Dissertationen zum Thema „VDA 6.3“

Menar du vad jag förstår? är en studie av barns språkutveckling i ett 3-6 -årsperspektiv. Syftet med följande studie är att vi vill undersöka specialpedagogens roll i barns språkliga utveckling. Vilka kunskaper behöver specialpedagogen för att upptäcka, stödja och stimulera barnens språkutveckling? Vår studie genomfördes genom litteraturstudier kring vår problemformulering, samt genom kvalitativa intervjuer med specialpedagoger. I problemformuleringen ingår barns språkutveckling, diagnosmaterial, språkträning, stimulans och konsekvenserna av en försenad språkutveckling. Respondenterna bestod av åtta specialpedagoger som främst arbetar inom förskola och förskoleklass. Vårt resultat av studien visar sammanfattningsvis att specialpedagogens roll i barns språkliga utveckling främst är att handleda, fortbilda, inspirera och medvetandegöra personal och föräldrar om barns språk. Specialpedagogen upptäcker tillsammans med föräldrar, förskolepersonal, BVC och logoped barn med sen språkutveckling. Specialpedagogen använder sig av observations- och diagnos- material. Barnet stimuleras framförallt i sin grupp i den dagliga verksamheten. Många specialpedagoger har nämnt att läs- och skrivinlärningen blir påverkad av sen språkutveckling, men även att barnet kan bli utåtagerande eller tyst och har svårt med det sociala samspelet. Vi har utgått ifrån Vygotskijs teori där den sociala miljön utvecklar barnet och barnet ska vara aktivt i sin inlärning och kunna utveckla sin personlighet och kreativitet.

Testou-se o xarope de alfarroba como fonte de carbono alternativa quer para crescimento quer para produção de DHA pela microalga heterotrófica marinha Crypthecodinium cohnii. Numa fermentação em fed-batch, utilizando xarope de alfarroba diluído, suplementado com extracto de levedura e sal do mar, as produtividades em biomassa e em DHA foram 420 mg/Lh e 18,5 mg/Lh, respectivamente, após 100,4 h. Investigou-se o efeito da adição de n-dodecano como vector de oxigénio, no crescimento e na produção de DHA por Crypthecodinium cohnii. Após 86,7 h de fermentação, a concentração de biomassa, a taxa específica de crescimento, os teores de DHA e de ácidos gordos totais foram superiores na fermentação contendo 1% (v/v) de n-dodecano, comparativamente à fermentação de controlo. Foi desenvolvido um procedimento simples e pouco dispendioso que envolve a saponificação e metilação da biomassa húmida, seguidas de winterização e complexação com ureia, de forma sequencial, para concentrar o DHA extraído da biomassa. A fracção mais pura em DHA (99,2% do total de ácidos gordos) foi obtida para uma razão ureia/ácidos gordos de 3,5 (m/m), às temperaturas de cristalização de 4 e 8 °C. ⓿⓿⓿ABSTRACT: Carob pulp syrup was tested as an alternative carbon source for either the heterotrophic marine microalga Crypthecodinium cohnii growth or DHA production. ln a fed-batch fermentation using diluted carob pulp supplemented with yeast extract and sea salt, biomass and DHA productivity were 420 mg/lh and 18.5 mg/lh, respectively after 100.4 h. The effect of n-dodecane as an oxygen vector on Crypthecodinium cohnii growth and DHA production was investigated. After 86.7 h of fermentation, biomass concentration, specific growth rate, DHA and total fatty acid production were higher in the 1% (v/v) n-dodecane fermentation, compared to control fermentation. A simple and inexpensive procedure involving saponification and methylation over wet biomass, winterization and urea complexation in a sequential way has been developed in order to concentrate DHA from algal biomass. The purest DHA fraction (99.2% of total fatty acids) was found at the urea/fatty acid ratio of 3.5 (w/w) at the crystallization temperatures of 4 and 8 °C.

Made available in DSpace on 2016-01-26T18:55:43Z (GMT). No. of bitstreams: 1 DANIELLE ALVES SILVA.pdf: 987458 bytes, checksum: 32662d7c7f3cc988d4d70c1f1d44b609 (MD5) Previous issue date: 2014-03-20
The keratoconjunctivitis sicca ( CCS ) , or dry eye, is a common chronic inflammatory eye disease in dogs and humans , which occurs due to deficiency of production of the aqueous portion of the tear film ( quantitative deficiency ) and / or excessive tear evaporation (disability qualitative ) , mainly affecting the cornea and conjunctiva may result in blindness . Treatment consists mainly in the use of tear substitutes as the use of immunosuppressive drugs (cyclosporine , tacrolimus and pimecrolimus ) (Stevenson et al , 2012) . Some studies in medicine and veterinary showed good results in controlling the CCS with the use of essential fatty acids (AGE ) , ω -3 and ω -6 , due to its ability to produce anti -inflammatory mediators ( BARABINO et al. 2003 , . NEVES et al , 2013 ) How fish oil and flaxseed oil are sources of AGE , but with differences in composition and concentration , and to the present time there is a comparative study of the efficacy of these compounds in the treatment of CCS . The objective of this study is to compare these two important sources of ω - 3 and ω - 6 , orally , in the treatment of experimentally induced in rabbits CCS .In order to compare the efficacy in the treatment of keratoconjunctivitis sicca ( CCS ) induced experimentally in rabbits , between two sources of omega 3 and 6 orally , fish oil ( FO) and linseed oil ( OL ) . We used 28 female rabbits of New Zealand breed , divided into 4 groups of 7 animals each : Group C (control ) , Group OP ( fish oil) , OL Group ( flaxseed oil ) and Group OPL ( Oil fish oil and flaxseed ) . The animals were evaluated by Schirmer Tear Test ( TLS ) , Rose Bengal Test ( TRB ) , Fluorescein test ( TF ) , Time Tear Film Break ( TRFL ) , ocular cytology and histopathology . The results showed a significant increase in the values of TLS and TRFL in all treatment groups , but this increase was earlier in the OP group . TRB in the performance of the groups was similar. With respect to the parameter TF , negative marking was delayed in group OPL . There was a significant decrease in the number of goblet cells in the OPL group in relation to other grupos.Os results showed that OL and OP orally improve the clinical signs of CCS , however this improvement was more rapid with the OP . The combined use of oils brought no additional benefit . These results can help in the future with new oral formulations useful in the adjuvant treatment of CCS .
A ceratoconjuntivite seca (CCS), ou olho seco, é uma doença ocular inflamatória crônica frequente em cães e humanos, que ocorre devido a deficiência de produção da porção aquosa do filme lacrimal (deficiência quantitativa) e/ou pela evaporação excessiva da lágrima (deficiência qualitativa), afetando principalmente a córnea e a conjuntiva podendo evoluir para cegueira. O tratamento consiste principalmente no uso como substitutos da lágrima e o uso de imunossupressores (ciclosporina, tacrolimus e pimecrolimus) (STEVENSON et al, 2012). Alguns estudos na Medicina e na Veterinária mostraram bons resultados no controle da CCS com a utilização de ácidos graxos essenciais (AGE), ω-3 e ω-6, devido à sua capacidade de produzir mediadores anti-inflamatórios (BARABINO et al., 2003; NEVES et al., 2013) Como o óleo de peixe e o óleo de linhaça são fontes de AGE, porém com diferenças na sua composição e concentração, e até o presente momento não há um estudo comparativo da eficácia destes compostos no tratamento da CCS. O objetivo deste estudo foi comparar a eficácia no tratamento de ceratoconjuntivite seca (CCS) induzida experimentalmente em coelhos, entre duas fontes de ômega 3 e 6 por via oral, o óleo de peixe (OP) e o óleo de linhaça (OL). Foram utilizados 28 coelhos, fêmeas, da raça Nova Zelândia, divididos em 4 grupos com 7 animais cada: Grupo C (controle), Grupo OP (óleo de peixe), Grupo OL (óleo de linhaça) e Grupo OPL (óleo de peixe e óleo de linhaça). Os animais foram avaliados pelo Teste Lacrimal de Schirmer (TLS), Teste de Rosa Bengala (TRB), Teste de Fluoresceína (TF), Tempo de Ruptura do Filme Lacrimal (TRFL), citologia ocular e análise histopatológica. Os resultados demonstraram que houve aumento significativo nos valores de TLS e TRFL em todos os grupos de tratamento, porém esse aumento foi mais precoce no grupo OP. No TRB o desempenho dos grupos foi similar. Com relação ao parâmetro TF, a marcação negativa foi mais tardia no grupo OPL. Houve uma diminuição significativa no número de células caliciformes no grupo OPL em relação aos demais grupos.Os resultados demonstraram que o OP e OL por via oral melhoram os sinais clínicos da CCS, porém essa melhora foi mais rápida com o OP. O uso combinado dos óleos não trouxe benefício adicional. Esses resultados podem contribuir no futuro com novas formulações orais úteis no tratamento adjuvante da CCS.

Submitted by PPG Pediatria e Sa?de da Crian?a (pediatria-pg@pucrs.br) on 2018-01-02T16:42:12Z No. of bitstreams: 1 Tese Lidiane.pdf: 1449534 bytes, checksum: 483272938ee77a60ad54caa8f898d243 (MD5)
Approved for entry into archive by Caroline Xavier (caroline.xavier@pucrs.br) on 2018-01-24T12:15:04Z (GMT) No. of bitstreams: 1 Tese Lidiane.pdf: 1449534 bytes, checksum: 483272938ee77a60ad54caa8f898d243 (MD5)
Made available in DSpace on 2018-01-24T12:17:42Z (GMT). No. of bitstreams: 1 Tese Lidiane.pdf: 1449534 bytes, checksum: 483272938ee77a60ad54caa8f898d243 (MD5) Previous issue date: 2017-08-31
Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES
Introduction: acute bronchiolitis (AB) is an inflammatory disease of the airways considered the most common pathology of the lower respiratory tract in childhood. Responsible for a large number of hospitalizations in infants is one of the leading respiratory diseases worldwide, raising the costs of health care in infants. According to epidemiological data, between 75,000 and 125,000 children are hospitalized in the United States each year with infections caused by respiratory syncytial virus (RSV), accounting for approximately 25% of pediatric pneumonia and up to 70% of hospitalizations for acute bronchiolitis. Children with deficiencies in cell-mediated immunity can develop more severe and prolonged infections. Activation of the mTOR, STAT-3 and STAT-6 signaling pathways have been identified as key regulators in different functions of the immune system. The aim of this study was to investigate the relationship between the gene expression of mTOR, STAT-3, STAT-6 and AB severity. Methods: it is a cohort study that included a group of infants less than 12 months old with AB admitted to a tertiary hospital in Porto Alegre, Brazil. Nasopharyngeal lavage was collected from all patients and stored in Trizol solution at -80?C at the Biomedical Research Institute (IPB) of PUCRS for subsequent extraction of RNA and cDNA synthesis. Specific primers were used to verify the relative expression of mTOR, STAT-3 and STAT-6 by means of real-time PCR. The results obtained were correlated with AB severity markers such as hospitalization time and wheezing time. Results: for the analysis of expression of the mTOR signaling protein and transcription factors STAT-3 and STAT-6, 23 patients hospitalized with AB were included. A general correlation was made between clinical markers (days of hospitalization and days of wheezing) and expression of signaling pathways. Data were stratified according to severity markers and showed a trend towards decreased mTOR expression in patients with a wheezing time equal to or greater than 5 days (r = -0.702 and p = 0.024). However, the STAT-3 and STAT-6 signaling pathways were not correlated with AB severity factors when applied in this group of patients. Conclusion: transcription factors are essential for generating effective immune responses. mTOR, STAT-3 and STAT-6 participate in the expression of a variety of genes in response to cellular stimuli and may play a key role in the manifestation of the disease. Our data demonstrate the decrease in mTOR expression, with improvement in clinical markers of severity, but other studies are needed to reinforce this finding.
Introdu??o: a bronquiolite aguda (BA) ? uma doen?a inflamat?ria das vias a?reas considerada a patologia mais comum do trato respirat?rio inferior na inf?ncia. Respons?vel por um grande n?mero de hospitaliza??es em lactentes ? uma das principais doen?as respirat?rias em todo o mundo, elevando os custos de cuidados de sa?de em lactentes. Segundo dados epidemiol?gicos, entre 75.000 e 125.000 crian?as s?o hospitalizadas nos Estados Unidos anualmente com infec??es causadas pelo v?rus sincicial respirat?rio (VSR), respondendo por aproximadamente 25% das pneumonias pedi?tricas e at? 70% das interna??es por bronquiolite aguda (BA). As crian?as com defici?ncia na imunidade mediada por c?lulas podem desenvolver infec??es mais graves e prolongadas. A ativa??o das vias de sinaliza??o mTOR, STAT-3 e STAT-6 t?m sido identificadas como reguladores-chave em diferentes fun??es do sistema imune. O objetivo deste estudo foi investigar a rela??o entre a express?o g?nica de mTOR, STAT-3, STAT-6 e a gravidade da BA. M?todos: trata-se de um estudo de coorte onde foi inclu?do um grupo de lactentes de idade inferior a 12 meses, com BA, internados em um hospital terci?rio de Porto Alegre, Brasil. Foi coletado lavado nasofar?ngeo de todos os pacientes e armazenados em solu??o de Trizol ? temperatura de -80?C no Instituto de Pesquisas Biom?dicas (IPB) da PUCRS para posterior extra??o de RNA e s?ntese de cDNA. Foram utilizados os iniciadores espec?ficos para verificar a express?o relativa de mTOR, STAT-3 e STAT-6 por meio de PCR em tempo real. Os resultados obtidos foram correlacionados com marcadores de gravidade da BA como tempo de interna??o e tempo de sibil?ncia. Resultados: para a an?lise da express?o da prote?na de sinaliza??o mTOR e fatores de transcri??o STAT-3 e STAT-6, foram inclu?dos 23 pacientes hospitalizados com BA. Foi realizada uma correla??o geral entre os marcadores cl?nicos (dias de interna??o e dias de sibil?ncia) e a express?o das vias de sinaliza??o. Os dados foram estratificados de acordo com os marcadores de severidade e mostraram uma tend?ncia para a diminui??o da express?o de mTOR em pacientes com tempo de sibil?ncia igual ou superior a 5 dias (r = -0,702 e p = 0,024). No entanto, as vias de sinaliza??o STAT-3 e STAT-6 n?o foram correlacionadas com fatores de gravidade da BA quando aplicadas neste grupo de pacientes. Conclus?o: os fatores de transcri??o s?o essenciais para gerar respostas imunes eficazes. O mTOR, STAT-3 e STAT-6 participam na express?o de uma variedade de genes em resposta a est?mulos celulares e podem desempenhar um papel-chave na manifesta??o da doen?a. Nossos dados demonstram a diminui??o da express?o de mTOR, com melhora dos marcadores cl?nicos de gravidade, por?m outros estudos s?o necess?rios para refor?ar este achado.

As mudanças pela quais vem passando a área de gestão de pessoas têm suscitado o desenvolvimento de novas práticas, algumas ainda não validadas pela ciência, como é o caso da grafologia e do shiatsu e, outras, consideradas “ocultas” e, na melhor das hipóteses, metafísica, por sua origem mística, e que, alguns anos atrás, seria impensável o seu emprego como ferramentas em gestão empresarial, dentre elas a astrologia, a numerologia, o feng shui e a radiestesia. Este estudo identificou, descreveu e consolidou os dados de empresas que aplicam uma ou mais dessas práticas, revelando suas expectativas, quando optam por utilizá-las e os resultados alcançados. O referencial teórico, que deu sustentação à pesquisa, pautou-se na dimensão psíquica, através da análise da psicodinâmica organizacional e da psicologia analítica de Jung, na dimensão sociológica, através da cultura organizacional, na dimensão holística, que incorporou a perspectiva espiritual, e na dimensão administrativa, via análise das mudanças na gestão de pessoas e qualidade de vida no trabalho. Abordou-se ainda, de forma resumida, informações acerca das principais práticas alternativas. A metodologia de pesquisa consistiu de levantamentos quantitativo e qualitativo em empresas localizadas no eixo São Paulo/Rio de Janeiro, com o aprofundamento do estudo através da análise de multicasos. Foram entrevistados especialistas que atuam como consultores externos e gestores de 11 empresas de distintos portes e segmentos de atuação, que utilizam uma ou mais dessas ferramentas. Concluiu-se, dentre outros aspectos, que práticas alternativas são adotadas por diversos tipos, segmentos e portes de empresas, na maior parte das vezes, por definição da alta direção, e apenas em alguns casos, por iniciativa da área de recursos humanos.

Les peptides aldéhydes sont connus comme inhibiteurs de protéases et précurseurs de différentes classes de composés biologiquement actifs. Les méthodes pour leur synthèse impliquent classiquement la transformation d'un précurseur (amide de Weinreb, ester, alcool, acétal) en aldéhyde en étape finale pour éviter l'épimérisation du stéréocentre en position α de l'aldéhyde. En revanche, les β-peptides aldéhydes, plus stables à l'épimérisation, ont été relativement peu explorés. Ils sont généralement obtenus par homologation de l'acide aminé correspondant malgré les faibles rendements, les problèmes d'épimérisation et de nombreuses étapes. Par conséquent, un nouvel accès synthétique aux β-peptides aldéhydes reste toujours un challenge difficile. Sur la base des travaux antérieurs dans notre équipe en hétérocycloaddition diastéréosélective [4+2] et [3+2], nous avons développé au cours de ce doctorat de nouvelles stratégies pour l'accès asymétrique à ces dérivés de β-aminoacides par deux voies complémentaires :1) Une voie utilisant les hétérocycles à six chaînons de type 6-ATO (6-alcoxytétrahydrooxazinone) qui ont été préparés par une réaction d'hétérocycloaddition hautement stéréosélective avec de bons rendements et ed. Ces cycloadduits ont été transformés par transacétalisation vers les aminoacétals intermédiaires "mixtes" ou "symétriques". Ces nouveaux acétals sont des intermédiaires parfaits pour la N-élongation par couplage peptidique, conduisant finalement aux aldéhydes peptidiques β3-C-terminaux monosubstitués. 2) Sur une autre approche, les hétérocycles à cinq chaînons 5-AISO (3,3'-disubstitué 5-alcoxy-isoxazolidines) ont été obtenus par cycloaddition dipolaire-1,3 entre des cétonitrones esters et des éthers vinyliques. Ces composés ont été utilisés avec succès en tant que précurseurs d'aminoaldéhydes β3-disubstitués après l'étape de transprotection de l'atome d'azote, suivie par la copure de la liaison N-O. L'extension asymétrique de l'étape de cycloaddition a été étudiée par des voies énantiosélective et diastéréosélective, ouvrant ainsi l'entrée vers les peptides aldéhydiques β3-disubstitués-C-terminaux énantioenrichis.

Adaptation and acclimation to different temperatures of obligate psychrophilic, facultative psychrophilic and mesophilic yeasts. Production of ω-3 and ω-6 polyunsaturated fatty acids by fermentative way. Obligate psychrophilic, facultative psychrophilic and mesophilic yeasts were cultured in a carbon rich medium at different temperatures to investigate if growth parameters, lipid accumulation and fatty acid composition were adaptive and/or acclimatory responses. Acclimation of facultative psychrophiles and mesophiles to lower temperature negatively affected their specific growth rate. Obligate psychrophiles exhibited the highest biomass yield (YX/S), followed by facultative psychrophiles, then by mesophiles. The growth temperature did not influence the YX/S of facultative psychrophiles and mesophiles. Acclimation to lower temperature caused the increase in lipid yield (YL/X) in mesophilic yeasts, but did not affect YL/X in facultative psychrophiles. Similar YL/X were found in both facultative and obligated psychrophiles, suggesting that lipid accumulation is not a distinctive character of adaptation to permanently cold environments. The extent of unsaturation of fatty acids was one major adaptive feature of the yeasts which colonize permanently cold ecosystems. Remarkable amounts of α-linolenic acid were found in obligate psychrophiles at the expenses of linoleic acid, whereas it was generally scarce or absent in all the others strains. Increased unsaturation of fatty acids was also an acclimatory response of mesophiles and facultative psychrophiles to lower temperature. It’s well known that omega-3 polyunsaturated fatty acids (PUFAs) display a variety of beneficial effects on various organ systems and diseases, therefore a process for the microbial production of omega-3 PUFAs would be of great interest. This work sought also to investigate if one of the better psychrophilic yeast, Rhodotorula glacialis DBVPG 4785, stimulated by acclamatory responses, produced omega-3 PUFAs. In fact, the adaptation of psychrophilic yeasts to cold niches is related to the production of higher amounts of lipids and to increased unsaturation degree of fatty acids, presumably to maintain membrane fluidity and functionality at low temperatures. Bioreactor fermentations of Rhodotorula glacialis DBVPG 4785 were carried out at 25, 20, 15, 10, 5, 0, and -3°C in a complex medium with high C:N ratio for 15 days. High biomass production was attained at all the temperatures with a similar biomass/glucose yield (YXS), between 0.40 and 0.45, but the specific growth rate of the strain decreased as the temperature diminished. The coefficients YL/X have been measured between a minimum of 0.50 to a maximum of 0.67, but it was not possible to show a clear effect of temperature. Similarly, the coefficient YL/S ranges from a minimum of 0.22 to a maximum of 0.28: again, it does not appear to be any significant changes due to temperature. Among omega-3 PUFAs, only α-linolenic acid (ALA, 18:3n-3) was found at temperatures below to 0°C, while, it’s remarkable, that the worthy arachidonic acid (C20:4,n-6), stearidonic acid (C20:4,n-3) C22:0 and docosahexaenoic acid (C22:6n-3) were produced only at the late exponential phase and the stationary phase of batch fermentations at 0 and -3°C. The docosahexaenoic acid (DHA) is a beneficial omega-3 PUFA that is usually found in fatty fish and fish oils. The results herein reported improve the knowledge about the responses which enable psychrophilic yeasts to cope with cold and may support exploitation of these strains as a new resource for biotechnological applications.

Den svenska skolan skall bl.a. vila på en kristen tradition enligt Lgr 11, men benämner inte närmre vems kristna tradition eller hur denna tradition bör ta sin form i klassrummet. Att tolka den kristna traditionen kan göras på många sätt, men för att exemplifiera problematiken i tolkningar så utgår uppsatsen från att belysa hur mångfacetterat ett resultat kan bli även vid ett par utvalda bibelberättelser från en relativt homogen grupp uttolkare. Syftet för den här konsumtionsuppsatsen är att undersöka vad kvinnliga exegeter belyser när de beskriver hur kvinnor interagerar med Jesus i två utvalda berättelser ur Nya testamentets evangelier. Exegeternas beskrivningar utreds också komparativt för att finna skiljaktigheter och liknelser. Vidare förs det även en didaktisk diskussion kopplat till skolans religionsundervisning om hur tolkningar kring en och samma berättelse som didaktiskt medel kan berika undervisningssammanhang i klassrummet.     Resultatet i uppsatsen visar både hur exegeterna har laborerat fram sina tolkningar och vad dessa tolkningar resulterat i för bibelberättelserna. I ett komparativt arbetssätt utvidgar exegeterna kontexten för bibelberättelserna på macronivå för att understödja den närmre analys de för på micronivå. De finner stöd i bl.a. lingvistik, utombibliska dokument och kulturella företeelser för att understödja deras argumentation om kvinnorna i de bibliska berättelserna. Kvinnorna i de båda bibliska berättelserna porträtteras på ett nytt sätt och utmärks av vissa exegeter till både apostel och lärjunge.     Resultatet för den religionsdidaktiska diskussionen utmynnas i både hur elever och främst lärare bör anamma en reflexivitet för att granska sig själva och hur tolkningar görs i vardagen för att kartlägga mönster där exotifiering och maktförskjutningar sker när religioner behandlas i klassrummet. Religionsdidaktikernas pedagogiska verktyg gynnar elevernas analyserande förmågor och kritiska tänkande vid exempelvis komparativa tolkningsövningar av urkunder. Hos läraren uppmanas en självkännedom genom att aktivt kunna belysa hur tolkningar av religioner förs i klassrummet och ifall det görs på någons bekostnad. Genus förs som en diskussionspunkt i förhållande till uppsatsens val att låta kvinnor ta plats och tolka religion. Genom genus kan en androgyn syn på religionsdidaktik framföras och låta en inkludering ske i religionsdiskursen där kvinnor inte längre är en åtskild minoritet inom religion, utan en aktiv och inkluderande part.

碩士
國立中正大學
化學研究所
89
Fulvenes usually react with benzoquinone to give the [4+2] cycloaddition adducts. We have found that reaction of the 6-dimethylaminofulvene and benzoquinone results in the formation of the oxatricyclic product. This methodology was applied to the first example of the synthesis of 11-oxasteroids In this thesis,we would like to explore the scope and limitation of this new reaction by using different starting materials with varies substituents. The explosive development of combinatorial chemistry over the past few years has led to a renaissance in the development of solid-phase synthetic methodologies. In this study,me have also developed a novel example of the construction of the 11-heterosteroids on solid supports. This strategy exploits a unique reaction for liberating the product from resin and offer a new approach toward combinaterial librarial of hetero steroids.

碩士
國立台灣工業技術學院
化學工程技術研究所
85
In this study，IM60 (Lipase from Mucor miehei immobilized on anionic resin) was employed to catalyze acidolysis between borage oil and n-3 polyunsaturated fatty acid (PUFA) obtained from the saponification of menhaden oil. The acidolysis between mixtures of acylglycerols obtained from the partial hydrolysis of borage oil (catalyzed by Candida rugosa lipase immobilized on microporous polypropylene) and PUFA (derived from menhaden oil) was also studied. The effects of temperature, enzyme loading, substrate concentrations, and substrate weight ratio on the reaction product were investigated. The purpose of this work is to obtain acylglycerols rich in both n-3 and n-6 fatty acids.For acidolysis catalyzed by IM60, with concentrations of borage oil and n-3 PUFA equal to 20mg/ml and 60mg/ml, respectively, and a reaction temperature of 50℃, the content of GLA, EPA and DHA in acylglycerols can reach 20.6%, 19.1%, and 14%, respectively.When borage oil was hydrolyzed for 4h before n-3 PUFA was added to the acidolysis for another 18h, GLA, EPA and DHA content in acylglycerols reach 26.5%, 19.8% and 18.1%, respectively.The hydrolysis of menhaden oil (catalyzed by immobilized Candida rugosa lipase) yields acylglycerols with EPA and DHA content of 19.4% and 25.6%, respectively, after a reaction time of 8h. The acidolysis of this acylglycerol and n-3 PUFA derived from saponification of borage oil (with weight ratio of 1:1) was catalyzed by IM60 for 12h. GLA, EPA and DHA content in acylglycerols in the product are 16.7%, 12.8% and 19.2%, espectively.

碩士
中國醫藥大學
藥學系
96
Many beneficial properties have been attributed to (-)-epigallocatechin-3-gallate (EGCG), including chemopreventive, anticarcinogenic, and antioxidant active. The antitumor effect of green tea compound EGCG have not been studied clearly in head and neck squamous cell carcinoma cells. Previous study indicated that the constitutive activation of singal-transducer-and-activator-3 (STAT3) were associated with the proliferation of HNSCC cells. Numerous reports suggest that interleukin-6 (IL-6) promotes survival and proliferation of tumor cells through the phosphorylation of STAT3. Constitutive of STAT3 in HNSCC was relative with its proliferation and survival. Thus, compound that can suppress STAT3 activation have potential for the treatment of HNSCC. Therefore, we examined in detail the molecular effect of EGCG on four HNSCC cell lines, SAS, Cal-27, Ca9-22 and HSC3. In the beginning, we found the great inhibition on HNSCC cells of EGCG. Further, we focused the effect of EGCG on STAT3 signal pathway. In this study, the 70% lethal dose (IC70) of EGCG for three cell lines, SAS, Cal-27 and Ca9-22, was 20 μM, and EGCG inhibited STAT3 phosphorylation in a dose- and time- dependent manner. Nuclear translocation of STAT3 was also inhibited by EGCG. Besides inhibiting constitutive expression, EGCG also abrogated the IL-6-induced activation of STAT3 and further inhibited IL-6-induced proliferation on HNSCC cell. Compare with Apigenin, Curcumin and AG490, EGCG was more effective inhibitor of IL-6-induced proliferation on HNSCC cells. Overall, our results strongly suggest that EGCG is a potent inhibitor of constitutive and IL-6-induced STAT3 phosphorylation. This mechanism may be at least partially responsible for EGCG’s ability to suppress proliferation of HNSCC cells. Taken together, these finding suggest that this naturally occurring compound may be useful, in the chemoprevention and/or treatment of HNSCC.

碩士
國立中正大學
化學研究所
88
Part I: Facile synthesis of 11-oxasteroid via the hetero [6+3] cycloaddition Cycloadditions of fulvenes (e.g.[4+3], [2+2], [4+2], [6+4], [6+2]) provide general and powerful approaches to various polycyclic systems and natural products. Fulvenes usually react with benzoquinones to give the [4+2] cyclo-addition adducts. In contrast, we have found that reaction of the 6-dimethylaminofulvene and benzoquinone results in the formation of the oxatricyclic product. This is the first example of the synthesis of 3-oxa-bicyclo[4.3.0]nonane system via the hetero [6+3] approach. Part II: Oxidative addition of 1,3-dicarbonyl compounds to dicyclopentadiene and norbornene Recently, cerium(IV) ammonium nitrate (CAN)-mediated addition of 1,3-dicarbonyl compounds to various alkenes was reported to exploit its synthetic potential. Tricyclo[5.2.1.02,6]decane system is a useful building block for the synthesis of natural and unnatural compounds. As the result, we decide to study the 1,3-dicarbonyl addition to endo-dicyclopentadiene and norbornene mediated by CAN.

博士
國立中正大學
化學研究所
91
1.Studies in Synthesis of C-1 Substituted Fulvenes via the Oxidation-Addition of Haloacetyl Halide to fulveneketene Acetal. In contrast to the [2+2] cycloaddition of fulvenes and ketenes, fulveneketene acetal, 2-chloropentadienylidene-1,3-dioxalane, reacts with a-halo acyl halides to give various C-1 substituted fulvene. Herein we describe the first example of oxidative-addition of a-chloroacetyl chloride to fulveneketene acetal, and formal synthesis of the carbocyclic analogs of Captopril. 2.Traceless Solid-Phase Synthesis of Cyclopenta[c]quinolines and Cyclopenta[c]chromenes via Hetero [6+3] Cycloadditions of Fulvene. A Facile Approach to the 11-Heterosteroids Framework. The hetero [6+3] cycloaddition of fulvenes to benzoquinones and indoanilines provides an efficient route to the synthesis cyclopenta[c]-4H-chromen-8-ol, benzo[d]cyclopenta[e]-3H-3-azin-8-ol and other 11-hetero steroids. The structure of the cyclopenta[c]chromene skeleton was confirmed by the X-ray structure analysis of the p-bromobenzoate of 109. The traceless solid-phase synthesis of the scaldfold, consist of 110 examples, was achieved by the reaction of benzoquinones or iodoanilines with aminofulvene resin 140 which was prepared from polystyrene amino resin 138 via 2-step reaction.