A diffuse reflectance comparative study of benzil inclusion within p-tert-butylcalix[n]arenes (n=4, 6, and 8) and silicalite

Diffuse reflectance and laser-induced techniques were used to access photochemical and photophysical processes of benzil in solid supports, namely p-tert-butylcalix[n]arenes with n = 4, 6, and 8. A comparative study was performed using these results and those obtained with another electronically inert support, silicalite, which is a hydrophobic zeolite. In the latter substrate, ground-state benzil has the two carbonyl groups in an s-trans planar conformation while in the calixarenes a distribution of conformers exists, largely dominated by skew conformations where the carbonyl groups are twisted one to the other. In all substrates, room-temperature phosphorescence was obtained in air-equilibrated samples. The decay times vary greatly and the largest lifetime was obtained for benzil/p-tert-butylcalix[6]arene, showing that this host cavity well accommodates benzil, enhancing its room-temperature phosphorescence. p-tert-Butylcalix[6] and [8]arene molecules provide larger hydrophobic cavities than silicalite, and inclusion complexes are formed with these hosts and benzil as guest; p-tert-butylcalix[4]arene does not include benzil. This probe is deposited outside the calix[41 cavity, in the form of microcrystals. Triplet-triplet absorption of benzil was detected in all cases and is predominant in the silicalite channel inclusion case. Benzil ketyl radical formation occurs with inclusion in calix[6]arene and calix[8]arene. In the three cases, benzoyl radical was detected at long times (in the millisecond time scale). Product analysis and identification clearly show that the main detected degradation photoproducts in all substrates are benzoyl radical derivatives. Calix[6] and [8]arenes are able to supply hydrogen atoms that allow also another reaction, the reduction to benzoin through benzil ketyl radical formation.

Oligodeoxynucleotide synthesis using protecting groups and a linker cleavable under non-nucleophilic conditions

Oligodeoxynucleotides (ODNs) containing latent electrophilic groups can be highly useful in antisense drug development and many other applications such as chemical biology and medicine, where covalent cross-linking of ODNs with mRNA, protein and ODN is required. However, such ODN analogues cannot be synthesized using traditional technologies due to the strongly nucleophilic conditions used in traditional deprotection/cleavage process. To solve this long lasting and highly challenging problem in nucleic acid chemistry, I used the 1,3-dithian-2-yl-methoxycarbonyl (Dmoc) function to protect the exo-amino groups on the nucleobases dA, dC and dG, and to design the linker between the nascent ODN and solid support. These protecting groups and linker are completely stable under all ODN synthesis conditions, but can be readily cleaved under non-nucleophilic and nearly neutral conditions. As a result, the new ODN synthesis technology is universally useful for the synthesis of electrophilic ODNs. The dissertation is mainly comprised of two portions. In the first portion, the development of the Dmoc-based linker for ODN synthesis will be described. The construction of the dT-Dmoc-linker required a total of seven steps to synthesize. The linker was then anchored to the solid support―controlled pore glass (CPG). In the second portion, the syntheses of Dmoc-protected phosphoramidites ODN synthesis monomers including Dmoc-dC-amidite, Dmoc-dA-amidite, Dmoc-dG-amidite are described. The protection of dC and dA with 1,3-dithian-2-yl-methyl 4-nitrophenyl carbonate proceeded smoothly giving Dmoc-dC and Dmoc-dA in good yields. However, when the same acylation procedure was applied for the synthesis of Dmoc-dG, very low yield was obtained. This problem was later solved using a highly innovative and environmentally benign procedure, which is expected to be widely useful for the acylation of the exo-amino groups on nucleoside bases. The reactions to convert the Dmoc-protected nucleosides to phosphoramidite monomers proceeded smoothly with high yields. Using the Dmoc phosphoramidite monomers dA, dC, dG and the commercially available dT, and the Dmoc linker, four ODN sequences were synthesized. In all cases, excellent coupling yields were obtained. ODN deprotection/cleavage was achieved by using non-nucleophilic oxidative conditions. The new technology is predicted to be universally useful for the synthesis of ODNs containing one or more electrophilic functionalities.

Pavimentações do plano : uma exploração com materiais manipulativos no 4º ano de escolaridade

Relatório de Estágio apresentado à Escola Superior de Educação do Instituto Politécnico de Castelo Branco para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Educação Pré- Escolar e 1º Ciclo do Ensino Básico.

Audio-Visual Information Processing across different age groups

People possess different sensory modalities to detect, interpret, and efficiently act upon various events in a complex and dynamic environment (Fetsch, DeAngelis, & Angelaki, 2013). Much empirical work has been done to understand the interplay of modalities (e.g. audio-visual interactions, see Calvert, Spence, & Stein, 2004). On the one hand, integration of multimodal input as a functional principle of the brain enables the versatile and coherent perception of the environment (Lewkowicz & Ghazanfar, 2009). On the other hand, sensory integration does not necessarily mean that input from modalities is always weighted equally (Ernst, 2008). Rather, when two or more modalities are stimulated concurrently, one often finds one modality dominating over another. Study 1 and 2 of the dissertation addressed the developmental trajectory of sensory dominance. In both studies, 6-year-olds, 9-year-olds, and adults were tested in order to examine sensory (audio-visual) dominance across different age groups. In Study 3, sensory dominance was put into an applied context by examining verbal and visual overshadowing effects among 4- to 6-year olds performing a face recognition task. The results of Study 1 and Study 2 support default auditory dominance in young children as proposed by Napolitano and Sloutsky (2004) that persists up to 6 years of age. For 9-year-olds, results on privileged modality processing were inconsistent. Whereas visual dominance was revealed in Study 1, privileged auditory processing was revealed in Study 2. Among adults, a visual dominance was observed in Study 1, which has also been demonstrated in preceding studies (see Spence, Parise, & Chen, 2012). No sensory dominance was revealed in Study 2 for adults. Potential explanations are discussed. Study 3 referred to verbal and visual overshadowing effects in 4- to 6-year-olds. The aim was to examine whether verbalization (i.e., verbally describing a previously seen face), or visualization (i.e., drawing the seen face) might affect later face recognition. No effect of visualization on recognition accuracy was revealed. As opposed to a verbal overshadowing effect, a verbal facilitation effect occurred. Moreover, verbal intelligence was a significant predictor for recognition accuracy in the verbalization group but not in the control group. This suggests that strengthening verbal intelligence in children can pay off in non-verbal domains as well, which might have educational implications.

Avaliação do potencial de desenvolvimento em meninos e meninas dos 4 aos 6 anos

Todos nós, educadores, devemos prestar uma atenção aprofundada às potencialidades e inclinações das crianças que constituem os nossos grupos, para que possamos estimular e desenvolver as suas competências. É nesse sentido que desenvolvemos este Estudo Exploratório, com o qual se pretende analisar a adaptação da avaliação de potencial derivada da Teoria das Inteligência Múltiplas ao contexto da Educação Pré-Escolar, com o objectivo de contribuir para a qualidade da intervenção educativa, articulando conceitos como Inteligência, Competência, Potencial, Currículo, Avaliação Dinâmica. Participam no estudo 42 crianças que frequentam Jardim de Infância e integram dois grupos heterogéneos e as respectivas educadoras. A metodologia é de natureza qualitativa e quantitativa, apoiando-se na aplicação dos seguintes instrumentos: modelo de avaliação de potencial baseado no Spectrum; Inventário de Quociente Emocional, versão para crianças e jovens (Bar-On Emocional Quotient Inventory: Youth Version), adaptado a educadores por Candeias e Monteiro (2010); questionário de Caracterização do ambiente educativo - Sala de Actividades, adaptado por Candeias e lglésias (2010); Teste de Avaliação de Habilidades Cognitivas de Solução de Problemas lnterpessoais (EVHACOSPI). Os resultados obtidos sugerem a importância de uma avaliação do potencial, baseada na Teoria das Inteligências Múltiplas, que utiliza instrumentos adequados a cada um dos domínios do potencial e da competência humana propostos por H. Gardner: verbal, Lógico-Matemática, Musical, Corporal-Cinestésica, Visuo-espacial, lnterpessoal, Intrapessoal e Naturalista. Apontam também para o papel que este tipo de avaliação pode desempenhar na intervenção educativa que se objectiva intencional e fundamentada. ABSTRACT: Ali of us, educators, must pay a special attention to the potentialities and inclinations of children who make up our groups, so enabling the stimulation and development of their competences. ln this sense we developed this Exploratory Study, through which is intended to analyse the adaptation of potential evaluation derived from the Theory of Multiple intelligences in the range of Pre-School Education, aiming at the contribution for the educative intervention: articulating concepts such as Intelligence, Competence Potential, Curriculum, and Dynamic Evaluation. The study involves 42 children attending Infant School, belonging to two heterogeneous groups and respective educators. Methodology is of qualitative and quantitative nature, supported by the following instruments: evaluation model based on Spectrum; Inventory of Emotional Quotient, version for children and youths, adapted to educators by Candeias e Monteiro (2010), Query of Characterization of Educative Environment - Activities Room, adapted by Candeias e lglésias (2010); Test for Evaluation of Cognitive Abilities of Interpersonal Problems Solution. (EVHACOSPI). The results suggest the importance of an assessment, based on the Theory of Multiple Intelligence, which uses instruments fitted to each of the domains of human potential and competence proposed by H. Gardiner: Verbal, Logical-Maths, Musical, Corporal¬ Kinaesthetic, Visuo-Spatial, Interpersonal, Intrapersonal and Naturalist. They also refer to the role that this type of assessment can play in the educational intervention aiming to be intentional and grounded.

A leitura no processo ensino aprendizagem em escolas da rede particular, na 4ª série do ensino fundamental em Belém do Pará: Uma busca para além decodificação

O presente estudo está baseado na Metodologia fenomenológica, com pesquisa bibliográfica e de campo. Apresenta como objetivo geral, analisar como se desenvolve o processo de ensino e aprendizagem de leitura, assim como, os estímulos e a prática do ato de ler em alunos de tenra idade em escolas particulares de Belém do Pará, em turmas da 4a Serie, do Ensino Fundamental. Tendo como objetivos específicos averiguar o ponto principal de indagação está centrado na questão se a leitura prática é apenas o desenvolvimento dos códigos linguísticos aprendidos, ou buscar não somente o processo de decodificar, sem considerar os aspectos mais abrangentes como a interpretação do texto, direcionado para o leitor ativo e atuante na compreensão das ideias do autor. Tal questionamento a respeito do processo de aprendizagem da leitura em nível fundamental das escolas particulares de Belém do Pará foi perguntado por meio de pesquisas de campo, a professores, alunos e para a coordenação, utilizando como instrumento de coleta de dados, questionário com perguntas abertas e fechadas de opinião entrevistas e grupos focais. No decorrer deste estudo, nota-se que para formar leitores mirins, serão exigidos alguns requisitos importantes, como a escolha de bons livros e atividades norteadoras de estimulação em classe e até mesmo fora dela. Afim de que principalmente o aluno em fase inicial de aprendizagem, seja e sinta-se preparado e ainda, conscientizado da importância da leitura para o seu questionamento crítico, como cidadão do futuro. Para tanto, fatores que interferem no processo de leitura, tais como: títulos variados, histórias que versem a respeito do imaginário cultural, textos direcionados ao público infantil, que despertem o interesse do alunado, além de apenas lei os códigos linguísticos na aquisição do texto, sem obtenção dos critérios interpretativos, que este possa evocar. A leitura é tida pela sociedade em geral, como um fator que pode levar o individuo a descobertas de novos patamares e horizontes sociais, mas somente indo além do mecanismo na apresentação dos textos cm sala de aula, é que o professor poderá atingir os níveis de compreensão integral do sistema escrito. Ensinando a ler, com elementos fundamentais para a iniciação de leitura interpretativa e proficiente no ensino fundamental. ABSTRACT: The present study is based upon the Phenomenological Methodology, with field and bibliographic research. It presents as a main objective the analysis on how the teaching and learning educational process develop upon the reading skills, as well as the encouragement and practice of reading in students of young ages in private schools in Belém, state of Pará (Brazil), in fourth grade groups, in elementary school. Having set specific goals, the search is centered in the practical reading ability matter, and if such ability is of linguistic code development solely learned or the search of not only the decoding process, without taking in consideration the broadening aspects, such as text comprehension, targeting the active reader especially when it comes to the author's ideas. Such discussion regarding the reading learning process in elementary levels in private schools in Belém, state of Para (Brazil) is questioned by field research, teachers, students and the coordination, using as data collecting instruments, questionnaires with open and closed questions, interviews and focal groups. Along the study, regarding the formation of young readers, it requires some aspects, such as, the choice of good titles and in-class stimulating activities or even outdoor ones, so the students - especially the ones in the initial phase of learning- are and feel prepared and even conscious of the importance of the reading for their critical thinking- as a future citizen. Therefore, the factors that may interfere in the reading process, for instance, varied titles, stories that verse towards the cultural imaginary, texts directed to the young public, that awaken the interest of the student body, beyond the linguistic codes acquired in the texts, not obtaining the interpreting criteria that it might evoke. The reading is, by the society, a fundamental factor that might lead the human being to discovering new standards and social horizons, but only going further the typical mechanisms in presenting the texts in class, is when the teacher may reach the whole levels of comprehension of the written system, teaching how to read, with fundamental elements to the initial reading in elementary school.

A new low temperature synthesis route of fraipontite (Zn,Al)3(Si,Al)2O5(OH)4

A low temperature synthesis method based on the decomposition of urea at 90°C in water has been developed to synthesise fraipontite. This material is characterised by a basal reflection 001 at 7.44 Å. The trioctahedral nature of the fraipontite is shown by the presence of a 06l band around 1.54 Å, while a minor band around 1.51 Å indicates some cation ordering between Zn and Al resulting in Al-rich areas with a more dioctahedral nature. TEM and IR indicate that no separate kaolinite phase is present. An increase in the Al content however, did result in the formation of some SiO2 in the form of quartz. Minor impurities of carbonate salts were observed during the synthesis caused by to the formation of CO32- during the decomposition of urea.

No evidence for association of ataxia-telangiectasia mutated gene T2119C and C3161G amino acid substitution variants with risk of breast cancer

Background There is evidence that certain mutations in the double-strand break repair pathway ataxia-telangiectasia mutated gene act in a dominant-negative manner to increase the risk of breast cancer. There are also some reports to suggest that the amino acid substitution variants T2119C Ser707Pro and C3161G Pro1054Arg may be associated with breast cancer risk. We investigate the breast cancer risk associated with these two nonconservative amino acid substitution variants using a large Australian population-based case–control study. Methods The polymorphisms were genotyped in more than 1300 cases and 600 controls using 5' exonuclease assays. Case–control analyses and genotype distributions were compared by logistic regression. Results The 2119C variant was rare, occurring at frequencies of 1.4 and 1.3% in cases and controls, respectively (P = 0.8). There was no difference in genotype distribution between cases and controls (P = 0.8), and the TC genotype was not associated with increased risk of breast cancer (adjusted odds ratio = 1.08, 95% confidence interval = 0.59–1.97, P = 0.8). Similarly, the 3161G variant was no more common in cases than in controls (2.9% versus 2.2%, P = 0.2), there was no difference in genotype distribution between cases and controls (P = 0.1), and the CG genotype was not associated with an increased risk of breast cancer (adjusted odds ratio = 1.30, 95% confidence interval = 0.85–1.98, P = 0.2). This lack of evidence for an association persisted within groups defined by the family history of breast cancer or by age. Conclusion The 2119C and 3161G amino acid substitution variants are not associated with moderate or high risks of breast cancer in Australian women.

Synthesis and characterization of K2Ca5(SO4)6· H2O, the equivalent of görgeyite, a rare evaporite mineral

Görgeyite, K2Ca5(SO4)6··H2O, is a very rare monoclinic double salt found in evaporites related to the slightly more common mineral syngenite. At 1 atmosphere with increasing external temperature from 25 to 150 °C, the following succession of minerals was formed: first gypsum and K2O, followed at 100 °C by görgeyite. Changes in concentration at 150 °C due to evaporation resulted in the formation of syngenite and finally arcanite. Under hydrothermal conditions, the succession is syngenite at 50 °C, followed by görgyeite at 100 and 150 °C. Increasing the synthesis time at 100 °C and 1 atmosphere showed that initially gypsum was formed, later being replaced by görgeyite. Finally görgeyite was replaced by syngenite, indicating that görgeyite is a metastable phase under these conditions. Under hydrothermal conditions, syngenite plus a small amount of gypsum was formed, after two days being replaced by görgeyite. No further changes were observed with increasing time. Pure görgeyite showed elongated crystals approximately 500 to 1000 µ m in length. The infrared and Raman spectra are mainly showing the vibrational modes of the sulfate groups and the crystal water (structural water). Water is characterized by OH-stretching modes at 3526 and 3577 cm–1 , OH-bending modes at 1615 and 1647 cm–1 , and an OH-libration mode at 876 cm–1 . The sulfate 1 mode is weak in the infrared but showed strong bands at 1005 and 1013 cm–1 in the Raman spectrum. The 2 mode also showed strong bands in the Raman spectrum at 433, 440, 457, and 480 cm–1 . The 3 mode is characterized by a complex set of bands in both infrared and Raman spectra around 1150 cm–1 , whereas 4 is found at 650 cm–1.