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Dissertations / Theses on the topic 'Bases(Chemistry)'

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Published: 4 June 2021
Last updated: 26 February 2023

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1

Drechsler, Michal. "Models in chemistry education : A study of teaching and learning acids and bases in Swedish upper secondary schools." Doctoral thesis, Karlstad University, Faculty of Technology and Science, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:kau:diva-783.

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This thesis reports an investigation of how acid-base models are taught and understood in Swedish upper secondary school. The definition of the concepts of acids and bases has evolved from a phenomenological level to an abstract (particle) level. Several models of acids and bases are introduced in Swedish secondary school. Among them an ancient model, the Arrhenius model and the Brønsted model. The aim of this study was to determine how teachers handle these models in their teaching. Further, to investigate Swedish upper secondary students’ ideas about the role of chemistry models, in general, and more specific, of models of acids and bases. The study consisted of two parts. First, a study was performed to get an overview of how acids and bases are taught and understood in Swedish upper secondary schools. It consisted of three steps: (i) the most widely used chemistry textbooks for upper secondary school in Sweden were analysed, (ii) six chemistry teachers were interviewed, and, (iii) finally also seven upper secondary school students were interviewed. The results from this study were used in the second part which consisted of two steps: (i) nine chemistry teachers were interviewed regarding their pedagogical content knowledge (PCK) of teaching acids and bases, and (ii) a questionnaire was administered among chemistry teachers of 441 upper secondary schools in Sweden. The results from the interviews show that only a few teachers chose to emphasise the different models of acids and bases. Most of the teachers thought it was sufficient to distinguish clearly between the phenomenological level and the particle level. In the analysis of the questionnaire three subgroups of teachers were identified. Swedish upper secondary chemistry teachers, on the whole, had a strong belief in the Brønsted model of acids and bases. However, in subgroup one (47 %) teachers’ knowledge of how the Brønsted model differs from older models was limited and diverse. Teachers in subgroup two (38 %) and three (15 %) seemed to understand the differences between the Brønsted model and older models, but teachers in subgroup 2 did not explain the history of the development of acids and bases in their teaching. Instead they (as teachers in subgroup one) relied more on the content in the textbooks than teachers in the third subgroup. Implications for textbook writers, teaching, and further research are discussed.

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2

Drechsler, Michal. "Models in chemistry education : a study of teaching and learning acid and bases in Swedish upper secondary schools /." Karlstad : Faculty of Technology and Science, Chemistry, Karlstad University, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:kau:diva-783.

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3

Ward, Nathan Andrew. "Resurrection of Organophosphorus-Aged Acetylcholinesterase via Mannich Bases Derived from Proline." The Ohio State University, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=osu1565714137331736.

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4

Joubert, Corli. "Heterogenization of Schiff base complexes on mesoporous silica and their application as catalysts in the oxidative transformation of alcohols." Thesis, Stellenbosch : Stellenbosch University, 2013. http://hdl.handle.net/10019.1/79979.

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Thesis (MSc)--Stellenbosch University, 2013.
ENGLISH ABSTRACT: In this thesis the synthesis of a range of model and siloxane functionalized salicylaldimine ligands and [N-(n-propyl)-(2-pyridyl)] diimine ligands are described. The functionalized ligands were obtained by the reaction of salicylaldehyde and 2-pyridinecarboxaldehyde with 3-aminopropyltriethyoxysilane. All ligands were characterized by FT-IR and 1H NMR spectroscopy. The salicylaldimine ligands were reacted with either Cu(II) or Pd(II) salts to form both the model and functionalized Cu(II) and Pd(II) complexes. The Cu(II) complexes were characterized using FT-IR, EPR and UV-VIS spectroscopy while the Pd(II) complexes were characterized using FT-IR, 1H NMR and 13C{1H} NMR spectroscopy. The diimine ligands were reacted with Cu(II) salts to form functionalized pyridinyl complexes which were characterized used FT-IR spectroscopy. Two mesoporous silica supports, MCM-41 and SBA-15 were synthesized. The siloxane functionalized salicylaldimine Cu(II) and Pd(II) complexes were immobilized onto these supports to produce heterogenized catalysts. These catalysts were characterized using a range of solid-state techniques: BET nitrogen adsorption/desorption, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), ICP-AES, and powder X-ray diffraction (XRD) analysis. The powder XRD and SEM analysis showed that the structural integrity of the catalyst supports was kept intact during the immobilization process. BET analysis and ICP-AES showed that the complexes had been attached to the silica supports. Both the model complexes and heterogenized catalyst systems were tested in the oxidation of benzyl alcohol to benzaldehyde. The model copper catalyst showed high activity in this reaction with molecular oxygen used as oxidant and the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical as co-oxidant. The immobilized copper complexes showed low activity in the same reaction. This was attributed to steric hindrance around the active site dye to its entrapment with the silica matrix thus hindering the formation of a key intermediate in the oxidation cycle due to steric hindrance. The palladium complexes were not active in the oxidation reaction when molecular oxygen was used as oxidant, but showed slight activity when hydrogen peroxide was used.
AFRIKAANSE OPSOMMING: In hierdie tesis word die sintese van ‘n reeks model sowel as gefunksioneerde salisielaldemien ligande en [N-(n-propiel)-(2-piridiel)] di-imien ligande beskryf. Die gefunksioneerde ligande is verkry deur die reaksie van salisielaldehied en en 2-piridienaldehied met 3-aminopropieltriëtoksiesilaan. Al die ligande is gekarakteriseer deur FT-IR en 1H-KMR spektroskopie. Die salisielaldimien ligande is met óf Cu(II) óf Pd(II) soute reageer om beide die model en gefunksioneerde Cu(II) en Pd(II) komplekse te vorm. Die Cu(II) komplekse is gekarakteriseer deur FT-IR, EPR en UV-Vis spektroskopie terwyl die Pd(II) komplekse deur FT-IR, 1H-KMR en 13C{1H}-KMR spektroskopie gekarakteriseer is. Die di-imien ligande is met Cu(II) soute reageer om gefunksioneerde piridinielkompekse te vorm wat deur FT-IR spektroskopie gekarakteriseer is. Twee mesoporeuse silika draers, MCM-41 en SBA-15 is gesintetiseer. Die siloksaan-gefunksioneerde salisielaldemien Cu(II) en Pd(II) komplekse is op hierdie draers geimobiliseer om geheterogeniseerde katalisatore te vorm. Hierdie katalisatore is gekarakteriseer deur van ‘n wye reeks vaste toestand tegnieke gebruik te maak: BET stikstof adsorpsie/desorpsie, skandeer elektron mikroskopie (SEM), termiese gravimetriese analise (TGA), ICP-AES en poeier-XRD analise. Die poeier-XRD en SEM analisies het aangetoon dat die strukturele integriteit van die katalisator draers behoue gebly het tydens die immobiliseringsproses. BET analise en ICP-AES het aangetoon dat die komplekse aan die silika draers geheg is. Beide die model komplekse en geimobiliseerde katalisators is getoets in die oksidasie van bensielalkohol na bensaldehied. Die model Cu(II) katalisator het hoë aktiwiteit in hierdie reaksie getoon met molekulêre suurstof as oksideermiddel en die (2,2,6,6-tetrametielpipiridien-1-iel)oksiel radikaal as ko-oksideermiddel. Die geimobiliseerde Cu(II) komplekse het lae aktiwiteit in dieselfde reaksie getoon. Dit is toegeskryf aan steriese hindernis rondom die aktiewe sentrum as gevolg van die verstrikking binne die silika matrys, wat die vorming van ‘n belangrike tussentoestand in die oksidasie-siklus verhinder. Die Pd(II) komplekse was nie aktief in die oksidasie-reaksie in die geval waar molekulêre suurstof as oksideermiddel gebruik is nie, maar het effense aktiwiteit getoon waneer waterstofperoksied gebruik is.
Sasol
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5

Schoeman, Jakob Johannes. "Electrodialysis of salts, acids and bases by electro-osmotic pumping." Thesis, Pretoria: [s.n.], 1992. http://upetd.up.ac.za/thesis/available/etd-03092010-090836/.

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6

Yuen, Lao-Duien. "Part I. Studies involving the formation of pyridoxamine-5'-phosphate Schiff bases and their zinc(II) complexes ; Part II. Activity of partly metallated polymer in the decarboxylation of oxalacetic acid /." The Ohio State University, 1985. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487262825075348.

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7

Gondin, Carolyne de Oliveira. "Sequência didática para o ensino de ácidos e bases: da experimentação ao jogo numa abordagem contextualizada." Universidade Tecnológica Federal do Paraná, 2016. http://repositorio.utfpr.edu.br/jspui/handle/1/2478.

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Acompanha: Sequência didática - Ensino de ácidos e bases: da experimentação ao jogo numa abordagem contextualizada
Esta pesquisa teve como objetivo avaliar a contribuição de uma sequência didática, para a aprendizagem de estudantes, no ensino de funções ácidos e bases, em que se utilizou da experimentação, e, de um jogo, numa abordagem contextualizada. A abordagem metodológica foi qualitativa de natureza interpretativa, com observação participante, de sua natureza aplicada. Participaram da pesquisa, 26 estudantes, do primeiro ano do ensino médio, do turno matutino, de um colégio da rede estadual de ensino da Região Centro Sul do Paraná, Brasil. A análise de dados foi realizada, a partir de categorias, e subcategorias, estratificadas do conteúdo das respostas dos estudantes, no programa MAXQDA. A análise e interpretação, dos dados foram realizadas a partir do desenvolvimento da sequência didática, que integrou diferentes atividades, em oito momentos, articulada desde uma experimentação problematizadora, a um jogo didático, numa abordagem contextualizada. Indicou contribuições da atividade experimental problematizadora, como uma estratégia eficiente, para problematização, contextualização, e, o estímulo a questionamentos de investigação. Possibilitou a realização de discussões, reflexão, registros, e, levantamento de hipóteses a respeito do tema, que foram fundamentais para geração de dados, a respeito das concepções iniciais dos estudantes, sobre ácidos e bases. Despertou a curiosidade dos estudantes para os acontecimentos experimentais, fazendo com que agissem como protagonistas na construção de seu conhecimento na busca de respostas, numa atitude cientifica. O desenvolvimento do jogo didático elaborado estimulou de forma unânime a motivação dos estudantes, potencializou o interesse, a curiosidade, participação ativa nas atividades, melhorando o relacionamento entre estudantes, e como consequência a evolução conceitual, social e emocional. De forma geral, a sequência didática, contribuiu para que os estudantes estabelecessem relações entre os conteúdos científicos de ácidos e base, e o seu contexto, sendo instigados na busca pelo saber. De forma que, foi possível observar contribuições nas dimensões de abrangência conceitual, procedimental, e atitudinal, previstas nas intenções educacionais.
The aim of this research was to evaluate the contribution of a didactic sequence for the learning of students in the teaching of acid functions and bases, in which experimentation and a game in a contextualized approach were used. The methodological approach was qualitative of an interpretative nature, with participant observation, of its applied nature. Twenty-six students participated in the study, from the first grade of high school, of the morning term, of a state school in the Southern Center Region of Paraná, Brazil. The data analysis was carried out, from categories, and subcategories, stratified of the content of the students' answers, in the MAXQDA program. The analysis and interpretation of the data were obtained from the development of the didactic sequence, which integrated different activities, in eight moments, articulated from a problematizing experimentation, to a didactic game, in a contextualized approach. It indicated contributions of problematizing experimental activity, as an efficient strategy, for problematization, contextualization, and the stimulation of research questions. It made possible the accomplishment of discussions, reflection, registers, and hypotheses about the subject, which were fundamental for data generation, regarding the initial conceptions of the students about acids and bases. It aroused the curiosity of the students for the experimental events, causing them to act as protagonists in the construction of their knowledge in the search for answers in a scientific attitude. The development of the elaborated didactic game unanimously stimulated students' motivation, enhanced interest, curiosity and active participation in activities, improving students’ relationships and as consequence a conceptual, social and emotional evolution has arisen. In general, the didactic sequence contributed to the students establishing relationships between the scientific contents of acids and base and their context, being instigated in the search for knowledge. Thus, it was possible to observe contributions in the dimensions of conceptual, procedural, and attitudinal scope, foreseen in educational intentions.
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8

Carvalho, Vítor Alexandre Nunes de. "Efeito da oxidação eletroquímica e da irradiação ultravioleta na formação de biomoléculas a partir do tiocianato de amônio em condições pré-bióticas." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/75/75134/tde-23102018-155416/.

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Desde o clássico experimento de Miller em 1953 evidenciando a formação de aminoácidos em condições de Terra primitiva, a química do período pré-biótico ainda é muito discutida. Cita-se, por exemplo, o papel da teoria sulfociânica, que descreve a origem de moléculas orgânicas a partir de compostos contendo enxofre, como o tiocianato de amônio (NH4SCN). Neste contexto, essa Tese aborda um estudo sobre a investigação do NH4SCN em condições pré-bióticas. Para isso, experimentos de oxidação eletroquímica e de irradiação ultravioleta (UV) em amostras contendo NH4SCN em diferentes condições experimentais foram conduzidos. Por eletroquímica acoplada à espectroscopia vibracional no infravermelho (FTIR in situ), identificou-se como o primeiro produto da oxidação do NH4SCN, o dímero tiocianogênio (SCN)2, que é um reconhecido precursor dos oligômeros do período pré-biótico. Em contrapartida, a irradiação UV do NH4SCN levou a formação de enxofre ortorrômbico (S8) e das bases nitrogenadas 4-(3H)-pirimidinona, citosina, purina e adenina, além de outras moléculas. Provavelmente, o cianeto de hidrogênio (HCN) é um dos precursores das biomoléculas supracitadas, contrariando uma possível rota via (SCN)2. Os resultados desse estudo também reforçam a hipótese de que não há formação direta de aminoácidos por irradiação do NH4SCN. Desta forma, propõe-se aqui que a formação dos blocos do DNA, as bases nitrogenadas, também possa ser inserida no contexto da teoria sulfociânica.
Since the classic Miller experiment in 1953 evidencing the amino acids formation under early Earth conditions, the chemistry of the prebiotic period is still very discussed. It is cited, for example, the role of sulfocyanic theory, which describes the origin of organic molecules from sulfur-containing compounds such as ammonium thiocyanate (NH4SCN). In this context, this thesis shows a study about the investigation of NH4SCN in prebiotic conditions. Thereby, experiments of electrochemical oxidation and ultraviolet (UV) irradiation were carried out with samples containing NH4SCN in different experimental conditions. By using electrochemistry coupled to Fourier transform infrared spectroscopy (FTIR in situ), the dimer thiocyanogen (SCN)2 was identified as the first oxidation product of NH4SCN, which is a recognized precursor of the oligomers from prebiotic period. In counterpart, UV irradiation of the NH4SCN led to the formation of orthorhombic sulfur (S8) and the nitrogenous bases 4-(3H)-pyrimidinone, cytosine, adenine and purine, besides other molecules. Probably, hydrogen cyanide (HCN) is one of the precursors of the biomolecules abovementioned, contradicting a possible route via (SCN)2. The results of this study also reinforce the hypothesis that there is no direct formation of amino acids by irradiation of NH4SCN. Thus, it is proposed here that the formation of DNA blocks, the nitrogenous bases, can also be inserted in the context of sulfocyanic theory.
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Langaro, Eloise Aparecida. "Cimento álcali ativado a partir da valorização da escória de alto forno a carvão vegetal." Universidade Tecnológica Federal do Paraná, 2016. http://repositorio.utfpr.edu.br/jspui/handle/1/1891.

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Enquanto que na produção do cimento Portland é feita a extração de matérias-primas não renováveis e o lançamento de CO2 de forma excessiva; a fabricação dos cimentos álcali ativados não envolve a calcinação dos materiais e pode utilizar como matéria-prima subprodutos da indústria. Nesse contexto, os cimentos álcali ativados surgem como uma nova classe de materiais aglomerantes de bom desempenho e baixo impacto ambiental, os quais podem ser sintetizados unicamente com resíduos, como por exemplo, escórias de alto forno ativadas com diferentes produtos alcalinos, gerando materiais com características interessantes para aplicações na construção civil. Em função da composição química, as escórias de alto forno geradas em fornos a coque são empregadas como adição ao cimento Portland; entretanto, aquelas oriundas de fornos a carvão vegetal não encontram a mesma destinação pois normalmente não se adequam aos módulos de basicidade prescritos nas normas, implicando assim um passivo ambiental. Esta pesquisa tem por objetivo à obtenção de cimentos álcali ativados (CAT) visando a valorização da escória A (ácida). Também foi utilizada uma escória proveniente de alto forno a coque (B) como matéria-prima, a fim de comparar a composição química de ambas. Foram elaboradas composições iniciais de CAT com hidróxido de sódio (NaOH) como ativador, as quais foram submetidas a dois processos de cura (úmida e imersa) para testes iniciais. A cura imersa se mostrou menos propícia no uso da escória como ligante, uma vez que o contato com a água lixivia o material diminuindo sua superfície de contato, o que traz consequências no desenvolvimento mecânico e da microestrutura. Já em cura úmida, com 5% de NaOH como ativador, as argamassas de escória A obtiveram ótimo desempenho mecânico, atingindo valores próximos a 45MPa aos 28 dias; sendo que o desenvolvimento da fase de C-S-H e hidrotalcita pôde ser observada a partir dos difratogramas de raios-X e análises térmicas. A escória B desenvolveu menor resistência na presença do ativador, mas as mesmas fases foram observadas em ambas as composições; constatando-se então que a composição química da matéria-prima tem forte influência no desempenho dos CAT’s.
While production of Portland cement is made the extraction of non-renewable raw materials and the release of CO2 excessively; the manufacture of alkali activated cement does not involve the calcination of materials and can be used as raw material byproducts of industry. In this context, the alkali activated cements emerge as a new class of binder materials of good performance and low environmental impact, which can be synthesized only with waste, such as slag in blast furnace activated with different alkalis generating materials with characteristics interesting for applications in construction. Depending on the chemical composition, blast furnace slag generated in coke ovens are used as addition to Portland cement; however, those from charcoal ovens are not the same destination as usually is inappropriate the basicity modules prescribed in the rules, thus implying an environmental liability. This research has the purpose to obtain activated alkali cements (CAT) aimed at the valorisation of the slag (acid). Also used was a blast furnace from coke (B) as raw material, in order to compare the chemical composition of both. CAT initial compositions with sodium hydroxide was prepared (NaOH) as an activator, which were subjected to two curing processes (wet and immersed) for initial testing. The immersed cure was less benign in the use of slag as a binder caused a lower compressive strenght, since the contact with the water solubilizing the material reducing its contact surface. In wet cure, with 5% NaOH as an activator, the slag mortars A obtained high mechanical performance, arriving values close to 45MPa at 28 days; the development of C-S-H and hydrotalcite phase was observed from the XRD patterns of X-rays and thermal analysis. Slag B developed less strenght in the presence of the activator, but the same phases were observed in both compositions. It was possible to verify that the chemical composition of raw material had strong influence on the performance of the CAT’s.
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Laranja, Marlon Larry [UNESP]. "Síntese e caracterização de híbridos orgânico-inorgânicos luminescentes para aplicação em ensaios biológicos." Universidade Estadual Paulista (UNESP), 2013. http://hdl.handle.net/11449/97783.

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Complexos de íons lantanídeos luminescentes tem se destacado em marcação biológica em função de sua alta eficiência de emissão atribuída ao “efeito antena”. A incorporação destes complexos em matrizes inorgânicas leva a formação de materiais híbridos orgânico-inorgânicos. Esse híbrido pode ser utilizado como marcador em ensaios biológicos desde que acoplado a moléculas de reconhecimento específico, p.e., o sistema avidina-biotina. Neste trabalho foi descrita a síntese e a caracterização do ligante SalenHSi (um tipo de base de Schiff), dos complexos Er(SalenHSi) e Eu(SalenHSi) e dos seus respectivos híbridos com matriz de sílica gel para potencial utilização como marcadores. A formação do ligante, dos híbridos e dos híbridos aminofuncionalizados foi comprovada por FTIR. Dados de titulação complexométrica indicaram estequiometria 3:1 (ligante:metal) no complexo Eu(SalenHSi). O diagrama de níveis de energia construído demonstrou a viabilidade de transferência de energia do ligante para os íons Eu 3+ e Er 3+ . O complexo de Er 3+ não é um bom emissor no visível, mas o de Eu 3+ apresenta emissão no vermelho devido as seguintes transições: 5 D0→ 7 FJ (J = 0, 1, 2, 3 e 4), sendo uma única transição 5 D0→ 7 F0 indicando a presença de somente um sítio emissor sem centro de inversão. Os parâmetros Ω 2, Ω 4, R 02 e os valores de τ e η foram determinados para o complexo Eu(SalenHSi) e a eficiência quântica estimada foi de 9,62%. Imagens de microscopia eletrônica de varredura indicaram uma modificação na morfologia dos complexos em função das formas de acondicionamento das amostras. Os testes preliminares de conjugação realizados com o híbrido aminofuncionalizado contendo Eu 3+ , a proteína albumina e um crosslinker foram acompanhados por espectroscopia de absorção na região do UV-Vis, e os resultados obtidos demonstram uma efetiva conjugação
Luminescent complexes of lanthanide ions have been applied in biological labeling because of their high emission efficiency assigned to the antenna effect. The incorporation of these complexes in inorganic materials leads to the formation of organic-inorganic hybrid materials. Such material may be used in biological assays once it is coupled to specific molecules, i.e., the avidin-biotin system. This work describes the synthesis and characterization of the ligand SalenHSi (a type of Schiff base), the complex Er(SalenHSi) and Eu(SalenHSi) and their hybrids with silica gel matrix for potential use as biological labels. The formation of ligand, hybrids and hybrids aminofunctionalized was confirmed by FTIR. Complexometric titration data, and elementary analysis indicated the stoichiometry 3:1 (ligand:metal) for the complexes I. The energy level diagram demonstrated the feasibility of energy transfer from the ligand to Eu 3+ and Er 3+ ions. Spectroscopic studies performed indicated that Er 3+ complex do not emit in the visible, on the other hand the Eu 3+ complex exhibit red emission the following transitions: 5 D0 → 7 FJ (J = 0, 1, 2, 3 and 4). The only 5 D0 → 7 F0 transition indicates the presence of a single site without inversion center. Yet for Eu(SalenHSi) was determined the Ω2 , Ω4, R 02 parameters and the values of τ and η, and the quantum efficiency value estimated as 9.62%. Images of scanning electron microscopy indicated a change in the morphology of the complex as a function of the storage forms of samples. Preliminary tests performed with the combination of the aminofunctionalized hybrid containing Eu 3+ , the albumin protein and crosslinker were accompanied by absorption spectroscopy in the UV-Vis and the results suggest the effectiveness of the conjugation, opening precedents for future testing by using the self-recognition system avidin-biotin
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Laranja, Marlon Larry. "Síntese e caracterização de híbridos orgânico-inorgânicos luminescentes para aplicação em ensaios biológicos /." São José do Rio Preto, 2013. http://hdl.handle.net/11449/97783.

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Orientador: Ana Maria Pires
Coorientador: Sergio A. M. Lima
Banca: Renata Danielli Adati
Banca: Eduardo José Nassar
Resumo: Complexos de íons lantanídeos luminescentes tem se destacado em marcação biológica em função de sua alta eficiência de emissão atribuída ao "efeito antena". A incorporação destes complexos em matrizes inorgânicas leva a formação de materiais híbridos orgânico-inorgânicos. Esse híbrido pode ser utilizado como marcador em ensaios biológicos desde que acoplado a moléculas de reconhecimento específico, p.e., o sistema avidina-biotina. Neste trabalho foi descrita a síntese e a caracterização do ligante SalenHSi (um tipo de base de Schiff), dos complexos Er(SalenHSi) e Eu(SalenHSi) e dos seus respectivos híbridos com matriz de sílica gel para potencial utilização como marcadores. A formação do ligante, dos híbridos e dos híbridos aminofuncionalizados foi comprovada por FTIR. Dados de titulação complexométrica indicaram estequiometria 3:1 (ligante:metal) no complexo Eu(SalenHSi). O diagrama de níveis de energia construído demonstrou a viabilidade de transferência de energia do ligante para os íons Eu 3+ e Er 3+ . O complexo de Er 3+ não é um bom emissor no visível, mas o de Eu 3+ apresenta emissão no vermelho devido as seguintes transições: 5 D0→ 7 FJ (J = 0, 1, 2, 3 e 4), sendo uma única transição 5 D0→ 7 F0 indicando a presença de somente um sítio emissor sem centro de inversão. Os parâmetros Ω 2, Ω 4, R 02 e os valores de τ e η foram determinados para o complexo Eu(SalenHSi) e a eficiência quântica estimada foi de 9,62%. Imagens de microscopia eletrônica de varredura indicaram uma modificação na morfologia dos complexos em função das formas de acondicionamento das amostras. Os testes preliminares de conjugação realizados com o híbrido aminofuncionalizado contendo Eu 3+ , a proteína albumina e um crosslinker foram acompanhados por espectroscopia de absorção na região do UV-Vis, e os resultados obtidos demonstram uma efetiva conjugação
Abstract: Luminescent complexes of lanthanide ions have been applied in biological labeling because of their high emission efficiency assigned to the "antenna effect". The incorporation of these complexes in inorganic materials leads to the formation of organic-inorganic hybrid materials. Such material may be used in biological assays once it is coupled to specific molecules, i.e., the avidin-biotin system. This work describes the synthesis and characterization of the ligand SalenHSi (a type of Schiff base), the complex Er(SalenHSi) and Eu(SalenHSi) and their hybrids with silica gel matrix for potential use as biological labels. The formation of ligand, hybrids and hybrids aminofunctionalized was confirmed by FTIR. Complexometric titration data, and elementary analysis indicated the stoichiometry 3:1 (ligand:metal) for the complexes I. The energy level diagram demonstrated the feasibility of energy transfer from the ligand to Eu 3+ and Er 3+ ions. Spectroscopic studies performed indicated that Er 3+ complex do not emit in the visible, on the other hand the Eu 3+ complex exhibit red emission the following transitions: 5 D0 → 7 FJ (J = 0, 1, 2, 3 and 4). The only 5 D0 → 7 F0 transition indicates the presence of a single site without inversion center. Yet for Eu(SalenHSi) was determined the Ω2 , Ω4, R 02 parameters and the values of τ and η, and the quantum efficiency value estimated as 9.62%. Images of scanning electron microscopy indicated a change in the morphology of the complex as a function of the storage forms of samples. Preliminary tests performed with the combination of the aminofunctionalized hybrid containing Eu 3+ , the albumin protein and crosslinker were accompanied by absorption spectroscopy in the UV-Vis and the results suggest the effectiveness of the conjugation, opening precedents for future testing by using the self-recognition system avidin-biotin
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Tamgho, Ingrid-Suzy. "Synthesis of Ligands and Macrocycles Based on 1,3-Diiminoisoindoline and Study of New Highly Fluorescent and Symmetric Pyrrole-BF2 Chromophores." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1412163224.

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Santos, Danielle das Chagas. "Desenvolvimento e aplicação de um quimiossensor baseado no ligante binuclear base de schiff N,N',N',N'- (1,2,4,5-Benzenotetrailtetranitrilo)Tetrafenol imobilizado em membranas poliméricas de PVC /." São José do Rio Preto, 2017. http://hdl.handle.net/11449/151297.

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Orientador: Marcos Fernando de Souza Teixeira
Coorientador: Sergio Antônio Marques de Lima
Banca: Heberth Juliano Vieira
Banca: Patrícia lexandra Antunes
Resumo: Os ligantes do tipo base de Schiff apresentam grandes sistemas π-conjugados e geralmente exibem alta intensidade de fluorescência com ou sem a incorporação de íons metálicos, o que possibilita o estudo desta classe de ligantes como sensores químicos ópticos. Assim, este trabalho, consiste no desenvolvimento de um quimiossensor óptico (optodo) baseado no ligante binuclear base de Schiff N,N',N',N'-(1,2,4,5-benzenotetrailtetranitrilo)tetrafenol (BTF) imobilizado em membranas poliméricas de PVC para determinação de íons metálicos. O ligante BTF foi sintetizado e a confirmação da estrutura obtida foi realizada através das técnicas de Espectroscopia de Absorção na Região do Ultravioleta-visível (UV-Vis) e Espectroscopia na Região do Infravermelho com Transformada de Fourier (FT-IR). As membranas de PVC contendo o ligante BTF também foram caracterizadas por Espectroscopia de UV-Vis e Luminescência. Posteriormente, verificou-se a interação do ligante imobilizado nessas membranas na detecção dos íons metálicos Al3+, Ba2+, Cd2+, Co2+, Cr3+, Cu2+, Fe3+, Li+, Mg2+, Mn2+, Ni2+, Sr2+ e Zn2+ por meio do espectro de emissão de luminescência. Com os resultados obtidos foi possível classificar o ligante BTF como um quimiossensor do tipo turn-off para os íons de Cu2+, uma vez que a interação do ligante apenas com este cátion metálico resultou na supressão da luminescência do BTF. A detecção dos íons cobre não foi afetada pela presença de outros metais e adicionalmente, o limite de detecção...
Abstract: The ligands of the Schiff base type feature large conjugated π-systems and generally exhibit high fluorescence intensity with or without the incorporation of metal ions, which makes the study of this class of ligands such as optical chemical sensors. Thus, this work consist in the development of an optical chemosensor (optode) based on binuclear Schiff base ligand N, N', N', N'-(1, 2, 4, 5-benzenetetrailtetranitrile) tetrafenol (BTF) immobilized in PVC polymeric membranes for determination of metal ions. The BTF ligand was synthesized and the confirmation of the structure obtained was performed through the techniques of absorption Spectroscopy in the ultraviolet-visible (UV-Vis) and spectroscopy in the Fourier transform infrared (FT-IR). PVC membranes containing the BTF ligand were also characterized by UVVis spectroscopy and Luminescence. Later, it was found the immobilized ligand interaction in these membranes in the detection of metallic ion Al3+, Ba2 +, Cd2+, Co2+, Cr3+, Cu2+, Fe3+, Li+, Mg2+, Mn2+, Ni2+, Sr2+ and Zn2+ through the spectrum of UV-Vis absorption and fluorescence. With the obtained results it was possible to classify the BTF ligand as a chemosensor of type turn-off to the ions Cu2+, since the only ligand interaction with this metallic cation resulted in the suppression of the luminescence of the BTF. The detection of copper ions was not affected by the presence of other and additionally, the limit of detection for the chemosensor was approximately 2.86 x 10-12 mol L -1 however the analytical parameters were determined for the quimiossensor solution, since the studies with the BTF immobilized on membrane did not submit results reproducibility. A research on the morphology and PVC membrane affinity with the ligand became important and some results obtained by means of Scanning Electron Microscopy and Confocal Microscopy showed that membrane produced was ...
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Mutti, Alessandra Mara Garbosa. "Estudo de nanocompósitos luminescentes baseados em complexos de Eu(III) e Ir(III) ancorados à nanopartículas de sílica por bases de Schiff /." São José do Rio Preto, 2015. http://hdl.handle.net/11449/127580.

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Orientador: Sergio Antonio Marques de Lima
Coorientador: Ana Maria Pires
Banca: Valdemiro Pereira de Carvalho Júnior
Banca: Andrea Simone Stucchi de Camargo Alvarez Bernardez
Resumo: A sílica apresenta características que a torna uma boa matriz hospedeira de moléculas e biomoléculas, fazendo dela um material promissor para inúmeras aplicações, destacando-se catálise, liberação controlada de fármacos, desenvolvimento de biomarcadores e demais aplicações. Um biomarcador à base de sílica deve possuir um composto luminescente ligado covalentemente à superfície da matriz. Sendo assim, complexos com íons lantanídeos e irídio são promissores, pois apresentam forte luminescência no visível, e desta forma são ótimos candidatos para o uso como sondas luminescentes. O presente trabalho tem como foco principal a síntese, caracterização e estudo das propriedades de nanopartículas de sílica funcionalizadas na superfície com compostos luminescentes. Esses novos luminóforos à base de nanopartículas de sílica foram preparados pelo método sol-gel e através da ancoragem de complexos de Eu3+ e Ir3+ à superfície da matriz inorgânica, utilizando ligantes do tipo Base de Schiff. Também foram sintetizados ligantes imínicos não sililados, sililados e ancorados à sílica; três complexos [Eu(salba)3], [Eu(salen)2] e [Ir(ppy)2(salba)]; e três conjugados [Eu(salpaSi)(H2O)x]-SiO2, [Eu(dbm)3(salpaSi)]-SiO2 e [Ir(ppy)2(salpaSi)]-SiO2. Todos tiveram sua formação comprovada pela análise via Espectroscopia Vibracional na região do Infravermelho. As partículas de sílica funcionalizadas foram analisadas por microscopia eletrônica de varredura e a morfologia avaliada, sendo observado partículas esferoidais e com tamanho na faixa de 200-250 nm. O íon Eu3+ nos complexos foi sensibilizado pelos ligantes utilizados, e o uso do Ir3+ causou aumento na intensidade de emissão por parte dos ligantes, causado pelo forte acoplamento spin-orbital
Abstract: Silica is a versatile material and has specific properties that make it a good host for molecules and biomolecules suggesting promising applications such as in catalysis, drug controlled release, biomarkers, and so on. To be used as a biomarker it requires a luminescent molecule covalently linked to its surface. For this application, lanthanide complexes are very promising since they exhibit intense multicolor emissions. Also, some transition metal complexes exhibit good luminescent properties, that makes them good candidates for use as luminescent probes in biological media. The main scope of this work is the synthesis, characterization and evaluation of luminescent functionalized silica nanoparticles. These new phosphors based on silica nanoparticles were obtained by sol-gel method, followed by covalent bounding with Eu3+-complexes or Ir3+-complexes, through a Schiff base ligand type. We also describe the synthesis and characterization of two Schiff base ligands: Salba and SalpaSi. The last one was attached to the silica nanoparticles surface to form SalpaSi- SiO2. Three complexes {[Eu(salba)3], [Eu(salen)2] and [Ir(ppy)2(salba)]} and three conjugates {[Eu(salpaSi)(H2O)x]-SiO2, [Eu(dbm)3(salpaSi)]-SiO2 and [Ir(ppy)2(salpaSi)]-SiO2} were prepared. All compounds were analyzed by Infrared Spectroscopy, confirming their synthesis. Functionalized silica nanoparticles were analyzed by Scanning Electronic Microscopy, from where we could observe these particles are spheroidal shaped with diameter in the range 200-250 nm. The Eu3+ ion in the complexes was sensitized by the ligands emitting a reddish color, while the use of Ir3+ caused an increase in the emission intensity of the ligand, caused by strong spin-orbital coupling
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15

Arrey, Lucas Nyenty. "Part I. Synthetic efforts towards 4H-cyclobuta(de);quinoline; chemistry of 4-quinolyldiazomethane. Part II. The effects of temperatures and bases on the stereochemistry of hydrogen rearrangements in alkyl 3- and 4-pyridylmethylenes /." The Ohio State University, 1997. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487942739806582.

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16

Cheng, Ying. "Part I: the 't-amino effect' in the Vilsmeier formylation of p-substituted tertiary anilines : part II: study of the chemistry of aminochlorocarbenes derived from Vilsmeier reagents by the action of bases." Thesis, University of Sunderland, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.297371.

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Martin, Cibely da Silva [UNESP]. "Estudo e caracterização da eletropolimerização de moléculas nanoestruturadas a Base de Schiff." Universidade Estadual Paulista (UNESP), 2013. http://hdl.handle.net/11449/97778.

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A presente dissertação de mestrado apresenta o estudo da eletropolimerização de monômeros à base de Schiff na ausência de cátions metálicos (N,N’-bis(5-aminosalicilidenoimina) – NH2 -salen) e do monômero a base de Schiff contendo níquel como cátion metálico no centro ligante tetradentado (N,N’,N’’,N’’’-tetrabis(salicilideno)3,3’,4,4’-bifenileno tetramino de níquel (II)) – Ni2 (Bisalphen). A obtenção do monômero NH 2 -salen foi realizada pela redução metálica em meio ácido do monômero NO 2 -salen (N,N’-bis(5-nitrosalicilidenoimina)), sendo confirmada pela técnica de espectroscopia no infravermelho (FTIR), espectrofotometria na região de UV-vís e por espectroscopia de massa (MS-EI). As análises dos voltamogramas de eletropolimerização, e dos perfis voltamétricos em solução aquosa, demonstram um mecanismo de por acoplamento C–N. O mecanismo foi confirmado pelo estudo de velocidade de varredura e número de ciclos de potenciais, como também pela caracterização por espectroscopia Raman. Em solução aquosa o filme de poli(NH-salen) apresentou um único par redox na ausência de oxigênio molecular, atribuído ao par redox R 1 -NH-C-R 2 /R 1 -N=C-R 2 , onde um aumento da concentração de espécie eletroativa foi obtida em função do aumento da razão [carga do íon]/[raio iônico] dos ânions presentes em solução, que pode ser atribuído a necessidade da difusão dos ânions no processo de transferência eletrônica. Para comparação dos mecanismos de formação, a obtenção do filme polimérico do complexo metálico Ni 2 (Bisalphen) foi realizada de modo semelhante, modificando apenas o solvente e eletrólito suporte utilizado. Na etapa de eletropolimerização, os resultados foram satisfatórios somente em solvente THF contendo...
This dissertation presents the study of electropolymerization of monomers to the Schiff base in the absence of metal cations (N, N'-bis (5-amine-salicylideneimine) - NH2 -salen) and the Schiff base monomer containing nickel as metallic cation in the tetradentate center (N,N',N'',N'''-tetrabis(salicylidene) 3,3',4,4'-biphenylene-tetramine of nickel (II) - Ni2 (Bisalphen)). The NH 2 -salen monomer synthesis was realized by metallic reduction in acid medium from NO2 -salen (N,N'-bis(5-nitro-salicylideneimine)), being confirmed by the infrared spectroscopy (FTIR), UV-Vis spectrophotometry, and mass spectroscopy of electronic impact (MS-EI). The voltammetric profiles obtained on electropolymerization stage and in aqueous solution show the mechanism formation based on C-N coupling. This mechanism was confirmed by scan rate, potential cycle number study, and by the Raman characterization. In aqueous solution the poli(NH-salen) film showed one redox couple in absence of molecular oxygen, which was ascribed to R 1 -NH-C-R 2 /R 1 -N=C-R 2 redox couple. The increase of surface coverage was obtained in function of [ion charge]/[ionic radius] ratio of the anions present in aqueous solution, which can be ascribed to necessity of anion diffusion on electronic transfer. In order to compare the electropolymerization mechanism, the polymeric film of Ni2 (Bisalphen) was also obtained by electropolymerization technique. However, the solvent and supporting electrolyte were different. In the electropolymerization stage, the results were satisfactory only in THF solvent using the TBAP as supporting electrolyte, which can be ascribed to low solubility of complex in other solvents, as well as the low dipole value, necessary to propagation of the reaction. Due to presence of the metallic cation on monomer structure, the electropolymerizatiom... (Complete abstract click electronic access below)
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Costa, André Lucas. "Desenvolvimento de híbridos orgânico-inorgânico do tipo core@shell luminescentes visando aplicação em marcação biológica /." São José do Rio Preto, 2017. http://hdl.handle.net/11449/150422.

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Orientador: Ana Maria Pires
Banca: Italo Odone Mazali
Banca: Carlos José Leopoldo Constantino
Resumo: Este trabalho apresenta o estudo estrutural e espectroscópico de híbridos inorgânicoorgânicos constituídos por partículas luminescentes aminofuncionalizadas do tipo core@shell (componente inorgânico) e ligantes coordenados a íons terra raras distintos daqueles presentes nas partículas luminescentes (componente orgânico) acorados no sistema inorgânico, com potencial aplicação em sistemas de imageamento celular. Óxido de ítrio de estrutura cúbica foi selecionado para atuar como "core" devido à sua reconhecida compatibilidade em hospedar íons ativadores, no caso Eu3+ e Tb3+. Sílica gel foi escolhida para recobrir o "core" por se tratar de um polímero inorgânico cuja superfície pode ser facilmente funcionalizada. Desta forma, estruturas core@shell esferoidais aminofuncionalizadas, com Y2O3:Eu3+ ou Y2O3:Tb3+ como "core", foram obtidas para a confecção de híbridos inorgânico-orgânicos. Através da ancoragem de ligantes do tipo base de Schiff na superfície dos luminóforos recobertos e da complexação desses com um segundo íon terra rara, foi obtido um sistema com dois centros emissores distintos. Estes por sua vez, foram complexados com ligantes β-dicetonas, a fim de promover emissões através do efeito antena. Os compostos produzidos tiveram suas propriedades estruturais, ópticas e morfológicas monitoradas pelas técnicas de difração de raios X, espectroscopias no IV, Raman, Luminescência e microscopia eletrônica de varredura e de transmissão, entre outras. As...
Abstract: This work presents the structural and spectroscopic study of inorganic-organic hybrids involving luminescent particles of aminofunctionalized core-shell type (inorganic component) and ligands coordinated to rare earth ions, different from those present in luminescent particles (organic component) anchored in the inorganic system, with potential application in cellular imaging systems. Cubic ittrium oxide was selected to act as "core" due to its recognized compatibility in host activator ions, in this case Eu3+ and Tb3 +. Silica gel was chosen to cover the core because it is an inorganic polymer whose surface can be easily functionalized. Thus, aminofunctionalized spheroidal core shell structures with Y2O3:Eu3+ or Y2O3:Tb3+ as core were obtained for the preparation of inorganic-organic hybrids by the anchoring of Schiff base-type ligands to be complexed to a second rare earth ion, thus promoting two different emitting centers. These in turn were complexed with β-diketone ligands in order to promote emissions through the antenna effect. The compounds produced had their structural, optical and morphological properties monitored by X-ray diffraction, IR, Raman, and Luminescence spectroscopy, and scanning and transmission electron microscopy, among others. The luminescent properties were evaluated by the study of intensity parameters in addition to the interpretation of chromaticity diagrams. It was verified that the dominant emission color for the hybrid synthesized phosphors can vary according to the excitation, with high color purity. From the analysis and interpretation of the obtained results, it was possible to conclude that the synthesis of the luminescent particles of the proposed and unpublished organic and inorganic hybrids was successfully carried out, and the morphology, homogeneity and size distribution are favorable for later applications in biological tests, mainly ...
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Martin, Cibely da Silva. "Estudo e caracterização da eletropolimerização de moléculas nanoestruturadas a Base de Schiff /." São José do Rio Preto, 2013. http://hdl.handle.net/11449/97778.

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Orientador: Marcos Fernando de Souza Teixeira
Banca: Luiz Henrique Dall'Antonia
Banca: Maria Valnice Zanoni
Resumo: A presente dissertação de mestrado apresenta o estudo da eletropolimerização de monômeros à base de Schiff na ausência de cátions metálicos (N,N'-bis(5-aminosalicilidenoimina) - NH2 -salen) e do monômero a base de Schiff contendo níquel como cátion metálico no centro ligante tetradentado (N,N',N'',N'''-tetrabis(salicilideno)3,3',4,4'-bifenileno tetramino de níquel (II)) - Ni2 (Bisalphen). A obtenção do monômero NH 2 -salen foi realizada pela redução metálica em meio ácido do monômero NO 2 -salen (N,N'-bis(5-nitrosalicilidenoimina)), sendo confirmada pela técnica de espectroscopia no infravermelho (FTIR), espectrofotometria na região de UV-vís e por espectroscopia de massa (MS-EI). As análises dos voltamogramas de eletropolimerização, e dos perfis voltamétricos em solução aquosa, demonstram um mecanismo de por acoplamento C-N. O mecanismo foi confirmado pelo estudo de velocidade de varredura e número de ciclos de potenciais, como também pela caracterização por espectroscopia Raman. Em solução aquosa o filme de poli(NH-salen) apresentou um único par redox na ausência de oxigênio molecular, atribuído ao par redox R 1 -NH-C-R 2 /R 1 -N=C-R 2 , onde um aumento da concentração de espécie eletroativa foi obtida em função do aumento da razão [carga do íon]/[raio iônico] dos ânions presentes em solução, que pode ser atribuído a necessidade da difusão dos ânions no processo de transferência eletrônica. Para comparação dos mecanismos de formação, a obtenção do filme polimérico do complexo metálico Ni 2 (Bisalphen) foi realizada de modo semelhante, modificando apenas o solvente e eletrólito suporte utilizado. Na etapa de eletropolimerização, os resultados foram satisfatórios somente em solvente THF contendo... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: This dissertation presents the study of electropolymerization of monomers to the Schiff base in the absence of metal cations (N, N'-bis (5-amine-salicylideneimine) - NH2 -salen) and the Schiff base monomer containing nickel as metallic cation in the tetradentate center (N,N',N'',N'''-tetrabis(salicylidene) 3,3',4,4'-biphenylene-tetramine of nickel (II) - Ni2 (Bisalphen)). The NH 2 -salen monomer synthesis was realized by metallic reduction in acid medium from NO2 -salen (N,N'-bis(5-nitro-salicylideneimine)), being confirmed by the infrared spectroscopy (FTIR), UV-Vis spectrophotometry, and mass spectroscopy of electronic impact (MS-EI). The voltammetric profiles obtained on electropolymerization stage and in aqueous solution show the mechanism formation based on C-N coupling. This mechanism was confirmed by scan rate, potential cycle number study, and by the Raman characterization. In aqueous solution the poli(NH-salen) film showed one redox couple in absence of molecular oxygen, which was ascribed to R 1 -NH-C-R 2 /R 1 -N=C-R 2 redox couple. The increase of surface coverage was obtained in function of [ion charge]/[ionic radius] ratio of the anions present in aqueous solution, which can be ascribed to necessity of anion diffusion on electronic transfer. In order to compare the electropolymerization mechanism, the polymeric film of Ni2 (Bisalphen) was also obtained by electropolymerization technique. However, the solvent and supporting electrolyte were different. In the electropolymerization stage, the results were satisfactory only in THF solvent using the TBAP as supporting electrolyte, which can be ascribed to low solubility of complex in other solvents, as well as the low dipole value, necessary to propagation of the reaction. Due to presence of the metallic cation on monomer structure, the electropolymerizatiom... (Complete abstract click electronic access below)
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Silva, Yan Fraga da. "Polimerização radicalar de acetato de vinila mediada por novos complexos de Co(II) coordenados à bases de Schiff não simétricas /." São José do Rio Preto, 2019. http://hdl.handle.net/11449/182578.

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Orientador: Beatriz Eleutério Goi
Coorientador: Valdemiro Pereira de Carvalho Júnior
Banca: Ana Maria Pires
Banca: Patrícia Alexandra Antunes
Resumo: Nas últimas décadas, a polimerização radicalar controlada (CRP) tem se tornado muito importante, pois permite a síntese de macromoléculas de arquiteturas específicas com um controle sobre as propriedades químicas e físicas. Sendo assim, este trabalho tem por objetivo a síntese de novos complexos de Co(II) coordenado a ligantes tipo Salen não simétricos. O precursor, os ligantes e os complexos foram caracterizados pelas seguintes técnicas: espectroscopia de absorção na região do UV-Vis, espectroscopia vibracional na região do infravermelho (FTIR), voltametria cíclica e Ressonância Magnética Nuclear (RMN 1H e 13C). Os complexos não simétricos contendo em sua composição aminas saturadas [CoII(CAYA 02)], [CoII(CAYA 03)] e o complexo contendo amina aromática [CoII(CAYA 04)] foram utilizados como mediadores na reação de polimerização radicalar controlada por organometálicos do acetato de vinila. Foram feitos estudos do efeito da temperatura na reação de OMRP (Polimerização Radicalar Mediada por Complexos Organometálicos) utilizando-se o complexo [CoII(CAYA 03)] sintetizado na razão molar de 1/3,25/542 (Co/AIBN/VAc). Após este estudo foram realizadas as cinéticas de polimerização para todos os complexos, pôde-se observar que cada complexo apresentou um perfil cinético de pseudo-primeira ordem com um aumento de Mn em determinados intervalos de tempo de acordo com a sua reatividade. Os complexos [CoII(CAYA 03)] e [CoII(CAYA 04)] apresentaram um aumento dos valores de Mn juntamente...
Abstract: In the last decades, controlled radical polymerization (CRP) has become very important because it allows the synthesis of macromolecules of specific architectures with a control over the chemical and physical properties. Thus, this work aims to synthesize new Co (II) complexes bound to non-symmetric Salen type ligands. The precursor, ligands and complexes were characterized by the following techniques: absorption spectroscopy in the UV-Vis region, infrared vibration spectroscopy (FTIR), cyclic voltammetry and Nuclear Magnetic Resonance (1H and 13C NMR). The non-symmetric complexes containing saturated amines [CoII (CAYA 02)], [CoII (CAYA 03)] and the aromatic amine-containing complex [CoII (CAYA 04)] were used as mediators in the radical polymerization reaction controlled by organometallic of vinyl acetate. It was studied the effect of temperature on the OMRP (Polymerization Radicalar Mediated by Organometallic Complexes) using the complex [CoII (CAYA 03)] synthesized in the molar ratio of 1 / 3.25 / 542 (Co / AIBN / VAc). After this study the polymerization kinetics were performed for all the complexes, it was observed that each complex presented a kinetic profile of pseudo-first order with an increase of Mn at certain time intervals according to their reactivity. The complexes [CoII (CAYA 03)] and [CoII (CAYA 04)] showed an increase of the Mn values together with the conversion maintaining the values of polydispersity (Ð) between 1 and 1,5 that characterizes the control of ...
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21

Ribeiro, Maria Fernanda Muzetti. "Desenvolvimento de métodos voltamétricos para a quantificação de LSD utilizando-se o eletrodo de pasta de carbono modificado com complexo de base de Schiff." Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-22122015-224845/.

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Nos últimos anos, vários métodos eletroanalíticos foram desenvolvidos a fim de tornarem mais práticas e acessíveis às análises químicas de substâncias entorpecentes realizadas pela polícia científica. Com a sensibilidade e seletividade compatíveis com as dos métodos instrumentais convencionais, é a portabilidade da técnica eletroanalítica que se sobressai e tem apresentado grande potencial para tais aplicações. O uso de complexos metálicos com as bases de Schiff como modificadores do eletrodo de trabalho, tornou ainda mais promissora a utilização destes métodos para a detecção e quantificação de entorpecentes. Os eletrodos de pasta de carbono também contribuem para a praticidade da eletroanalítica, uma vez que são produzidos de forma simples e barata. Desta forma, neste projeto foram desenvolvidos métodos voltamétricos para a quantificação da dietilamida do ácido lisérgico (LSD), utilizando-se o eletrodo de pasta de carbono modificado com o complexo [UO2(Ac-ophen)]·H2O. A aplicação do KCl como eletrólito suporte, em solução aquosa, diferencia estes métodos do encontrado na literatura. Nas análises, foram empregadas as técnicas de voltametria cíclica, onda quadrada e de pulso diferencial. A linearidade no aumento da corrente frente às variações da concentração do LSD possibilitou a obtenção das curvas analíticas com desvio padrão e limites de detecção e quantificação de 2,45, 0,62 e 1,02 mol L-1, respectivamente, como melhores resultados. As análises de recuperação das amostras, 103 e 108%, demostra a possibilidade da utilização destas no âmbito forense.
The development of electroanalytical methods for forensic science has been growing in recent years by the fact of their practicality and low cost. Once sensibility and selectivity values are compatible to conventional methods, as chromatography and spectrometry, the portability of this system consists on interesting advantages. The simple modification of the carbon paste working electrode with Schiff bases complexes became even more promising to use this method for the detection and quantification of narcotics. The carbon paste electrode itself contributes for the practicality of the analyses, once it is made of simple carbon powder, which can be disposable. This project aimed to develop voltammetric methods for the quantification of the lysergic acid diethylamide (LSD) using a carbon paste electrode modified with the complex [UO2(Ac-ophen)]·H2O. The use of aqueous solution of KCl as supporting electrolyte characterizes a less pollutant methodology, differently of other methods that still use toxic solvents The combination of the differential pulse and square wave voltammetries with the modified carbon paste was crucial for the detection of trace levels of the LSD. The linear response in various concentrations of LSD results on analytical curves with standard deviation, detection, and quantification limits of 2,45, 0,62, 1,02 mol L-1, respectively. And the recovery values of 103 and 108 % indicates the possibility of using this method in the forensic science
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22

Cetin, Dindar Ayla. "The Effect Of 5e Learning Cycle Model On Eleventh Grade Students." Phd thesis, METU, 2012. http://etd.lib.metu.edu.tr/upload/12614290/index.pdf.

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The purpose of this study was to investigate the effect of 5E learning cycle model compared to traditional teacher-centered instruction on eleventh grade students&rsquo
conceptual understanding of acids and bases concepts and student motivation to learn chemistry. The measuring tools were Three-tier Acids-Bases Test (TABT) and Chemistry Motivation Questionnaire (CMQ). There were two groups, which were the experimental and traditional group, consisting of 78 students. Before the implementation, the tools were administered as pre-tests to both groups and the semi-structured pre-interviews were conducted with eight students to determine students&rsquo
prior knowledge about acids-bases and motivation to learn chemistry. During the implementation, 5E learning cycle model was used in the experimental group and the traditional teacher-centered instruction was used in the traditional group throughout eight weeks. After the implementation, the tools were administered as post-tests to both groups and the semi-structured post-interviews were conducted with the same students to determine their post knowledge about acids-bases and motivation to learn chemistry. Afterwards, the data were analyzed and descriptive and inferential statistics were obtained. Based on MANCOVA results, there was a statistical significant mean difference between the groups in favor of experimental group. Similarly, the students from experimental group scored higher motivation and this difference was found to be statistically significant. The results were analyzed in terms of gender as well, and there was found no statistically significant differences between the post-test mean scores of girls and boys for the effect of the implementation on understanding of acids-bases concepts or motivation to learn. The inferential statistics results were also supported with the students interviews.
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23

Elisseva, Tatiana V. "Synthesis and Characterization of Imidazole Complexes of Silanes." University of Akron / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=akron1201715430.

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24

Shaibu, Rafiu Olarewaju. "A bioinorganic study of some cobalt(II) Schiff base complexes of variously substituted hydroxybenzaldimines." Thesis, Rhodes University, 2008. http://hdl.handle.net/10962/d1006009.

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Syntheses of Schiff bases were carried out by reacting salicylaldyhde, ortho-vanillin, para-vanillin or vanillin with aniline, 1-aminonaphthalene, 4- and 3-aminopyridine, and also with 2- and 3-aminomethylpyridine. The various Schiff bases obtained from the condensation reaction were reacted with CoCl₂.6H₂0, triethylamine stripped CoCl₂.6H₂0 or Co(CH₃COO)₂ to form cobalt(Il) complexes of ratio 2:1. The complexes obtained from cobalt chloride designated as the "A series" are of the general formulae ML₂X₂.nH₂0 , (L = Schiff base, X = chlorine) while those obtained from cobalt acetate or triethylamine stripped cobalt chloride denoted as "B" and C" are of the general formulae ML₂. nH₂0. The few complexes that do not follow the general formulae highlighted above are: IA [M(HL)₃.Cl₂], (L = N-phenylsalicylaldimine), 4A = (MLCl₂), (L = N-phenylvanaldiminato), 7 A and 21 A (ML₂), (L = N-naphthyl-o-vanaldiminato, and N-methy-2-pyridylsalicylaldiminato respectively), 8A = MLCI, (L = N-naphthylvanaldiminato), 12A = M₂L₃Cl₂, (L = N-4-pyridylvanaldiminato), 15A (MLCI), (L = N-3-pyridyl-o-vanaldiminato). The ligands and their complexes were characterized using elemental analyses and cobalt analysis using ICP, FT-IR spectroscopy (mid and far-IR), NIR-UV/vis (diffuse reflectance), UV/vis in an aprotic and a protic solvents, while mass spectrometry, ¹HNMR and ¹³CNMR, was used to further characterized the ligands. The tautomeric nature of the Schiff bases were determined by examining the behaviour of Schiff bases and their complexes in a protic (e.g. MeOH) and non-protic (e.g. DMF) polar solvents. The effects of solvents on the electronic behaviour of the compounds were also examined. Using CDCl₃, the NMR technique was further used to confirm the structures of the Schiff bases. The tentative geometry of the complexes was determined using the spectra information obtained from the far infrared and the diffuse reflectance spectroscopy. With few exceptions, most of the "A" series are tetrahedral or distorted tetrahedral, while the "B + C" are octahedral or pseudooctahedral. A small number of complexes are assigned square-planar geometry owing to the characteristic spectral behaviour shown. In order to determine their biological activity, two biological assay methods (antimicrobial testing and brine shrimp lethality assay) were used. Using disc method, the bacteriostatic and fungicidal activities of the various Schiff bases and their respective complexes to Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa as well as Aspergillus niger, were measured and the average inhibition zones are tabulated and analysed. Both the Schiff bases and their complexes showed varying bacteriostatic and fungicidal activity against the bacteria and fungus tested. The inhibition activity is concentration dependent and potential antibiotic and fungicides are identified. To determine the toxicity of the ligands and their corresponding cobalt(II) complexes, brine shrimp lethality assay was used. The LD₅₀ of the tested compounds were calculated and the results obtained were tabulated for comparison.
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25

Oliveira, Laura Siqueira de. "Desenvolvimento de um sistema eletroquímico de análise por injeção em fluxo para detecção de cocaína." Universidade de São Paulo, 2012. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-15022012-110539/.

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O aumento nos índices de criminalidade, na maioria das vezes decorrente de atividades ligadas ao tráfico de drogas, afeta drasticamente a qualidade de vida do ser humano. A análise instrumental de entorpecentes é realizada comumente por métodos cromatográficos, oferecendo limites de detecção (LDs) em torno de 1 ng mL-1. As técnicas analíticas como voltametria, amperometria, potenciometria, dentre outras, assemelham-se às técnicas convencionais de análise, pois além de se mostrarem sensíveis para a análise de traços de substâncias orgânicas e inorgânicas, oferecem vantagens operacionais como a compreensão de mecanismos pato-fisiológicos de várias drogas, dentre elas a cocaína e seus metabólitos. Os eletrodos quimicamente modificados (EQMs) com bases de Schiff (grupos funcionais que contém uma ligação dupla carbono-nitrogênio com o átomo de nitrogênio conectado a um grupo arila ou alquila) desenvolvidos para a determinação de cocaína em amostras de interesse forense podem ser empregados em situação de análise por injeção em fluxo (FIA). Cuja metodologia consiste na inserção de uma alíquota de amostra em um fluido carregador que a transporta do ponto de injeção até a unidade de detecção. Atualmente a análise de cocaína está limitada à dosagem posterior de amostras apreendidas, uma vez que não há nenhum dispositivo portátil para a detecção da mesma em local de crime. Assim, este projeto visa desenvolver uma metodologia voltamétrica, por meio de eletrodos quimicamente modificados com bases de Schiff, e da aplicação dos mesmos em FIA para a detecção de cocaína em amostras de interesse forense.
The increase in crime occurrences, mostly due to activities linked to drug trafficking, dramatically affects the quality of human life. The instrumental analysis of drugs is commonly performed by chromatographic methods, offering limits of detection (LD) around 1 ng mL-1. Analytical techniques such as voltammetry, amperometry, potentiometry, among others, are similar to conventional analysis techniques, as well as prove sensitive for trace analysis of organic and inorganic substances, provide operational advantages as the understanding of pathophysiological mechanisms of several drugs, among them cocaine and its metabolites. The chemically modified electrodes (CMEs) with Schiff bases (functional groups containing a carbon-nitrogen double bond with the nitrogen atom attached to an alkyl or aryl group) developed for the determination of cocaine in samples of forensic interest can be used in situation of flow injection analysis (FIA). The methodology consists of inserting a sample rate of a carrier fluid that carries the point of injection to the detection unit. The analysis is limited to the dosage cocaine samples seized previously, since there is no portable device for detection in the same scene. Thus, this project aims to develop a voltammetric methodology, by means of chemically modified electrodes with Schiff bases, and applying them in the FIA for the detection of cocaine in samples of forensic interest.
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26

Sadr-Arani, Leila. "Étude de l'ionisation et de la fragmentation de bases de l'ADN-ARN par la théorie de la fonctionnelle de la densité." Phd thesis, Université Claude Bernard - Lyon I, 2014. http://tel.archives-ouvertes.fr/tel-01015739.

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Les rayonnements ionisants (RI) traversent les tissus humains, y déposent de l'énergie et la dissipent en fragmentant des molécules. Les fragments obtenus peuvent être mis en évidence par spectrométrie de masse. Malgré la quantité d'informations obtenue expérimentalement à partir du spectre de masse, l'expérience seule ne peut pas répondre à toutes les questions concernant les mécanismes de fragmentation des bases de l'ADN/ARN, et l'étude issue des méthodes quantiques est un complément précieux à ces informations. L'étude théorique permet de connaître les liaisons moléculaires rendues faibles dans chaque base par ionisation et ainsi de prévoir les mécanismes de fragmentation et les fragments produits. Le but de ce travail est d'étudier l'ionisation et les mécanismes de fragmentation de bases de l'ADN/ARN (Uracile, Cytosine, Adénine et Guanine) et d'identifier les cations correspondants à chaque pic des spectres de masse. Nous avons effectué nos calculs en utilisant la DFT avec la fonctionnelle PBE. Dans cette thèse, pour toutes les bases d'ARN, la réaction de rétro Diels-Alder est une des voies principales de dissociation (élimination de HNCO ou de NCO*) à l'exception de l'adénine qui n'a pas d'atome d'oxygène. La perte d'une molécule NH3 (NH2*) est aussi un chemin commun à toutes les bases contenant un ou plusieurs groupes amine. Egalement, la possibilité de la perte d'un hydrogène à partir des cations est également envisagée, ainsi que la dissociation de ces cations déshydrogénés et des bases protonées, en se limitant à l'uracile. Ce travail montre tout l'intérêt de l'apport de calcul (DFT) à l'interprétation des spectres de masse de bases de l'ADN
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27

Mopp, Estelle. "A bioinorganic investigation of some metal complexes of the Schiff base, N,N'-bis(3-methoxysalicylaldimine)propan-2-ol." Thesis, Rhodes University, 2010. http://hdl.handle.net/10962/d1006768.

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This thesis includes the synthesis, characterisation, antioxidant and antimicrobial activities of Cu(II)-, Co(II)- and Co(III) complexes with N,N'-bis(3- methoxysalicylaldimine)propan-2-ol, 2-OH-oVANPN. The Schiff base ligand, 2-OHoVANPN, is derived from o-vanillin and 1,3-diaminopropan-2-ol. The o-vanillin condensed with 1,3-diaminopropan-2-ol in a 2:1 molar ratio yields this potential tetraor pentadentate ligand. The complexes synthesized are tetra (or penta or hexa) coordinated. Formation of the complexes is symbolized as follows:- MX₂ + 2-OH-oVANPN (2:1) -> [M(2-OH-oVANPN)Xn] + HnX MX₂ + 2-OH-oVANPN (2:1) -> [Mn(2-OH-oVANPN)OH] + H₂X₂ MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M(1:1)X₂] MX₂ + (o-vanillin : diaminopropanol) (1:1) -> [M₃(1:1)X₄] M = Cu(II), Co(II) or Co(III); X = Cl; n = 1, 2. Their structural features have been deduced from their elemental analytical data, IR spectral data, and electronic spectral data. With the exception of {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆}(A4), the Cu(II) complexes were monomeric with 2-OH-oVANPN acting as a tetradentate ligand. A binuclear Co(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), was synthesised and the rest of the Co(II) and Co(III) complexes were monomeric with chloride ions coordinating to the metal centre in some cases. Electronic data suggest that the cobalt(II) complexes have octahedral geometries and the copper(II) complexes have square planar structures – Co(III) is likely to be octahedral. Thermal analyses, which included the copper-block-method for determining sublimation temperatures, revealed that some copper(II) and cobalt(II) complexes are hygroscopic and sublime at 200 °C and below. DSC analyses of the Cu(II) complexes gave exotherms around 300 °C for complexes K[Cu(C₁₉H₂₀N₂O₅)(OH)]·2H₂O (A1) and [Cu(C₁₁H15N₂O₃)(Cl)₂]·2H₂O (A2) and above 400 °C for [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3) and {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4). Antioxidant studies were carried out against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·). The cobalt(II) complex, [Co₂(C₁₉H₁₉N₂O₅)(OH)] (B1), which was synthesized in the presence of KOH, had no antioxidant activity, whilst the other cobalt(II) complexes, [Co(C₁₇H₁₇N₂O₅(Cl))]·1½H₂O (B2), [Co(C₁₉H₂₂N₂O₅) (Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B4), which were synthesised in the absence of KOH, demonstrated antioxidant activity. The latter complexes are candidates for cancer cell line testing, while [Cu(C₁₁H₁₆N₂O₃)(Cl)₂] (A3), {Cu₃(C₁₁H₁₄N₂O₃)(Cl)₄(H₂O)₆} (A4), [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) may show anticancer activity through possible hydrolysis products. Most of the complexes synthesized displayed antimicrobial activity against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Aspergillus niger and Candida albicans. The results indicated that complexes [Cu(C₁₁H₁₆N₂O₃)(Cl)₂](A3), [Co(C₁₉H₂₂N₂O₅)(Cl)₂]·5½H₂O (B3) and [Co(C₁₉H₂₁N₂O₅)(Cl)₂ ]·5H₂O (C2) are active against the Gram-negative Ps. aeruginosa and that the ligand, 2-OH-oVANPN, did not have any activity. The same trend was observed with 2-OH-oVANPN, {Cu₃(C₁₁H₁₄N₂O₃)(Cl)4(H₂O)₆} (A4) and [Co(C₁₉H₂₀N₂O₅)(Cl)]·3H₂O (C3) against the Gram-positive S. aureus. As for activity against E. coli and C. albicans, some complexes showed more activity than the ligand. There is an observed trend here that the metal complexes are more active (toxic) than the corresponding ligand, which is in agreement with Tweedy’s chelation theory.
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28

Ryazantsev, Mikhail N. "Computational Investigation of the Photoisomerization of Novel N-Alkylated Indanylidene Pyrroline Biomimetic Switches." Bowling Green State University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1277150544.

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29

Kilavuz, Yeliz. "The Effects Of 5e Learning Cycle Model Based On Constructivist Theory On Tenth Grade Students." Master's thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12608670/index.pdf.

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The main purpose of this study was to compare the effectiveness of 5E learning cycle model based on constructivist theory approach over traditionally designed chemistry instruction on ninth grade students&rsquo
understanding of acid-base concepts. Sixty tenth grade students from two classes of a chemistry course taught by the same teacher in Ankara Atatü
rk Anatolian High School 2004-2005 spring semester were enrolled in the study. The classes were randomly assigned as control and experimental groups. Students in the control group were instructed by traditionally designed chemistry instruction whereas students in the experimental group were taught by the instruction based on constructivist approach. Acid-Base Concepts Achievement Test was administered to both groups as a pre-test and post-test in order to assess their understanding of concepts related to acid-base. Students were also given Attitude Scale Toward Chemistry as a School Subject at the beginning and end of the study to determine their attitudes and Science Process Skill Test at the beginning of the study to measure their science process skills. The hypotheses were tested by using analysis of covariance (ANCOVA) and t-test. The results indicated that instruction based on constructivist approach caused significantly better acquisition of scientific conceptions related to acid-base and produced significantly higher positive attitudes toward chemistry as a school subject than the traditionally designed chemistry instruction. In addition, science process skill was a strong predictor in understanding the concepts related to acid-base.
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30

Hoxha, Kreshnik. "DNA bases in crystal engineering." Thesis, University of Hull, 2014. http://hydra.hull.ac.uk/resources/hull:11660.

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The work described in this thesis focuses on understanding the solid state interactions of organic molecules such as DNA nucleobases using established principles from crystal engineering and the synthon theory. Studying the intermolecular interactions is an indispensable tool to the crystal engineer when it comes to identifying functional groups which generate synthons that govern molecular recognition and self-assembly. Chapter 3 focuses on the growth and design of single crystal materials of DNA bases and their carboxylic acid derivatives with various other molecules. The aim of the chapter was to probe the hydrogen bonding displayed by these systems. The challenges associated with dissolving the nucleobases in organic and aqueous solvents prompted alternative synthetic route to mitigate solubility challenges. Altering the pH of the system was found useful in aiding dissolution. Such synthetic approach has led to the preparation of novel nucleobase salts of bis-guaninium sulphate in three different hydrate forms. The material obtained was a channel hydrate and it was possible to remove water partially and fully while retaining crystallinity. No structural collapse was observed upon full dehydration and the material obtained contained an empty channel hydrate. Co-crystallisation of cytosine with 1,10-phenanthroline is discussed in depth and the results are compared to crystal structure prediction results to rationalise co-crystal formation from an energetic perspective. Calculations on the energy landscape revealed that in the case of cytosine and 1,10-phenanthroline there is a favourable energetic driving force for co-crystallisation. This, however, does not apply to the co-crystallisation of the other DNA bases with 1,10-phenanthroline as these systems did not produce co-crystals and remained as mixtures of precursors. The chapter also describes structural features of thymine acetic acid, melaminium nitrilotriacetate trihydrate and co-crystals of caffeine with 2-nitroterepthalic acid. These structures are closely examined for their hydrogen bonding motifs. Chapter 4 covers a wide range of coordination compounds which relate to hydrogen-bonded networks of DNA nucleobases and their carboxylic acid derivatives. These complex architectures contain both coordination bonds as well as intermolecular interactions in the form of hydrogen bonding and stacking interactions. Metal-dipicolinate complexes treated with adenine and cytosine afforded hydrogen-bonded networks where protonated DNA bases interacted with the ligand via hydrogen bonding. The chapter discusses the role of water molecules in acting as spacers and stabilising crystal structure, especially in cases where there is an imbalance of hydrogen bond donors and acceptors. Orotic acid was heavily used owing to its chelating nature. This part of Chapter 4 focuses on novel crystal structures where orotic acid utilises its hydrogen bonding capability. An extensive discussion is provided on how the level of hydration impacts crystal packing and alters synthon formation. In addition, the chapter also focuses on the structural changes resulting from changing the position of the functional group in the ligands.
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31

Melo, Andréa Lopes. "Síntese de novos compostos acridínicos e mostardas com potencial atividade antitumoral." Universidade Federal de Alagoas, 2015. http://www.repositorio.ufal.br/handle/riufal/1566.

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Cancer is a disease that kills the world and it is estimated that in 2030 the incidence of this disease in the world reach 21.4 million new cases with 13.2 million deaths. Due to the resistance, non-selectivity and high cytotoxicity, many of the current drugs produce side effects such as bone marrow depression, sterility, risk of non-lymphocytic leukemia, among others. Thus it is necessary to the development of new anticancer drugs that have less harmful effects. Thus, six new compounds were synthesized, four acridínicos derivative, a derivative of bis (cloroetila) and palladium (II) complex acridínico, whose acronyms, respectively (Acri)2N, AcriPro, ACDMA, ACBr2MAN, (Most)2N and ACDMAPd. All these compounds derived from Schiff base had satisfactory yields and characterized by NMR techniques (1H, 13C, COSY, J solved) spectroscopy in the infrared, mass spectrometry and elemental analysis. The strains used human tumor cells were HT-29 (human colon cancer), MCF-7 (human breast cancer), Hep-2 (human larynx carcinoma), NCI-H292 (carcinoma human pulmonary mucoepidermoid) and HL -60 (acute promyelocytic leukemia) and derivatives AcriPro, ACDMA, (Most)2N and ACDMAPd showed the best results of IC50 for the HL-60 cells.
Conselho Nacional de Desenvolvimento Científico e Tecnológico
O câncer é uma das doenças que mais mata no mundo e estima-se que em 2030 a incidência no mundo desta doença alcance 21,4 milhões de novos casos com 13,2 milhões de mortes. Devido à resistência, a não seletividade e a alta citotoxicidade, grande parte dos fármacos atuais produzem efeitos indesejáveis tais como: depressão na medula óssea, esterilidade, risco de leucemia não linfocítica, entre outros. Desta forma faz-se necessário o desenvolvimento de novos fármacos antitumorais que possuam menos efeitos agressivos. Assim, foram sintetizados seis novos compostos, sendo quatro derivados acridínicos, um derivado bis(cloroetila) e um complexo de paládio(II) acridínico, que tem como acrônimos, respectivamente, (Acri)2N, AcriPro, ACDMA, ACBr2MAN, (Most)2N e ACDMAPd. Todos esses compostos derivados de base de Schiff tiveram rendimentos satisfatórios e foram caracterizados pelas técnicas de RMN (1H, 13C, COSY, J resolvido), espectroscopia na região do infravermelho, espectrometria de massas e Análise Elementar. As linhagens de células tumorais humanas utilizadas foram HT-29 (câncer de cólon humano), MCF-7 (câncer de mama humano), HEp-2 (carcinoma de laringe humana), NCI-H292 (carcinoma mucoepidermoide de pulmão humano) e HL-60 (leucemia promielocitica aguda) e os derivados AcriPro, ACDMA, ACDMAPd e (Most)2N apresentaram os melhores resultados de CI50 para a células HL-60.
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32

Haurena, Caroline. "Synthèse multicomposant d'amines α, α-disubstituées." Phd thesis, Université Paris-Est, 2010. http://tel.archives-ouvertes.fr/tel-00596881.

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Les réactions multicomposant sont des réactions faisant intervenir au minimum trois composés pour la préparation d'un produit contenant la majeure partie des atomes de départ. Elles constituent l'un des procédés les plus performants en synthèse organique. En diminuant les coûts et les rejets par rapports aux réactions classiques de chimie organique, elles sont également plus économes et plus respectueuses de l'environnement. De plus, en permettant la formation rapide et efficace d'une large librairie de molécules complexes à partir de substrats simples, elles représentent un outil à forte valeur ajoutée dans le domaine pharmaceutique pour l'élaboration de chimiothèques. Face à ces enjeux, le laboratoire a développé en 2006 une réaction multicomposant de type Mannich entre des organozinciques aromatiques, des amines secondaires et des aldéhydes. Cette réaction permet la synthèse en une étape d'une variété de diarylméthylamines, dont la structure amine α,α-disubstituée est rencontrée dans de nombreux composés d'intérêt pharmacologique. A partir de ces travaux, le premier objectif du projet de thèse a été d'étendre la réaction multicomposant à d'autres types d'amines α,α-disubstituées. Tout d'abord, la préparation de nombreuses β-aryléthylamines, et notamment d'α-aminoesters, a été mise au point de manière rapide et efficace à l'aide d'organozinciques benzyliques formés in situ dans des conditions de type Barbier. Ces conditions opératoires présentent l'avantage d'éviter l'étape préliminaire de formation de l'organozincique. En raison de l'intérêt de ces composés, la synthèse d'α-aminoesters à partir d'organozinciques aromatiques a ensuite été réalisée, en préformant l'organométallique à partir du dérivé bromé correspondant par une catalyse au cobalt. Au delà de l'extension de cette réaction, le deuxième objectif du projet de thèse a été de développer des versions diastéréosélectives de la réaction multicomposant à partir d'amines chirales. Des résultats corrects en termes de diastéréosélectivité ont été obtenus, notamment à l'aide de (R)-phényléthylamine. Dans un dernier temps, le mécanisme réactionnel a été étudié par suivi de la réaction par infrarouge à l'aide d'un appareillage ReactIR. Les données receuillies sur les intermédiaires réactionnels potentiels serviront de base pour l'élaboration de stratégies énantiosélectives
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33

Brookes, Paul Craig. "Aminoalcohols as chiral lithium amide bases." Thesis, Bangor University, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267140.

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34

Raminelli, Cristiano. "Estudo da relação quantitativa entre a estrutura química e atividade citotóxica de séries de derivados de bases de Mannich." Universidade de São Paulo, 2001. http://www.teses.usp.br/teses/disponiveis/46/46135/tde-27032019-103221/.

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Bases de Mannich têm sido sintetizadas como pró-fármacos de cetonas α,β-insaturadas, 22, 20 sendo estas importantes no tratamento do câncer. 20 Assim, toma-se de interesse o desenvolvimento de estudos de QSAR envolvendo bases de Mannich com propriedades citotóxicas e/ou anticâncer, contribuindo-se, para o entendimento da(s) interação(ões) destes compostos (agentes alquilantes) no sistema biológico. 40, 5, 36, 53 Neste trabalho, destinado a dissertação de mestrado, foram preparadas e purificadas por métodos triviais descritos na literatura 8 47 duas séries de derivados de bases de Mannich, a saber: nove cloretos de 3-(dimetilamino)-propiofenonas-4-X-substituidas (série I, compostos I.1 a I.9), e seis dos correspondentes iodetos de 3-(trimetilamino )propiofenonas-4-X-substituídas (série II, compostos II.1 a II.6). Destes, quatro não estão descritos na literatura. A seleção dos substituintes foi feita visando obter intercorrelações não significativas entre os correspondentes valores dos parâmetros físico-químicos analisados (π, σp e MR4). 45 Outro critério considerado, se refere as faixas de variação para cada parâmetro físico-químico analisado. 62, 31, 15 Para a série II, estes critérios foram parcialmente contemplados. Em seguida, para cada composto preparado, foram determinados experimentalmente e/ou retirados da literatura 45 e/ou calculados parâmetros parâmetros fisico-químicos/estruturais descritores de propriedades, respectivamente: hidrofóbicas/lipofílicas (π, logPcalc e logP app (sendo os valores este último determinados somente para os compostos da serie I)); eletrônicas/polares (σp, σp+, σp-, σI, σR, T, R, γ13C=0 e νC=0) e, ainda aquela relativa à polarizabilidade (MR4). Como parâmetro biológico para os compostos das series I e II foram determinados os valores da potência citotóxica, expressos por log(1/IC50). A seguir, com o objetivo de se desenvolver estudos de QSAR, aplicando a abordagem tradicional 40 para os compostos respectivamente das séries I e II, e a abordagem mista, 62, 63, 53 que considera as duas séries conjuntamente, foram propostos respectivamente modelos expressos pelas equações IV.4 e IV.6: log(1/IC50)= -0,27(±0,23)δ13C=0 -0,48(±0,35)logPcalc + 56,32(±44,30) eq.IV.4 (n=9;r=0,87;s=0,17;F=9,23;Q2=0,36;SPRESS=0,28) log(1/IC50)=-0,56(±0,27)π+0,35(±0,29)MR4+0,23(±0,22)I[N(Me)3]+-I+1,53(±0,22) eq.IV.6 (n=15;r=0,82;s=0,18;F=7,64;Q2=0,43;SPRESS=0,24 Primeiramente, através da análise do modelo expresso pela equação IV.4 foi possível avaliar as naturezas e contribuições relativas dos parâmetros estruturais responsáveis pela citotoxicidade dos compostos da série I. Em seguida, através da análise do modelo expresso pela equação IV.6 foi possível avaliar a contribuição dos parâmetros físico-químicos, bem como a contribuição da variação estrutural existente entre as séries I e II, responsáveis pela citotoxicidade dos compostos. A interpretação e significado de I[N(Me)3]+I-, que assume valor 0 para os compostos da série I e valor 1 para os compostos da série II, foi discutida em termos estruturais. Nenhum modelo com significado estatístico foi obtido para os compostos da série II. E, tanto para a série I, bem como para as séries I e II, a aplicação dos modelos tanto parabólico como bilinear não resultou em correlações estatisticamente significativas. Pela análise dos modelos foi possível, pelo menos em parte, o entendimento da(s) interação(ões) dos derivados de bases de Mannich no sistema biológico. 40, 5, 36, 53.
Mannich bases have been used as prodrugs of α,β-unsaturated ketones that are important in the cancer therapy 80, 22. In this way, a QSAR study 20, 81 was performed with two sets of Mannich bases derivatives, namely: 3-(dimethylamine)-propiophenon-4-X-substituted hydrochlorides (set I, composed of nine derivatives) and 3-(trimethylamine)propiophenon-4-X-substituted iodines (set II, composed of six derivatives). The sets I and II were prepared by trivial methods described in the literature 58,8. For each compound the physicochemical/structural descriptors, hydrophobic/lipophilic (π, logPcalc and logP app (it was determined only for set I), electronic/polar (σp, σp+, σp-, σI, σR, T, R, γ13C=0 e νC=0) and the polarizability related (MR4), were determined experimentally and/or calculated and/or obtained from the literature 7. The biological parameter was the cytotoxic potency, expressed by values of log(1/IC50). In order to investigate 1he interaction of this class of compounds wi1h the biological system a QSAR study was performed 20, 81. The most significant QSAR models obtained for set I and sets I and II altogether, were expressed respectively by equations 1 and 2. log(1/IC50)= -0,27(±0,23)δ13C=0 -0,48(±0,35)logPcalc + 56,32(±44,30) eq.1 (n=9;r=0,87;s=0,17;F=9,23;Q2=0,36;SPRESS=0,28) log(1/IC50)=-0,56(±0,27)π+0,35(±0,29)MR4+0,23(±0,22)I[N(Me)3]+-I+1,53(±0,22) eq.2 (n=15;r=0,82;s=0,18;F=7,64;Q2=0,43;SPRESS=0,24 To equation 2 was included an variable indicator I[N(Me)3]+I- that assumed the value 0 for set I compounds and the value of 1 for set II compounds. The interpretation and meaning of I[N(Me)3]+I-, were discussed in structural terms. No significant models were obtained for the compounds of the set II. For set I and sets I and II altogether, the application of the parabolic and the bilinear models were verified and showed to be not statistically significant.
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35

Morgan, J. J. G. "The reactions of endoperoxides with nucleophiles and bases." Thesis, Cardiff University, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.388230.

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36

Ruddick, Clare Louise. "Studies relating to aldehydic bridging of DNA bases." Thesis, University of Exeter, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.359747.

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37

Hardie, Ailsa Ghillaine. "Decontamination of soils by activation with acids and bases." Thesis, Stellenbosch : Stellenbosch University, 2004. http://hdl.handle.net/10019.1/49901.

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Thesis (MSc)--University of Stellenbosch, 2004.
ENGLISH ABSTRACT: New, more receptive surfaces can be generated in soils by a partial dissolution of existing, crystalline solids followed by re-precipitation as poorly crystalline colloids with a larger capacity to adsorb ionic and molecular contaminants. This priming process can be carried out by treating the soil with strong acid or base and then neutral ising it again. The aim of this study was to investigate the effectiveness of acid and base treatments in reducing inorganic contaminant availability in different soil types. The first study involved investigating the change in cation (cadmium[II], copper[II]) and anion (phosphate) sorption of four different soils before and after priming. Hydrochloric acid and KOH were used to adjust the pH of soils to below pH 2 or above pH 12 in the dissolution stage of the priming treatment. After neutralisation it was found that base priming resulted in an increase in metal cation adsorption in all the soils, most notably in the sesquioxidic (increase from 19.5 to 73.5 mmol Cd.kg-1 soil) and kaolinitic soils (from 16.9 to 38.3 mmol Cd.kg-1 soil), whereas acid priming decreased it or had little effect on cation sorption. However, acid priming increased anion sorption in all soil types, to a greater extent than base priming, most notably in the organic soil (from 6.3 to 14.7 mmol P04.kg-1 soil). This can be attributed to the differences in the nature of the precipitate (more aluminous or alumino-siliceous) depending on whether the dissolution was carried out in acid or basic conditions, and the final pH of the soil solution, as the hydroxyaluminium and hydroxyaluminosilicate precipitates which form are known to enhance pH-dependent sorption of metals. In the second study, the soil was suspended in Cd or Cu solutions and then the pH was adjusted to below 2 or above 12 using HCI or KOH. After 5 days of shaking the pH was adjusted to a neutral pH again. The availability of the Cd and Cu was determined at each of the stages in the treatment, and it was found that both the acid and base treatments were effective in removing Cu from solution, whereas only the base treatment was effective in removing Cd. Determinations were also carried out using H2S04 and Ca(OH)2 and it was found that they were equally effective. It can be proposed that this acid-base pair would be of most practical importance as the salt generated is gypsum which is generally considered benign, and can actually help to improve the soil structure. Activation of soils by acid or base conditioning could have some useful applications in decontaminating soils or decreasing the mobility of inorganic contaminants in soils. Primed soils could also be used as cheap absorbents for decontaminating water.
AFRIKAANSE OPSOMMING: DEKONT AMINERING VAN GROND DEUR AKTIVlERING MET SURE EN BASISE Nuwe, meer ontvanklike oppervlakke kan in gronde gegenereer word deur middel van gedeeltelike oplossing van bestaande, kristallyne vaste stowwe gevolg deur herpresipitasie as swak kristallyne kolloïede met 'n groter kapasiteit om ioniese en molekulêre kontaminante te adsorbeer. Hierdie behandelingsproses kan uitgevoer word deur die grond met sterk suur of basis te behandel en dit daarna te neutraliseer. Die doel van hierdie studie was om die effektiwiteit van suur- of basisbehandelings om anorganiese kontaminante te verminder, in verskillende grond tipes te ondersoek. Die eerste studie het die ondersoek na die verandering in katioon- (kadmium[II], koper[lI]) en anioon- sorpsie (fosfaat) van vier verskillende gronde voor en na suur of basis voorbehandeling behels. Soutsuur en KOH was gebruik om die pH van die gronde tot onder pH 2 of bo pH 12 aan te pas gedurende die oplosstadium van die behandelingsproses. Na neutralisasie is dit gevind dat basis voorbehandeling tot 'n toename in metaal katioonadsorpsie in al die gronde gelei het, en dit was veral waarneembaar in die seskwioksied (toename van 19.5 tot 73.5 mmol Cd.kg" grond) en kaolinitiese (van 16.9 tot 38.3 mmol Cd.kg-1 grond) gronde, terwyl suur voorbehandeling dit verlaag het of 'n klein effek op katioonsorpsie gehad het. Suur voorbehandeling, egter, het anioonsorpsie in al die gronde verhoog, tot 'n groter mate as basis voorbehandeling, veral in die organiese grond (van 6.3 tot 14.7 mmol fosfaat.kg' grond). Dit kan toegeskryf word aan die verskille in die aard van die neerslag wat meer alurninium- of alurniniumsilika-ryk kan wees afhangede of die oplossing uitgevoer was in suur of basis kondisies, en ook die finale pH van die grondoplossing omdat die hidroksi-aluminium en hidroksi-aluminiumsilikaat presipitate wat vorm bekend daarvoor is om pH-afhanklike sorpsie van metale te bevorder. In die tweede studie, was die grond in Cd- of Cu-oplossings gesuspendeer en die pH was aangepas tot onder 2 of bo 12 met HCI of KOH. Na vyf dae van skud was die pH weer aangepas tot by neutraal. Die beskikbaarheid van Cd en Cu was bepaal by elke stadium in die behandeling, en dit is gevind dat beide suur- en basisbehandeling meer effektief was in die verwydering van Cu uit oplossing, terwyl slegs die basisbehandeling effektief was in die verwydering van Cd. Bepalings was ook uitgevoer met die gebruik van H2S04 en Ca(OH)2 en dit is gevind dat dit net so doeltreffend was soos HCI en KOH. Dit kan voorgestel word dat hierdie suur-basis paar in die praktyk belangriker sal wees omdat die sout wat gegenereer word, nl. gips, as 'n gunstige sout beskou word. Aktivering van grond deur suur- of basis-kondisionering kan sekere bruikbare toepassings in die dekontaminering van gronde hê of dit kan gebruik word om die mobiliteit van anorganiese kontaminante te verlaag. Suur of basis voorbehandelde gronde kan ook gebruik word as goedkoop absorbante vir die dekontaminering van water.
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38

Nilov, Denis I. "Photoaffinity Labeling Strategies Using Purine Nucleic Acid Bases." Bowling Green State University / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1321406382.

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39

Campbell, Craig D. "Lewis base-promoted organocatalysis : O- to C-carboxyl transfer reactions." Thesis, University of St Andrews, 2010. http://hdl.handle.net/10023/2609.

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This work describes the application of a variety of Lewis bases, encompassing predominantly N-heterocyclic carbenes (NHCs), but also the use of imidazoles, aminopyridines, amidines and isothioureas, as effective catalysts in the dearomatisation of heterocyclic carbonates, predominantly the rearrangement of oxazolyl carbonates to their C-carboxyazlactone isomers by means of the Steglich rearrangement. This rearrangement reaction has been investigated extensively, with the development of simplified reaction procedures and the invention of domino cascade protocols incorporating this transformation. In an attempt to understand the mechanism of this O- to C-carboxylation process, a number of interesting observations have been made. Firstly, the class of NHC has an important factor in promoting the rearrangement, with triazolinylidenes being the most effective. Secondly, an interesting chemoselectivity has been delineated using triazolium-derived NHCs, prepared using weak bases (typically Et₃N) or strong metallated bases; both alkyl and aryl oxazolyl carbonates undergo smooth rearrangement with triazolinylidenes derived from strong metallated bases such as KHMDS, while only aryl oxazolyl carbonates undergo rearrangement using Et₃N. Extensive effort has focused towards the development of asymmetric variants of these protocols, primarily towards the design, synthesis and evaluation of chiral NHC precatalysts. To this end, a number of chiral azolium salts have been prepared, encompassing a number of different NHC classes, including C₁- and C₂-imidazolinium salts, C₂-imidazolium salts and a range of triazolium salts. Efforts towards the asymmetric catalysis of the Steglich rearrangement of oxazolyl carbonate substrates have given an optimal 66% ee. Similar rearrangements have been demonstrated with the related furanyl heterocyclic substrate class, producing a mixture of α- and γ-carboxybutenolides. In contrast to the analogous oxazolyl carbonates, the regioselectivity of this rearrangement is dependent upon the nature of the Lewis base employed. Amidines and aminopyridines give a mixture of the α- and γ- regioisomers with generally the α-regioisomer being preferred, while a triazolium-derived NHC gives rise to predominantly the thermodynamically more stable γ-carboxybutenolide. Using amidines or aminopyridines, this rearrangement has been shown to proceed via an irreversible C-C bond-forming process, but in contrast, the rearrangement using the NHC proceeds via an equilibrium process with an optimised regioselectivity of >98:2 for the γ-carboxybutenolide regioisomer over the α-regioisomer. Whilst the asymmetric variant using chiral NHCs has proven unfruitful, rearrangements using a chiral isothiourea have given high levels of regioselectivity towards the α- regioisomer and with excellent levels of enantiodiscrimination (77–95% ee).
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40

Ciobanu, Mihai. "DNA display : a novel strategy for the rapid selection of small molecule ligands." Thesis, Strasbourg, 2012. http://www.theses.fr/2012STRAF018.

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La découverte de petites molécules capables de moduler les systèmes biologiques présente un intérêt majeur dans l'étude des mécanismes cellulaires et la mise au point de nouvelles méthodes thérapeutiques. Bien que les techniques de criblage haut débit soient régulièrement utilisées, il y a un vrai besoin de réduire le coût et le temps associés à la découverte de ligands, afin de valider la fonction de nombreuses cibles potentielles dans notre protéome ou ceux d' organismes pathogènes. A cette fm, l'émergence de technologies basées sur l'encodage de chimiothèques par des acides nucléique offre une alternative répondant à ces critères. Nous avons développé un système permettant une synthèse rapide de bibliothèques de structures variées,conjuguées à des codes PNA (acide peptidique nucléique) uniques, ainsi qu'une technologie de criblage basée sur la sélection par affinité, qui permet une étude rapide de l'interaction avec une protéine-cible et par conséquent l'identification de nouveaux ligands. Plusieurs chimiothèques ont déjà été synthétisées et criblées, et compte tenu de la stabilité chimique remarquable du PNA, nous avons également développé une nouvelle gamme de réactions compatibles avec la synthèse PNA-encodée, la voie étant maintenant ouverte pour la génération de chimiothèques plus complexes et pour l'étude de cibles biologiques très variées
The discovery of srnall molecules capable of modulating biological systems is of major interest for the understanding of cellular mechanisms as weil as for the drug discovery process. In spite of established high throughput techniques routinely used, there is a clear need to reduce the time and cost •associated to ligand discovery, in order to validate the function of numerous potential targets in our proteome or the one of pathogens. In this perspective, the emergence of technologies based on nucleic acid encoding of chemical libraries presents an alternative that fulfills these criteria. We have developed a system enabling the rapid synthesis of libraries containing various structures, conjugated to unique PNA (peptide nucleic acid) tags, a weil as a screening technique based on affinity selection that allows for the rapid study of the interaction witb a target protein and the consequent identification of new ligands. Several libraries have already been synthesized and screened, and based on the remarkable chemical stability of PNA, we have also developed a new palette of reactions compatible with PNA-encoded synthesis, the path now being open for the generation of more complex libraries, and the study of various biological targets
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41

Herrick, Doug James. "The Effects of Color Concentrates on the Rheology of Tint Bases." DigitalCommons@CalPoly, 2012. https://digitalcommons.calpoly.edu/theses/915.

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ABSTRACT THE EFFECTS OF COLOR CONCENTRATES ON THE RHEOLOGY OF TINT BASES Douglas James Herrick Waterborne coatings are formulated with a number of different ingredients; water, latex polymers, pigments, surfactants, dispersants, defoamers, biocides, coalescing aids, and rheology modifiers or thickeners. Rheology modifiers are necessary in order to improve the physical properties of the coating before, during, and after application to a substrate. There are two kinds of rheology modifiers used in waterborne coatings; associative thickeners and non-associative thickeners. Coatings formulated with associative thickeners are quite sensitive to coating variations; the slightest change in the formulation has profound effects on the rheology of the coating. The opposite is true for coatings formulated with non-associative thickeners, where the rheology of the coating is not affected by minor changes in the formulation. The rheological properties of coatings are most influenced by the latex, thickener, and surfactant components of the coating. Previous studies have shown that the most ideal balance of rheological properties come from using associative thickeners. However, when waterborne coatings with associative thickeners are tinted with colorants containing high levels of surfactants they exhibit a significant decrease in viscosity. This change in viscosity results in poor sag resistance, poor brush loading, and may also cause a reduction in tint strength of the coating. In this work, the effect of tinting paints with six different colorants on the viscosity of the paint was studied for four different paint formulations: a pastel base and a deeptone base formulated with hydroxyethylcellulose (HEC-type) non-associative thickeners, and a pastel base and a deeptone base formulated with hydrophobically-modified, ethoxylated polyurethane (HEUR-type) associative thickeners. Gloss values and tinting strengths were obtained in accordance with ASTM methods D523-08 and D4838-88. In addition, dynamic stress and frequency sweeps were taken in order to study the effect of colorant addition on the viscoelastic properties of each sample. Colorant addition had little to no effects on the viscosity of the bases formulated with HEC thickeners, while there was a dramatic decrease in viscosity upon colorant addition to the bases with HEUR thickeners. Similar results were observed in the viscoelastic property analysis: little to no effects on the elastic and viscous moduli was seen with the tinted coatings formulated with the non-associative thickeners, while both the elastic and viscous moduli decreased for the coatings formulated with associative thickeners. A few of the deeptone bases showed increased moduli upon tinting compared to the parent deeptone base. The addition of colorant resulted in a decrease in tinting strength and an increase in gloss for those samples with associative thickeners, while the opposite was found for those samples with non-associative thickeners.
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42

Armer, Richard E. "Enantioselective reactions of cyclic sulphoxides using homochiral lithium amide bases." Thesis, University of Nottingham, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240297.

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43

Roman, Miguel Angel. "Synthesis of branched nucleosides and oligonucleotides containing flexible alkylamine linkers on the heterocyclic bases." Thesis, McGill University, 1995. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=22797.

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The N3 position of thymidine was alkylated with different sized bromoalkyl phthalimide linkers in generally good yields, with no alkylation observed on the sugar ring. The free amino group, available after methylamine deprotection of the phthalimide linker, was protected with the levulinyl protecting group (e.g., 20). Branched 'Y'-shaped nucleic acids containing branching monomer 20 were synthesized using standard solid phase synthetic methodology and complexes of these branched nucleic acids with one and two mole-equivalents of linear complement dA$ sb{10}$ are investigated by thermal melting. At the branching point the levulinic amide exhibited poor lability to Letsinger's hydrazine solution and proved to be incompatible with the solid phase synthesis of branched nucleic acids. The primary amino group provided a handle which was used to extend the size of the linker incorporating a primary hydroxyl group at the site of levulinic protection (e.g., 37, 38). The levulinic ester showed much better lability to hydrazinolysis rendering it more compatible with the solid phase synthesis of branched nucleic acids. An extensive one and two dimensional NMR characterization of the functionalized nucleosides is reported.
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44

Sovdat, Tina. "Toward understanding speed, efficiency and selectivity in retinal photochemistry." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:cfa19bb3-b399-4d26-9b9a-0ca1ff34dfa2.

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This Thesis describes the synthesis, structural, photochemical and photophysical studies of modified retinal protonated Schiff bases in solution. Ultrafast laser spectroscopy, NMR and circular dichroism studies were employed to investigate speed, yield and selectivity of photoisomerisation in these chromophores. Chapter 1 introduces relevant biological, photophysical and photochemical aspects of retinal protonated Schiff base photoisomerisation. It includes an overview of synthetic approaches to modified retinal synthesis pertinent to this this work. Chapter 2 discuses the investigation of the hypothesis that twisting of the chromophore’s isomerising double bond is responsible for ultrafast photoisomerisation in the protein environment. In these studies it was discovered that addition of a methyl group to the retinal backbone in solution results in protein-like photophysics. Chapter 3 presents photopysical and photochemical studies of modified all-trans retinal protonated Schiff bases that culminate in a qualitative model for the influence of electronic factors on photochemical and photophysical behaviour of these chromophores in solution. Chapter 4 describes structural and photophysical investigations of 11-cis retinal protonated Schiff bases. NMR studies indicate conformational flexibility of the chromophores. The first synthetic solution-based chromophore to reach rhodopsins’s speed of photoisomerisation is described. Chapter 5 presents an attempt to gain conformational information on retinal protonated Schiff bases using circular dichroism spectroscopy. Transfer of stereochemical information from the covalently attached stereogenic centre to the retinal backbone is demonstrated.
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45

Mota, Valeri Fernando. "Bases mínimas adaptadas al entorno molecular." Doctoral thesis, Universitat de Barcelona, 1986. http://hdl.handle.net/10803/667662.

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Una de las principales dificultades que presenta, aun hoy en día, la utilización de los métodos "ab initio" en la química cuántica es la de elegir un conjunto de funciones de base con el que poder transformar las ecuaciones integro-diferenciales, difíciles de resolver, a ecuaciones de tipo matricial mucho más sencillas de resolver numéricamente. La dificultad reside en que los conjuntos de base no pueden ser nunca completos, ya que serían de dimensión infinita, teniéndose por lo tanto que truncar arbitrariamente dichos conjuntos de base. Según el grado de truncado de la base, los resultados podrán ser de mejor o peor calidad. Evidentemente, la elección de una base no sólo depende de la calidad de resultados que se quieran obtener, sino que también dependen de los medios reales de cálculo de que se dispone, siendo éste de hecho el factor que más suele pesar a la hora de la elección de la base. Es evidente que, para unos medios de cálculo dados, siempre existirá alguna molécula, de un tamaño tal que sea imposible el uso de bases adecuadamente grandes, viéndonos forzados a la utilización de bases pequeñas que suelen producir resultados de calidad limitada en mayor o menor grado. En este contexto se enmarca la finalidad de la presente tesis, que no es más que la de estudiar una posible forma de mejorar la calidad de lo que se denomina normalmente conjuntos de base mínima. Dicha mejora se ha buscado de dos formas: a través del uso del esquema de contracción general, y por medio de la optimización de la contracción, adecuándola al entorno molecular. La presente memoria se ha organizado de la siguiente forma. En el capítulo II, "Fundamento Teórico", se hace una breve descripción de los sucesivos pasos que se siguen en la metodología cuántica hasta llegar al problema de la base. En el capítulo III, "Conjuntos de Base", se lleva a cabo una descripción del "estado de la cuestión" en lo referente a conjunto de bases. Dicha descripción no es en absoluto exhaustiva, pretendiéndose únicamente poder dejar lo más claro posible en qué lugar, dentro de la gran cantidad de trabajos existentes hoy en día en la bibliografía sobre bases, podemos enmarcar los conjuntos de base con que trabajaremos en la tesis. En el capítulo IV, "Metodología", se lleva a cabo el estudio, propiamente dicho, de la contracción de bases mínimas adaptadas al entorno molecular. Por último, en el capítulo V, "Aplicaciones", se lleva a cabo la aplicación de las bases mínimas desarrolladas en el capítulo anterior a una serie de problemas en los que, dentro de la bibliografía existente, se emplean usualmente bases mínimas por necesidades de cálculo. Dicho estudio se enfoca desde el punto de vista de la base, y no de la metodología o técnica empleadas en la descripción del problema a tratar, lo que queda fuera del ámbito de esta tesis.
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46

Dennis, Joseph Michael Jr. "Palladium- and nickel-catalyzed C-N cross-coupling reactions featuring soluble organic bases." Thesis, Massachusetts Institute of Technology, 2020. https://hdl.handle.net/1721.1/128408.

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Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2020
Cataloged from the PDF of thesis. "The Table of Contents does not accurately represent the page numbering"--Disclaimer page.
Includes bibliographical references.
Chapter 1: Breaking the Base Barrier: An Electron-Deficient Palladium Catalyst Enables the Use of a Common Soluble Base in C-N Coupling Due to the low intrinsic acidity of amines, palladium-catalyzed C-N cross-coupling plagued continuously by the necessity to employ strong, inorganic, or insoluble bases. To surmount the many Due to the low intrinsic acidity of amines, palladium-catalyzed C-N crosscoupling has been practical obstacles associated with these reagents, we utilized a commercially available dialkyl triarylmonophosphine-supported palladium catalyst that facilitates a broad range of C-N coupling reactions in the presence of weak, soluble bases. The mild and general reaction conditions show extraordinary tolerance for even highly base-sensitive functional groups. Additionally, insightful heteronuclear NMR studies using ⁻¹⁵N-labeled amine complexes provide evidence for the key acidifying effect of the cationic palladium center.
Chapter 2: Pd-Catalyzed C-N Coupling Reactions Facilitated by Organic Bases: Mechanistic Investigation Leads to Enhanced Reactivity in the Arylation of Weakly Binding Amines The ability to use soluble organic amine bases in Pd-catalyzed C-N cross-coupling reactions has provided a long-awaited solution to the many issues associated with employing traditional, heterogeneous reaction conditions. However, little is known about the precise function of these bases in the catalytic cycle or about the effect of variations in base structure on catalyst reactivity. We used ¹⁹F NMR to analyze the kinetic behavior of C-N coupling reactions facilitated by different organic bases. In the case of aniline coupling reactions employing DBU, the resting state was a DBU-bound oxidative addition complex, LPd(DBU)(Ar)X, and the reaction was found to be inhibited by base.
Generally, however, depending on the binding properties of the chosen organic base, increasing the concentration of the base can have a positive or negative influence on the reaction rate. Furthermore, the electronic nature of the aryl triflate employed in the reaction directly affects the reaction rate. The fastest reaction rates were observed with electronically neutral aryl triflates, while the slowest were observed with highly electron-rich and electrondeficient substrates. We propose a model in which the turnover-limiting step of the catalytic cycle is dependent on the relative nucleophilicity of the base, compared to that of the amine. This hypothesis guided the discovery of new reaction conditions for the coupling of weakly binding amines, including secondary aryl amines, which were unreactive nucleophiles in our original protocol.
Chapter 3: Use of a Droplet Platform to Optimize Pd-Catalyzed C-N Coupling Reactions Promoted by Organic Bases Recent advances in Pd-catalyzed carbon-nitrogen cross-coupling have enabled the use of soluble organic bases instead of insoluble or strong inorganic bases that are traditionally employed. The single-phase nature of these reaction conditions facilitates their implementation in continuous flow systems, high-throughput optimization platforms, and large-scale applications. In this work, we utilized an automated microfluidic optimization platform to determine optimal reaction conditions for the couplings of an aryl triflate with four types of commonly employed amine nucleophiles: anilines, amides, primary aliphatic amines, and secondary aliphatic amines.
By analyzing trends in catalyst reactivity across different reaction temperatures, base strengths, and base concentrations, we have developed a set of general recommendations for Pd-catalyzed crosscoupling reactions involving organic bases. The optimization algorithm determined that the catalyst supported by the dialkyltriarylmonophosphine ligand AlPhos was the most active in the coupling of each amine nucleophile. Furthermore, our automated optimization revealed that the phosphazene base BTTP can be used to facilitate the coupling of secondary alkylamines and aryl triflates. Chapter 4: The Quest for the Ideal Base: Rational Design of a Nickel Precatalyst Enables Mild, Homogeneous C-N Cross-Coupling Palladium-catalyzed amination reactions using soluble organic bases have provided a solution to the many issues associated with heterogeneous reaction conditions. Still, homogeneous C-N crosscoupling approaches cannot yet employ bases as weak and economical as trialkylamines.
Furthermore, organic base-mediated methods have not been developed for Ni(0/II) catalysis, despite some advantages of such systems over analogous Pd-based catalysts. We designed a new air-stable and easily prepared Ni(II) precatalyst bearing an electron-deficient bidentate phosphine ligand that enables the cross-coupling of aryl triflates with aryl amines using triethylamine (TEA) as base. The method is tolerant of sterically-congested coupling partners, as well as those bearing base- and nucleophile-sensitive functional groups. With the aid of density functional theory (DFT) calculations, we determined that the electron-deficient auxiliary ligands decrease both the pK[subscript a] of the Ni-bound amine and the barrier to reductive elimination from the resultant Ni(II)-amido complex. Moreover, we determined that precluding Lewis acid-base complexation between the Ni catalyst and the base, due to steric factors, is important for avoiding catalyst inhibition.
by Joseph Michael Dennis, Jr.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Chemistry
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47

Thomas, Veena Lily. "The structural bases of stability-function tradeoffs inantibiotic resistance enzymes." Diss., Search in ProQuest Dissertations & Theses. UC Only, 2009. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:3390102.

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48

Ross, Andrew Thomas. "Lead, indium and tin complexes of Schiff bases derived from salicylaldehydes." Thesis, Loughborough University, 1998. https://dspace.lboro.ac.uk/2134/26886.

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A number of lead(II) complexes prepared from the reactions of various disalicylaldimines with lead(II) salts have been characterised spectroscopically, and in two cases have been analysed by X-ray diffraction. The reaction of N,N'-bis(salicylidene)ethane-1,2-diamine (H2salen) with Pb(ClO4)2·6H2O produced a novel complex [Pb3(salen)2][ClO4]2 in which the ligand bonds to the lead in two different modes. The interaction of N,N'-bis(3-methoxy-salicylidene)ethane-1,2-diamine with Pb(ClO4)2·6H2O yielded a mononuclear complex wherein the ligand bonds to the lead(II) atoms only through its phenolic oxygens.
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49

Hume, Stephen Christopher. "The asymmetric synthesis of novel phosphines using chiral lithium amide bases." Thesis, University of Nottingham, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.299708.

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50

Rahman, S. K. "Preparation and use of chiral lithium amide bases in organic synthesis." Thesis, University of Salford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.384061.

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