 for all lipase preparations was found. Yet, pCPL-Indo possessed the highest activity at pH ranged from 7 to 10. For the kinetic resolution, the thermodynamic analysis implied that pCPL-Indo has changed the conformation at 60 oC and the enantiomer discrimination was dominated by ΔΔH. The kinetic analysis also indicated that the enantiomeric discrimination was mainly due to the difference of k2S and k2R in the acylation step. Agreements between the experimental time-course conversions XS and best-fitted results were illustrated by considering product inhibition and enzyme deactivation effects.

博士
國立成功大學
化學工程學系碩博士班
94
ABSTRACT The papaya lipase stored in the crude papain from spay-dried latex of Carica papaya has been discovered as a versatile enentioselective biocatalyst to obtain chiral acids by using hydrolytic resolution of their racemic esters. The dogma of this dissertation is to improve the lipase-catalyzed hydrolysis of (R,S)-naproxen ester practised by adopting the enzyme screening, purification, medium engineering, and substrate engineering concepts. In terms of the enzyme screening and purification, we employed the hydrolytic resolution of (R,S)-naproxen 2,2,2-trifluoroethyl ester via a crude Carica papaya lipase in water-saturated organic solvents as the model system, where effects of temperature and solvents on the lipase activity and enantioselectivtiy were studied. The optimal temperature of 60℃ for the maximum initial rate of (S)-ester with a high enantiomeric ratio (E = 122) in water-saturated isooctane is obtainable. Additionally, less hydrophobic solvents of cyclohexane and MTBE than isooctane are vital on decreasing the lipase activity and enentioselectivity. A kinetic analysis is further performed by using a Michaleis-Menten mechanism combined with the product inhibition and lipase deactivation, leading to good agreements of experimental and best-fitted conversions. Comparisons of enzyme performances for Carica papaya and Candida rugosa lipases indicate that the former is more enantioselective, active, and stable for (S)-naproxen ester. A crude lipase stored in Caraica pentagona Heilborn latex was explored as an effective enantioselective biocatalyst for the hydrolytic resolution of (R,S)-naproxen 2,2,2-trifluoroethyl ester in water-saturated solvents. A comparison of the enzyme performances in terms of activity or enantioselective with those from Carica papaya lipase indicates that both enzymes display low tolerance to the hydrophilic solvent and are inhibited by (S)-naproxen or 2,2,2-trifluoroethanol. Improvements on the lipase activity and enantioselectivity are found when using both lipases in partially purified form as the biocatalysts. By utilizing the thermodynamic analysis, the enantiomeric discrimination is mainly driven by the difference of activation enthalpy for all reaction systems except for the hydrolysis of (R,S)-fenoprofen 2,2,2-trifluoroethyl thioester employing Carica papaya lipases as the biocatalyst. As for medium engineering, the performance of pCPL for the hydrolytic resolution of (R,S)-naproxen 2,2,2-trifluoroethyl ester in water-saturated isooctane is altered when adding a variety of organo-soluble bases that act as either enzyme activators (i.e. TEA, MP, TOA. DPA, PY, and DMA), or enzyme inhibitors (i.e. PDP, DMAP, and PP). Triethylamine (TEA) was selected as the best enzyme activator as 2.24-fold increase of the initial rate for (S)-naproxen ester was achieved when adding 120 mM of the base. Furthermore, the activity enhancement for all lipases can also be observed, but with a negative effect on enantioselectivity, except for the partially purified lipase from Carica pentagona Heilborn as 60 mM TEA is added. By applying an expanded Michaelis-Menten mechanism for the acylation step, the kinetic analysis indicates that the proton transfer for the breakdown of tetrahedral intermediates to acyl-enzyme intermediates is more affected than that for the formation of tetrahedral intermediates when adding an enzyme activator. However, no correlation for the proton transfer in the acylation step is found when adding the base acting as an enzyme deactivator. As for substrate engineering, with the hydrolytic resolution of (R,S)-naproxen ester via pCPL in water-saturated isooctane at 45℃ as the model system, the substrate containing a leaving group of different electron-withdraw capability has an extreme influence on the enzyme activity. About 630-fold enhancement of the initial rate for (S)-ester are obtainable when increasing the inductive parameter from 0.01 to 0.4 for the alcohol without containing a dimethylamino group. This implies that the acylation step must be the rate-limiting step. Meanwhile, we also assume that the bond-breaking of tetrahedral intermediate to acyl-enzyme intermediate may be the rate-limiting step for the compounds that alcohol group is hard to leave (e.g. 0.01 to 0.11). On the other hand, a novel means of using substrate-assisted catalysis indicates that the proton shuttle device acts as an effective tool for improving the lipase activity by forming an extra intramolecular hydrogen bond in the transition state. For the substrates with the same inductive parameter of 0.01 or 0.03, about 61-fold enhancement of lipase activity is obtainable. Moreover, about 80 ~ 90-fold increase of k2S/KmS implies the free energy difference of 11.5 ~ 11.9 kJ/mol between the transient states if one assumes the same ground states for both substrates. These values agree well with the stabilization by an additional hydrogen bond. Similar results for the activity enhancement are also found for using other lipases.

碩士
南台科技大學
生物科技系
98
Branched chain fatty acids (BCFAs) are fatty acids substituted with alkyl groups. Many of them are chiral and therefore occur in two enantiomeric forms. Chiral BCFAs have been recognized as important flavour components. 2-Methylalkanoic acids and their derivates of high enantiomeric purities have also served as valuable synthetic intermediates. The purpose of this research is aimed to study the effect of organic solvents, reaction temperature, and different alkyl chain length of the chiral center of (R,S)-2-methylhexanoic acid esters by using partilly purified Carica papaya lipase ( pCPL ). The hydrolytic resolution of (R,S)-butyl-2-methylhexanoic ester via pCPL in different water-saturated solvents at 35℃ is employed as the model system for studying the effects of solvents on the lipase activity and enantioselectivity, where water-saturated isooctane are beneficial for giving better lipase activity and enantioselectivity. A comparison of pCPL enantioselectivity of alkyl chain straight for (R,S)-2-methylhexanoic acid esters of different indicates that (R,S)-butyl-2-methylhexanoic ester gives the best lipase activity. The thermodynamic analysis indicates that the enantiomer discrimination is driven by the difference of activation enthalpy ( ΔΔH ) and that of activation entropy ( ΔΔS ), yet the former is dominated for most of the reacting systems and has a good linear compensation relationship with the latter. Similar of the E value for different alkyl chain lengths of the chiral center of (R,S)-2-methylhexanoic acid esters were mainly attentted by both enthalpic and entropic changes.

碩士
銘傳大學
國際事務研究所碩士班
98
Most research about Haiti’s integration into CARICOM stresses the stakes of the adhesion, mainly the plausible detriments that could be followed. This research, instead, discusses the economic upshot of this integration on Haiti’s economic development by assessing the economic performance and global trade of Haiti from 1998 to 2008, analyzes the evolution of intra-CARICOM trade and that between CARICOM members and the rest of the world for the same period, and figures out the significance of Haiti’s trade volume in intra-CARICOM trade.The research also identifies policies that could play a major role in helping the integration of Haiti into CARICOM lead to economic growth and development. The research shows that, unlike the Bahamas, Trinidad & Tobago, Barbados, and Guyana, there is no clear sign of the classical benefits of trade creation and competitiveness enhancing that Haiti has gained from joining CARICOM. For the past decade, Haiti’s GDP growth rate has been showing an undulatory trend and therefore could not been sustained. The research indicates that the contribution of CARICOM to the development of Haiti’s economy is quasi negligible despite trade between Haiti and the Caribbean Community, in terms of volume, has slightly increased for the past ten years. The research also formulates some valuable suggestions for Haiti to, beyond doubt, benefit from its integration into CARICOM.

博士
國立成功大學
化學工程學系碩博士班
93
(I) An analytical solution for the dynamic kinetic resolution of enzyme-catalyzed irreversible acyl transfer was employed to study the side-reaction effects on the yield and optical purity of the desired enantiomeric product. A lipase-catalyzed enantioselective thiotransesterification between (R, S)-naproxen 2,2,2-trifluoroethyl thioester and 4-morpholine ethanol with in situ racemization of (R)-thioester using trioctylamine as the racemization catalyst in isooctane was designed as a model system to compare the theoretical predictions. Under an initial water activity of 0.113, adding trioctylamine was found to have profound effects on the hydrolysis side-reactions, thus enhancing the chemoselectivity of the lipase to the alcohol in comparison with water. Theoretical analysis also indicated that the time-course yield and the enantiomeric excess for the desired enantiomer could be improved if the employed lipase had higher activity and enantioselectivity for the hydrolysis and esterification side-reactions, especially when the base had a similar racemization rate compared with the rate of the fast-reaction substrate. 　(II) A partially purified Carica papaya (pCPL) was explored as an effective biocatalyst for the esterification resolution of various (RS)-2-chlorophenoxypropionic acids (CPP) with trimethylsilylmethanol in anhydrous isooctane. In comparison with the performance of crude Candida rugosa lipase, pCPL has high E value (> 100) for 2-chloro and 4-chloro but not 3-chloro substituted CPP. More than an order-of-magnitude lower reactivity was obtained for the hindered substrate of (RS)-2-(2-chlorophenoxy)propionic acid. The thermodynamic analysis indicates that the enantiomeric discrimination for all reaction systems is mainly driven by the difference of activation enthalpy. A good enthalpy-entropy compensation effect between -ΔΔH and -ΔΔS is demonstrated and elucidated for the region-effect of substrates containing 2-, 3- or 4-chloro substituent. The kinetic analysis indicates that pCPL is inhibited strongly by the acid substrate, but to a less extent by the alcohol substrate. However with the penalty of decreasing pCPL activity, the E value in isooctane can be greatly enhanced when trimethylsilylmethanol concentration higher than 40 mM is employed.