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Zeolite encapsulated metal complexes as heterogeneous catalysts for oxidation reactionsWillingh, Gavin Von January 2012 (has links)
>Magister Scientiae - MSc / This study describes the synthesis and characterisation of Cu(II) and V(IV) complexes of tri- and quadridentate ligands L1 and L2 formed by condensation of ethylenediamine with acetylacetonate in 1:1 and 1:2 molar ratio, respectively. Encapsulation of these metal complexes in the nanocage of zoilite-Y generates new heterogeneous catalysts. These catalysts were synthesized employing the flexible ligand method encapsulation technique.The structures of these encapsulated complexes were established on the basis of various physico-chemical and spectroscopic studies. The results indicated that the complexes did not hinder or modify the framework or structure of the zeolite, confirming successful immobilization of Schiff-bases through the voids of zeolite Y.These encapsulated complexes were screened as heterogeneous catalysts for various oxidation reactions such as such as phenol, benzene, styrene and cyclohexene using a
green oxidant (H2O2).For comparison, the corresponding neat complexes were screened as potential homogeneous catalysts for these oxidation reactions. The results proved that the corresponding homogeneous systems described here represent an efficient and inexpensive method for oxidation of phenol, benzene, styrene and cyclohexene, having advantages over heterogeneous catalysis are its high activity and selectivity and short reaction times. Its major problem is its industrial application regarding principally the separation of the catalyst from the products.The size of the substrate has a significant effect on the conversion by encapsulated complexes such as in styrene oxidation. Therefore, it was established that steric effects of the substrates play a critical role in the poor reactive nature of the encapsulated complexes.In general, the percentage conversion decreased upon encapsulation of complexes in zeolite Y. All catalysts studied proved to be potential catalysts for the various oxidation reactions.It has been shown in this study that encapsulation can effectively improve product selectivity but requires a longer reaction time in most cases for maximum activity.Furthermore,oxovanadium complexes were more reactive than copper-based catalysts in all oxidation reactions tested in this study.A reaction mechanism study revealed that the activity of the encapsulated and neat complexes occurs through either formation of peroxovanadium (V) or hydroperoxidecopper(II) intermediate species.The studies in this thesis, therefore, conclude that the Cu(II) and V(IV) complexes encapsulated in Y-zeolite are active heterogeneous catalysts for the selective oxidation of various substrates. Encapsulation of the metal complexes in the super cages (-cages) of the zeolite matrix has the advantages of solid heterogeneous catalysts of easy separation and handling, ruggedness, thermostability, reusability (regeneration of the deactivated catalysts) as well as share many advantageous features of homogeneous catalysts.
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Reading and academic performance of first and second English language grade 8 learners.Krishnan, Khatpagam 19 March 2009 (has links)
Ten years into a democratic South Africa, significant changes have been witnessed in
economic, social, political and educational development. Changes in the education system have
resulted in many of the learners being encouraged to attend English medium schools although
this is not their L1. Hence, there has been an increase of learners learning to read in a language
that is not their first language. The transition from their home language to the language of
learning is often not easy and impacts on their academic proficiency as well as academic
development. This study investigated English reading abilities and academic performance of
Grade 8 L1 and L2 learners attending an Ex-Model C school. The SDRT – Brown Level was
used to assess the level of reading and its impact on academic achievement was investigated.
Results show that the SDRT was highly correlated with, and a significant predictor of
academic performance with certain tests being stronger predictors than others for L1 and L2
learners. Implications of these findings for the education of L1 and L2 learners are discussed.
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An intervention to develop English reading abilities of second language grade 9 learnersLong, Susanne Ingeborg 26 May 2008 (has links)
In support of educational equity, the White Paper 6 (Department of Education, 2001) states that every learner in South Africa has the right to pursue their learning potential to the best of their ability. The South African Schools Act of 1996 states that a school’s language policy may not exclude learners from different backgrounds. As a result, many English second language (L2) learners struggle to understand the learning material and perform poorly academically. Poor literacy and reading skills have been identified in the literature (for example Pretorius, 2005) as a significant cause for poor academic performance. In an endeavour to work within the Outcomes Based Education (OBE) system, teachers are increasingly seeking ways to improve group learning. These factors motivated the present study and a paired reading intervention was selected and administered to Grade 9 English second language learners. Volunteer participants consisted of an Experimental Group (n 53) and a Comparison Group (n 53). Each group was divided into strong (mentor) and weak (mentee) readers. Pre-tests and post-tests were conducted regarding the Experimental and Comparison Group’s scores on the Vocabulary and Comprehension subtests of the Stanford Reading Diagnostic Test (SDRT): Brown Level and the Academic Performance of both groups were recorded at pre and post-test phases. After an 11 week intervention programme a statistical analysis of the results was conducted. The overall means for the groups were analysed using t-tests to establish any significant differences between the pre-test and post-test results. An Analysis of Covariance (ANCOVA) was also conducted to determine whether any significant differences existed between the Experimental and Comparison Group. A null hypothesis was supported. It would appear that the whole-hearted commitment and participation of all role-players is essential for the effective implementation of a peer reading intervention at a school.
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Mutation-function analysis in vivo of the nuclear localization signals of L2 minor capsid proteins of high risk HPV16 and low risk HPV11Bockstall, Katy Elizabeth January 2008 (has links)
Thesis advisor: Junona Moroianu / During the papillomavirus replication cycle, the L2 minor capsid protein enters the nucleus in the initial phase after uncoating of the incoming virions and in the productive phase when L2 together with L1 major capsid protein mediate the encapsidation of the newly replicated viral genome. L2 proteins of both high risk HPV16 L2 and low risk HPV11 L2 have two nuclear localization signals (NLSs): one at the N-terminus (nNLS) and one at the C terminus (cNLS). The purpose of these experiments is to determine the minimal mutations necessary to inhibit the function of the NLSs. In this study, subcellular localization of enhanced green fluorescent protein (EGFP) fusions with full length L2 and L2 mutants lacking either the cNLS (EGFP-L2ΔC), nNLS (EGFP-L2ΔN), or both NLSs (EGFP-L2ΔNΔC) was analyzed in HeLa cell transfection assays. Full length HPV16 L2 and HPV11 L2 proteins localize to the nucleus. For both HPV16 and 11 L2, each NLS could independently mediate nuclear import in vivo. EGFP fusions were also made with mutated nNLS (EGFP-L2ΔCSbN) or mutated cNLS (EGFP-L2ΔNSbC). Transfected HeLa cells were examined by fluorescence microscopy and quantitative studies were done. In both HPV16 and 11 L2 proteins, mutation of basic residues in either NLS inhibited its nuclear import ability. / Thesis (BS) — Boston College, 2008. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Biology. / Discipline: College Honors Program.
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Characterization of the Nuclear Export Signal of Human Papillomavirus 16 L2 Minor Capsid ProteinHalista, Courtney Ellen January 2011 (has links)
Thesis advisor: Junona Moroianu / The L2 minor capsid protein of human papillomavirus is one of two structural proteins that comprise the icosahedral shell. Two potential, leucine-rich nuclear export signals (NESs) had been identified in the HPV16 L2 sequence, one in the n-terminus (51MGVFFGGLGI60) and one in the c-terminus (462LPYFFDSVSL471). DNA primers for mutant L2 proteins were designed to specifically target these two potential NES regions. Two primers had mutations in the n-terminal located NES (nNES), while the other two primers had mutations in the c-terminal NES (cNES). L2 nuclear retention mutants, RR297AA (“MS4”) and RTR313AAA (“MS5”), served as the templates for these NES mutations. Using mutagenesis, the desired secondary mutations were introduced into the mutant L2 genes in order to create four, distinct mutants: RR297AA + P463_ (“MS4 T1”), RR297AA + V469_ (“MS4 T2), RTR313AAA + P463_ (“MS5 T1”), and RTR313AAA + V469_ (“MS5 T2”). In contrast to the pancellular localization of the MS4 and MS5 L2 mutants, the “MS4 T1,” “MS4 T2,” “MS5 T1”, and “MS5 T2” mutants were all localized nuclearly. These results suggest that deletion of the cNES inhibits nuclear export of the HPV16 L2 minor capsid protein. / Thesis (BS) — Boston College, 2011. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: College Honors Program. / Discipline: Biology Honors Program. / Discipline: Biology.
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Why not "English only"? : Patterns of code-switching between Swedish and English in Swedish upper secondary EFL educationVestin, Johan January 2019 (has links)
English education in Sweden tends to be viewed as a second language, rather than a foreign language. Therefore, it is generally expected that instruction is performed, and content is taught in English. However, previous research shows that English is generally not the sole language used, even in classrooms with explicit “English only” policies. The following essay has investigated how this translates into classroom practice through observations of classroom interactions between students and teachers, as well as between students and students. Three different teachers were observed at two upper secondary schools. Shorter interviews were also conducted with the teachers. The results showed large differences between observations, but some clear trends were observed nonetheless. Socializing and metalanguage were more prevalent than other code-switches among students, while floor-holding was very rare and in most observations, non-existent. All teachers claimed to use English as much as possible although they also recognized the utility of using Swedish as a tool in the classroom. The view that English should be used as the language of instruction to a great extent was additionally observed in teacher interviews. However, there were no categorical opinions arguing for “English only”. The teachers also largely concurred with the use of Swedish, or other first languages as a language of comparison. This was supported by observations in the classrooms and significant differences existed between teachers. An investigation with a larger cohort in this field could be fruitful for future researchers. The results of the study could be used to further examine strategies to find a balance in the classroom between English and Swedish. The differences between classrooms show that there is no clear consensus on the extent of Swedish use in the EFL classroom. In order to improve teaching it is important to know why students use code-switching and in what situations it might be helpful to them, such as in translation or grammatical rules. However, different classrooms may require different approaches, which highlight the importance of discussing these issues.
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O uso das rotas de leitura no bilinguismo e sua rela??o com a profundidade ortogr?fica e a profici?ncia nas l?nguasSiqueira, Ellen Cristina Gerner 28 March 2018 (has links)
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Previous issue date: 2018-03-28 / Conselho Nacional de Pesquisa e Desenvolvimento Cient?fico e Tecnol?gico - CNPq / Reading involves multiple interdependent processes and, according to the dual route model, this is basically achieved through two routes, the phonological route (normally used to read new words or pseudowords) and the lexical route (for reading familiar and irregular words). Reading in the mother tongue (L1) requires explicit instruction and it is a great challenge. By learning a second language (L2), new elements (phonological, orthographic and semantic, among others) are introduced into reading, requiring the speaker to choose between two written codes each time one has to read. Moreover, during this process of choice, more characteristic reading strategies of one language may interfere with the reading strategy of the other. Research indicates that, just as in the case of monolingual subjects, several factors influence the reading strategy used by bilingual subjects, the orthographic depth of the language and the reader's proficiency being the key elements. This study aims at identifying how these factors influence the strategy of reading in late bilinguals (beginners or proficient), native speakers of Brazilian Portuguese with English as a second language. In order to do this, accuracy and the latencies required to word and nonword reading in both L1 and L2 were measured. Among the main results we found that the most proficient group (MaP) had a shorter reading time in the words and pseudowords of PB than the less proficient group (MeP), suggesting an interference of L2 (more opaque) in L1 (more transparent) and a larger use of the lexical route in L1. In addition, the study revealed that in the MeP group there was no difference between the time of reading of words and pseudowords in English, suggesting a predominance of the use of the phonological route in the reading of L2 (more opaque). Such findings are important to reinforce that the choice of reading strategies and the use of routes are susceptible to multiple factors, which act together and interrelated. / A leitura envolve m?ltiplos processos interdependentes e, segundo o modelo de dupla rota, tal habilidade se d? basicamente por duas vias, a fonol?gica (normalmente utilizada para a leitura de palavras novas ou pseudopalavras) e a lexical (utilizada para palavras familiares e irregulares). Ler na l?ngua materna (L1) requer um aprendizado sistem?tico e ? um grande desafio. Ao aprender uma segunda l?ngua (L2), novos elementos (fonol?gicos, ortogr?ficos e sem?nticos dentre outros) s?o introduzidos na leitura, exigindo que o falante escolha entre dois c?digos escritos a cada vez que ? preciso ler. Al?m disso, durante esse processo de escolha, estrat?gias de leitura mais caracter?sticas de uma l?ngua podem influenciar na estrat?gia de leitura da outra. Pesquisas indicam que diversos fatores influenciam a escolha da rota de leitura, sendo a profundidade ortogr?fica da l?ngua e a profici?ncia do leitor os principais. Assim, este estudo tem como objetivo identificar de que forma esses fatores influenciam a escolha da rota de leitura por bil?ngues sucessivos (mais ou menos proficientes) falantes nativos do Portugu?s Brasileiro (PB) tendo o Ingl?s como L2. Para isso, foram medidas a acur?cia e o tempo de leitura de palavras e pseudopalavras tanto na L1 como na L2. Dentre os principais resultados encontrados, destacamos que o grupo mais proficiente (MaP) teve um menor tempo de leitura nas palavras e pseudopalavras do PB do que o grupo menos proficiente (MeP), sugerindo uma influ?ncia da L2 (mais opaca) na L1 (mais transparente) e uma utiliza??o maior da rota lexical na L1. Al?m disso, o estudo revelou que no grupo MeP n?o houve diferen?a entre o tempo de leitura de palavras e pseudopalavras no Ingl?s, sugerindo uma predomin?ncia do uso da rota fonol?gica na leitura da L2 (mais opaca). Tais achados s?o importantes para refor?ar que a escolha das estrat?gias de leitura e o uso das rotas s?o suscet?veis a m?ltiplos fatores, que atuam de forma conjunta e interrelacionada.
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A TRANSFERÊNCIA GRAFO-FÔNICO-FONOLÓGICA L2 (FRANCÊS) - L3 (INGLÊS): UM ESTUDO CONEXIONISTABlank, Cintia Avila 06 March 2008 (has links)
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Previous issue date: 2008-03-06 / The research in the area of second language acquisition presents a strong tendency to
investigate the relationship between an L1 and an L2, leaving out the process of transfer
which can occur when one is learning more than one foreign language. The present study
aims at analyzing the transfer of grapho-phonic-phonologic patterns of an L2 into an L3 in a
connectionist perspective. For that purpose, a case study was carried out with one male adult
Brazilian Portuguese native speaker, who speaks French (L2) in an advanced level and is
learning English (L3) in a pre- intermediate level. Therefore, the main goals of this research
were: 1) to investigate whether the vowel assimilation in the L3 would happen towards the
vocalic characteristics (F1, F2 and duration) of subject s L1 or L2; and 2) to assess whether
the effects produced by the L2 orthography would cause L2-L3 grapho-phonic-phonologic
transfer. The data relative to the first objective of this research was obtained via naming tasks
performed in the three languages spoken by the subject, whose productions were analyzed
acoustically with the aid of Praat (version 4.4.2.2). The results regarding the acoustic vowel
analysis suggest the creation of hybrid categories between the L1 and L2, which were
assimilated by the L3 vowels of the subject. As for the data concerning the second goal,
obtained by a lexical access task in the participant s L2 and L3, the software E-Prime was
used together with a Serial Response Box. For the lexical access task, apart from graphophonic-
phonologic transference from the L2 (French) into the L3 (English), evidence of
grapho-phonic-phonologic transference from the L3 into the L2 were also found. The results
obtained are in consonance with a connectionist view of the processing of memory systems,
which would work in a collaborative way, which would enable the interaction between
previous knowledge from the L1 and the L2 (more consolidated), and the knowledge of a new
L3 (less stabilized) / As pesquisas na área de língua estrangeira apresentam uma forte tendência em
investigar a relação entre a L1 e a L2, deixando de lado a explicação dos processos de
transferência que podem ocorrer quando da aprendizagem de mais de uma língua estrangeira.
No presente estudo, tem-se por objetivo analisar a transferência de padrões grafo-fônicofonológicos
da L2 para a L3, através de uma abordagem conexionista. Para tanto, um estudo
de caso foi desenvolvido, contando com um sujeito adulto do sexo masculino falante nativo
do português brasileiro, falante de francês como L2 em nível avançado e falante de inglês
como L3 em nível pré-intermediário. A partir do objetivo geral estipulado acima, procurou-se
investigar: se a assimilação vocálica durante a tarefa de recodificação leitora em L3 ocorreria
em direção às características vocálicas (F1, F2 e duração) da L1 ou da L2 do sujeito; e se o
efeito exercido pela ortografia da L2 suscitaria a transferência grafo-fônico-fonológica da L2
para a L3. Os dados coletados para verificar o primeiro objetivo desta pesquisa, obtidos
através da gravação de tarefas de recodificação leitora nas três línguas faladas pelo sujeito,
foram analisados acusticamente com o programa Praat (versão 4.4.2.2). Os resultados da
análise acústica das vogais apontam para a criação de categorias híbridas entre a L1 e a L2
para as vogais da L3 do sujeito. Já para os dados relativos ao segundo objetivo, obtidos
através da aplicação de uma tarefa de acesso lexical na L2 e na L3 do sujeito, fez-se uso do
programa E-Prime em conjunto com uma Serial Response Box. Para o teste de acesso lexical,
além de uma forte transferência grafo-fônico-fonológica da L2 (francês) para a L3 (inglês),
foram encontrados também indícios de transferência grafo-fônico-fonológica da L3 sobre a
L2. Os resultados alcançados estão em consonância com a visão conexionista a respeito do
processamento dos sistemas de memória, que funcionariam de forma colaborativa,
possibilitando a interação entre o conhecimento prévio da L1 e da L2 (mais consolidados) e o
conhecimento novo da L3 (menos estabilizado)
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A EPÊNTESE NO PORTUGUÊS BRASILEIRO (L2), EM SEGMENTOS PLOSIVOS EM CODAS MEDIAIS, POR FALANTES NATIVOS DO ESPANHOL COLOMBIANO (L1): UMA ANÁLISE VIA TEORIA DA OTIMIDADE ESTOCÁSTICA E GRAMÁTICA HARMÔNICAAzevedo, Roberta Quintanilha 13 July 2011 (has links)
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Previous issue date: 2011-07-13 / This study aims to describe and analyze, according to the frameworks of Harmonic Grammar HG (LEGENDRE, MIYATA & SMOLENSKY, 1990; SMOLENSKY & LEGENDRE, 2006) and Stochastic Optimality Theory OT, (BOERSMA & HAYES, 2001), the production, by Colombian Learners of Brazilian Portuguese (BP), of stop segments in word-mid codas, liable for the production of epenthetical segments. This investigation was motivated by the possibility of occurrence of stop codas in the learners‟ L1, but not in the L2, as Brazilian Portuguese tends to avoid this syllabic structure. In order to build the corpus, an instrument composed of Portuguese and Spanish cognate words was proposed, so that vehicle phrases could be recorded in AUDACITY 1.3.5 (ANSI) software. Four Colombian students, who remained in Brazil for a period of six months, in an academic mobility program in the city of Pelotas-RS, were chosen to take part in the investigation. In the selection of the participants, extralinguistic factors such as sex, age and scholarity were homogenized. The data were submitted to an acoustic analysis using PRAAT (5.1.12), developed by Paul Boersma and David Weenick. We confirmed the hypothesis that even in cognate words, there is a different treatment to plosive in coda position in both analyzed languages, depending on the language system which is being used by the speaker. Such fact was collected, according to the Harmonic Grammar and Stochastic Optimality Theory, through a hierarchy of universal constraints / Este trabalho tem por objetivo descrever e analisar, à luz da Gramática Harmônica - HG, (LEGENDRE, MIYATA & SMOLENSKY, 1990; SMOLENSKY & LEGENDRE, 2006) e da Teoria da Otimidade Estocástica - OT (BOERSMA & HAYES, 2001), o emprego de segmentos plosivos em codas mediais de palavras, passíveis de motivação de epêntese por parte de aprendizes colombianos de Português Brasileiro (PB), falantes nativos de Espanhol. A realização da pesquisa foi motivada pela licença que a L1 dos informantes oferece para a presença de segmentos plosivos em final de sílaba em oposição à evitação de tal estrutura silábica por falantes do PB. Para a constituição do corpus, foi proposto um instrumento composto de palavras cognatas do Português e Espanhol para a leitura em frases veículo, gravadas no Programa AUDACITY 1.3.5 (ANSI). Foram escolhidos, para este trabalho, quatro estudantes colombianos que permaneceram no Brasil por um período médio de seis meses, em mobilidade acadêmica na cidade de Pelotas-RS, com o cuidado de serem homogeneizados fatores extralinguísticos, como sexo, idade e nível de escolaridade. Os dados foram submetidos a uma análise acústica com o uso do software PRAAT, desenvolvido por Paul Boersma e David Weenink (versão 5.1.12). Foi confirmada a hipótese de que, mesmo em palavras cognatas nas duas línguas analisadas, há diferente tratamento às plosivas em coda, dependendo do sistema linguístico que está sendo utilizado pelo falante de Espanhol aprendiz de PB. Tal fato foi captado, à luz da HG e da OT Estocástica, via hierarquia de restrições universais
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NOTAR E APRENDER: O PAPEL DA INSTRUÇÃO EXPLÍCITA NA AQUISIÇÃO DA PRAGMÁTICA DA L2Mulling, Lydia Tessmann 27 June 2007 (has links)
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Previous issue date: 2007-06-27 / This study aims to investigate the role played by explicit instruction on L2
pragmatic acquisition. The main objective of the present study is to find out whether
high-proficient students of English are able to recognize pragmatic violations and make
appropriate requests in English. Besides that, this study investigates the role played by
the student s attention in situations that require pragmatic production and perception.
Seventeen English students, from Universidade Federal de Pelotas (UFPEL), were
divided into two groups according to their proficiency: experimental and control. In
order to find out the role played by explicit instruction on L2 pragmatics, only the
experimental group received special classes based on L2 pragmatics. To reach the
objective of this work, two tests were applied in two different moments, called as preand
post-test.
The analysis, carried out through the comparison of students performances in
both tests and different moments, indicates that the instruction enabled the development
of perception on pragmatic violations. Moreover, it led the students to make more
appropriate requests in the post-test. Thus, the explicit instruction on L2 pragmatics
caused the student to draw their attention to the pragmatic aspect of the input as well as
to the context that involves the communicative act / Este estudo tem como objetivo analisar o papel que a instrução de caráter
explícito desempenha em relação à aquisição da pragmática da L2, nesta pesquisa, a
língua inglesa. Investiga-se, portanto, se alunos proficientes, futuros professores de
inglês como língua estrangeira, conseguem perceber inadequações pragmáticas e
produzir pedidos em inglês como L2, e que papel a atenção ao insumo, ativada pela
instrução explícita, pode desempenhar frente às situações de escolhas pragmáticas na
percepção e na produção dos sujeitos da amostra. Dezessete alunos, estudantes de Letras
Inglês da Universidade Federal de Pelotas (UFPEL) tiveram sua produção pragmática
analisada por dois avaliadores e realizaram um teste de percepção e julgamento acerca
de enunciados que continham violações tanto de ordem pragmática quanto gramatical.
Para analisar o efeito desempenhado pela instrução explícita, os dados foram coletados
em duas etapas: uma anterior à instrução explícita, e consequentemente, uma posterior á
instrução. Além disso, os sujeitos foram divididos em dois grupos, experimental e
controle segundo o nível de proficiência lingüística. Com base no objetivo geral de
verificar a influência da instrução explícita, o trabalho pedagógico acerca da pragmática
da L2, especialmente sobre a realização de pedidos, foi realizado somente com o grupo
experimental. Análise dos dados e comparação entre as duas etapas, demonstrou o efeito
benéfico da instrução explícita tanto em relação à percepção de enunciados
pragmaticamente inadequados quanto a produção de pedidos em língua inglesa. Assim,
a instrução acerca da pragmática auxiliou os aprendizes a prestar atenção ao aspecto
pragmático do insumo junto à análise do contexto que ambienta o ato comunicativo
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