Síntese e atividade anti-HCV, anti-candida e antibacteriana de nitrochalconas

Pós-graduação em Química - IBILCE

A ressignificação na terapia cognitiva: uma análise a partir do modelo do Sistema de Esquema de Ações e Operações sobre Símbolos e Signos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Etnofaulismos e os dicionários monolíngues brasileiros

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Paralisia cerebral: efeitos da escrita sobre a escrita

The aim of this research was to apprehend the effects of text reading in S.'s writing productions, a child in literacy process. S. is a child who can't speak or write by her own due to a dystonic quadriplegic CP. S. communicates with Blissymbols which were introduced in a school-clinic in São Paulo city when she was six years old. At the same time the literacy process took place and she indicated symbols, letters and numbers in a board by scanning. The teacher related S.'s difficulties concerning reading activities, so a weekly activity was proposed by the speech therapist in the classroom. The teacher and her assistant participated in the activity. A cutout of the activity involving a book reading when S. was between eight years and seven months old and nine years and one month old was analysed. The research was based in Borges (2006) grounded in The Brazilian Interactionism according to De Lemos (1992; 1995 and others) and proposes a literacy process among students from the first series in a regular school by the reading of different texts. The activity guided by the speech therapist took place side by side with the literacy program guided by the teacher and resulted in various S's text productions. The data was collected through film transcriptions from the activities in the classroom and from materials produced by S. through the reading of the chosen book. These data integrates NALíngua-CNPq databases coordinated by Dr. Alessandra Del Ré whose aim is to investigate the language acquisition process. S.'s reading and writing acquisition occurred in a singular way, affected by the using of Blissymbols that became S.'s speech modality: a written-speech with symbols and alphabetic writing

The Importance of Teaching Students How to Read to Comprehend Mathematical Language

In this action research study of my classroom of 8th and 9th grade Algebra I students, I investigated if there are any benefits for the students in my class to learn how to read, translate, use, and understand the mathematical language found daily in their math lessons. I discovered that daily use and practice of the mathematical language in both written and verbal form, by not only me but by my students as well, improved their understanding of the textbook instructions, increased their vocabulary and also increased their understanding of their math lessons. I also found that my students remembered the mathematical material better with constant use of mathematical language and terms. As a result of this research, I plan to continue stressing the use of mathematical language and vocabulary in my classroom and will try to develop new ways to help students to read, understand, and remember mathematical language they find daily in their textbooks.

Why Are We Writing? This is Math Class!

In this action research study of my classroom of 8th grade mathematics, I investigated writing in the content area. I have realized how important it is for students to be able to communicate mathematical thoughts to help gain a deeper understanding of the content. As a result of this research, I plan to enforce the use of writing thoughts and ideas regarding math problems. Writers develop skills and generate new thoughts and ideas every time they sit down to write. Writing evolves and grows with ongoing practice, and that means thinking skills mature along with it. Writing is a classroom activity which offers the possibility for students to develop a deeper understanding of the mathematics they are learning. Writing encourages students to reflect on and explore their reasoning and to extend their thinking and understanding. Students are often content with manipulating symbols and doing routine math problems, without ever reaching a deep and personal understanding of the material. My goal through this project was to help students understand why they were doing certain operations to solve math problems. Writing is an essential tool for thinking and is fundamental in every class, in every subject, and on every level of thinking; skills in writing must be practiced and refined, and students must have frequent opportunities to write across the curriculum. Communication in mathematics is not a simple and unambiguous activity.

Paralisia cerebral: efeitos da escrita sobre a escrita

The aim of this research was to apprehend the effects of text reading in S.'s writing productions, a child in literacy process. S. is a child who can't speak or write by her own due to a dystonic quadriplegic CP. S. communicates with Blissymbols which were introduced in a school-clinic in São Paulo city when she was six years old. At the same time the literacy process took place and she indicated symbols, letters and numbers in a board by scanning. The teacher related S.'s difficulties concerning reading activities, so a weekly activity was proposed by the speech therapist in the classroom. The teacher and her assistant participated in the activity. A cutout of the activity involving a book reading when S. was between eight years and seven months old and nine years and one month old was analysed. The research was based in Borges (2006) grounded in The Brazilian Interactionism according to De Lemos (1992; 1995 and others) and proposes a literacy process among students from the first series in a regular school by the reading of different texts. The activity guided by the speech therapist took place side by side with the literacy program guided by the teacher and resulted in various S's text productions. The data was collected through film transcriptions from the activities in the classroom and from materials produced by S. through the reading of the chosen book. These data integrates NALíngua-CNPq databases coordinated by Dr. Alessandra Del Ré whose aim is to investigate the language acquisition process. S.'s reading and writing acquisition occurred in a singular way, affected by the using of Blissymbols that became S.'s speech modality: a written-speech with symbols and alphabetic writing

Uso da RMN como um sensor online em processos industriais

Nuclear magnetic resonance (NMR) is one of the most versatile analytical techniques for chemical, biochemical and medical applications. Despite this great success, NMR is seldom used as a tool in industrial applications. The first application of NMR in flowing samples was published in 1951. However, only in the last ten years Flow NMR has gained momentum and new and potential applications have been proposed. In this review we present the historical evolution of flow or online NMR spectroscopy and imaging, and current developments for use in the automation of industrial processes.

Studies on Oxidative Couplings in H-Phosphonate Chemistry

In this thesis oxidative coupling of H-phosphonate and H phosphonothioate diesters with different alcohols and amines are presented. Since the reactions with alcohols previously have been particularly unfavourable due to competing side reactions, a modified protocol leading to high coupling yields of structurally diverse hydroxylic components was developed. The phosphorylation reaction was studied using 31P NMR spectroscopy and for the first time the previously only postulated reactive intermediate involved in these reactions was observed. The use of iodine in combination with a bulky chlorosilane in pyridine was found to have a profound effect on both the suppression of side reactions and the rate of the oxidative couplings, and led to a clean formation of phosphorylated products in high yields. This synthetic protocol was then extended to include coupling reactions with bis-functional reagents containing hexamethylene linkers to provide handles for derivatisations of oligonucleotides. A synthetic protocol consisting of the stereospecific oxidative coupling of amines with H-phosphonate diesters to produce phosphoroamidates was designed in such a way that it permitted control of the stereochemical outcome of the reactions. Based on a silylation-mediated reaction utilising phenyl H phosphonothioate monoester as a thiophosphonyl transferring agent, a method was developed and used for the preparation of H-phosphonothioate building blocks for the synthesis of DNA analogues.

Analisi degli aspetti di qualità nella gestione dei sistemi di drenaggio urbano attraverso modellazione numerica e indagini di campo

In order to protect river water quality, highly affected in urban areas by continuos as intermittent immissions, it is necessary to adopt measures to intercept and treat these polluted flows. In particular during rain events, river water quality is affected by CSOs activation. Built in order to protect the sewer system and the WWTP by increased flows due to heavy rains, CSOs divert excess flows to the receiving water body. On the basis of several scientific papers, and of direct evidences as well, that demonstrate the detrimental effect of CSOs discharges, also the legislative framework moved towards a stream standard point of view. The WFD (EU/69/2000) sets new goals for receiving water quality, and groundwater as well, through an integrated immission/emissions phylosophy, in which emission limits are associated with effluent standards, based on the receiving water characteristics and their specific use. For surface waters the objective is that of a “good” ecological and chemical quality status. A surface water is defined as of good ecological quality if there is only slight departure from the biological community that would be expected in conditions of minimal anthropogenic impact. Each Member State authority is responsible for preparing and implementing a River Basin Management Plan to achieve the good ecological quality, and comply with WFD requirements. In order to cope with WFD targets, and thus to improve urban receiving water quality, a CSOs control strategy need to be implemented. Temporarily storing the overflow (or at least part of it) into tanks and treating it in the WWTP, after the end of the storm, showed good results in reducing total pollutant mass spilled into the receiving river. Italian State Authority, in order to comply with WFD statements, sets general framework, and each Region has to adopt a Water Remediation Plan (PTA, Piano Tutela Acque), setting goals, methods, and terms, to improve river water quality. Emilia Romagna PTA sets 25% reduction up to 2008, and 50% reduction up to 2015 fo total pollutants masses delivered by CSOs spills. In order to plan remediation actions, a deep insight into spills dynamics is thus of great importance. The present thesis tries to understand spills dynamics through a numerical and an experimental approach. A four months monitoring and sampling campaign was set on the Bologna sewer network, and on the Navile Channel, that is the WWTP receiving water , and that receives flows from up to 28 CSOs during rain events. On the other hand, the full model of the sewer network, was build with the commercial software InfoWorks CS. The model was either calibrated with the data from the monitoring and sampling campaign. Through further model simulations interdependencies among masses spilled, rain characteristics and basin characteristics are looked for. The thesis can be seen as a basis for further insighs and for planning remediation actions.

Progettazione e sintesi di nuovi derivati azetidinonici biologicamente attivi

In this PhD-thesis new synthetic approaches towards new azetidinone derivatives are described. In particular, 4-alkyliden-β-lactams were used as starting materials for the preparation of new biologically active compounds. The carbapenem Thienamycin has got a broad spectrum of activity as antibiotic. It has got 3 stereocenters and apart of one epimer, all isomers have been synthesized. Using the 4-alkyliden-β-lactam benzilyc ester as precursor, we developed a synthesis for this missing epimer, which is described in chapter II. Biological tests in order to establish its biological activity are under way. The Hunsdiecker-Borodine reaction was extensively studied for the preparation of the mono halogenated and – surprisingly – the dihalogenated derivative from the 4-alkyliden-azetidinone carboxylic acid. The herein described synthetic procedures allowed the preparation of chloro-, bromo- and iodo derivatives in good to excellent yield. Furthermore, the reaction mechanism was investigated by NMR-experiments and is described in detail in chapter III. In chapter IV, synthetic approaches towards new β-lactam derivatives for inhibition of the histone deacetylase enzymes (HDACs) are reported. In collaboration with the company Sigma-Tau (Rome), 14 new β-lactams were synthesized. The new β-lactams were evaluated for the activity showing a promising activityparticulary, 10 of the β-lactams synthesized were evaluated for the in vitro inhibitory activity against the 11 human HDACs isoforms and they showed a selective inhibition of HDAC6 or HDAC8 in micromolar range. Finally, preliminary studies were conducted for the employment of 4-alkyliden-β-lactams as precursors for the synthesis of chiral β-amino acids by an opening of the β-lactam ring. In chapter V is described the ring opening reaction catalyzed by the enzyme lipase Cal-B. Preliminary results have shown that the enzyme not only catalyzes the ring opening of the β-lactam precursor, moreover, it leads to the formation of a cyclic dimer by the reaction of two molecules of β-amino acid obtained.

Poly(para-phenylenethinylen)e - Synthese, Charakterisierung und Eigenschaften von endfunktionalisierten Polymeren und Stäbchen-Knäuel-Diblockcopolymeren

Der erste Teil der vorliegenden Dissertation beschäftigt sich mit der Eignung des ?,?-dithiolfunktionalisierten Poly(para-phenylenethinylen)s (PPE) als sogenannter „molekularer Draht“ für die molekulare Elektronik. Über die HECK-CASSAR-SONOGASHIRA-Reaktion wurden vollständig endfunktionalisierte, defektfreie Polymere mit durchschnittlichen Polymerisationsgraden von bis zu 45 Repetitionseinheiten synthetisiert. Die starke Aggregationsneigung der PPE, die die Anordnung der Polymerketten zwischen den Goldelektroden unterstützen soll, wurde mittels Rasterkraft- und Rastertunnelmikroskopie untersucht. Für die Untersuchungen zur Dotierbarkeit wurden ESR-, ENDOR-, UPS- und XPS-Messungen durchgeführt. Es konnte gezeigt werden, dass sich das PPE reduzieren lässt.Im zweiten Teil der Arbeit wurden die PPE zur Synthese von Stäbchen-Knäuel-Diblockcopolymeren eingesetzt. Die Darstellung erfolgte nach der 'grafting onto'-Methode, indem monocarboxyl-endfunktionalisiertes PPE mit flexiblen monohydroxyl-endfunktionalisiertem Polyethylenglykol, Polydimethylsulfoxid bzw. Polytetrahydrofuran verestert wurde. Den Nachweis der Diblockcopolymerbildung erbrachten die 1H?NMR-Spektroskopie und die für Diblockcopolymere noch wenig angewandte MALDI-TOF-Massenspektrometrie. Mittels Rasterkraftmikroskopie und Computersimulationen zur Molekularmechanik und -dynamik wurden die Aggregationseigenschaften der Diblockcopolymere untersucht.

L'idea di metafora nell'opera di Oswald Mathias Ungers

This research focuses on the definition of the complex relationship that exists between theory and project, which - in the architectural work by Oswald Mathias Ungers - is based on several essays and on the publications that - though they have never been collected in an organic text - make up an articulated corpus, so that it is possible to consider it as the foundations of a theory. More specifically, this thesis deals with the role of metaphor in Unger’s theory and its subsequent practical application to his projects. The path leading from theoretical analysis to architectural project is in Ungers’ view a slow and mediated path, where theory is an instrument without which it would not be possible to create the project's foundations. The metaphor is a figure of speech taken from disciplines such as philosophy, aesthetics, linguistics. Using a metaphor implies a transfer of meaning, as it is essentially based on the replacement of a real object with a figurative one. The research is articulated in three parts, each of them corresponding to a text by Ungers that is considered as crucial to understand the development of his architectural thinking. Each text marks three decades of Ungers’ work: the sixties, seventies and eighties. The first part of the research deals with the topic of Großform expressed by Ungers in his publication of 1966 Grossformen im Wohnungsbau, where he defines four criteria based on which architecture identifies with a Großform. One of the hypothesis underlying this study is that there is a relationship between the notion of Großform and the figure of metaphor. The second part of the thesis analyzes the time between the end of the sixties and the seventies, i.e. the time during which Ungers lived in the USA and taught at the Cornell University of Ithaca. The analysis focuses on the text Entwerfen und Denken in Vorstellungen, Metaphern und Analogien, written by Ungers in 1976, for the exhibition MAN transFORMS organized in the Cooper - Hewitt Museum in New York. This text, through which Ungers creates a sort of vocabulary to explain the notions of metaphor, analogy, signs, symbols and allegories, can be defined as the Manifesto of his architectural theory, the latter being strictly intertwined with the metaphor as a design instrument and which is best expressed when he introduces the 11 thesis with P. Koolhaas, P. Riemann, H. Kollhoff and A. Ovaska in Die Stadt in der Stadt in 1977. Berlin das grüne Stadtarchipel. The third part analyzes the indissoluble tie between the use of metaphor and the choice of the topic on which the project is based and, starting from Ungers’ publication in 1982 Architecture as theme, the relationship between idea/theme and image/metaphor is explained. Playing with shapes requires metaphoric thinking, i.e. taking references to create new ideas from the world of shapes and not just from architecture. The metaphor as a tool to interpret reality becomes for Ungers an inquiry method that precedes a project and makes it possible to define the theme on which the project will be based. In Ungers’ case, the architecture of ideas matches the idea of architecture; for Ungers the notions of idea and theme, image and metaphor cannot be separated from each other, the text on thematization of architecture is not a report of his projects, but it represents the need to put them in order and highlight the theme on which they are based.

Struktur- und Reaktionsaufklärung durch Kombination von Theorie und Experiment

Die vorliegende Dissertation beinhaltet Anwendungen der Quantenchemie und methodische Entwicklungen im Bereich der "Coupled-Cluster"-Theorie zu den folgenden Themen: 1.) Die Bestimmung von Geometrieparametern in wasserstoffverbrückten Komplexen mit Pikometer-Genauigkeit durch Kopplung von NMR-Experimenten und quantenchemischen Rechnungen wird an zwei Beispielen dargelegt. 2.) Die hierin auftretenden Unterschiede in Theorie und Experiment werden diskutiert. Hierzu wurde die Schwingungsmittelung des Dipolkopplungstensors implementiert, um Nullpunkt-Effekte betrachten zu können. 3.) Ein weiterer Aspekt der Arbeit behandelt die Strukturaufklärung an diskotischen Flüssigkristallen. Die quantenchemische Modellbildung und das Zusammenspiel mit experimentellen Methoden, vor allem der Festkörper-NMR, wird vorgestellt. 4.) Innerhalb dieser Arbeit wurde mit der Parallelisierung des Quantenchemiepaketes ACESII begonnen. Die grundlegende Strategie und erste Ergebnisse werden vorgestellt. 5.) Zur Skalenreduktion des CCCSD(T)-Verfahrens durch Faktorisierung wurden verschiedene Zerlegungen des Energienenners getestet. Ein sich hieraus ergebendes Verfahren zur Berechnung der CCSD(T)-Energie wurde implementiert. 6.) Die Reaktionsaufklärung der Bildung von HSOH aus di-tert-Butyl-Sulfoxid wird vorgestellt. Dazu wurde die Thermodynamik der Reaktionsschritte mit Methoden der Quantenchemie berechnet.

Rational design of selective anion receptors

The new family of the anion receptors based on oligoureas with varied flexibility was developed and studied. The preparation of the urea chains containing two different units in various sequences was elaborated. The complete sets of four cyclic trimers and six tetramers based on the two units were prepared. Their conformational and complexation properties were studied with NMR spectroscopy and X-ray structure determinations, their behaviour towards various anions was evaluated and compared. The synthesis and the same studies were performed also with four different cyclic hexamers. During these studies the remarkable templation by two halide anions was observed.