Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

Neuropeptide Y at the cellular level – Studies on PreproNPY L7P Polymorphism and the Mitochondrial Form of NPY

Neuropeptide Y (NPY) is a widely expressed neurotransmitter in the central and peripheral nervous systems. Thymidine 1128 to cytocine substitution in the signal sequence of the preproNPY results in a single amino acid change where leucine is changed to proline. This L7P change leads to a conformational change of the signal sequence which can have an effect on the intracellular processing of NPY. The L7P polymorphism was originally associated with higher total and LDL cholesterol levels in obese subjects. It has also been associated with several other physiological and pathophysiological responses such as atherosclerosis and T2 diabetes. However, the changes on the cellular level due to the preproNPY signal sequence L7P polymorphism were not known. The aims of the current thesis were to study the effects of the [p.L7]+[p.L7] and the [p.L7]+[p.P7] genotypes in primary cultured and genotyped human umbilical vein endothelial cells (HUVEC), in neuroblastoma (SK-N-BE(2)) cells and in fibroblast (CHO-K1) cells. Also, the putative effects of the L7P polymorphism on proliferation, apoptosis and LDL and nitric oxide metabolism were investigated. In the course of the studies a fragment of NPY targeted to mitochondria was found. With the putative mitochondrial NPY fragment the aim was to study the translational preferences and the mobility of the protein. The intracellular distribution of NPY between the [p.L7]+[p.L7] and the [p.L7]+[p.P7] genotypes was found to be different. NPY immunoreactivity was prominent in the [p.L7]+[p.P7] cells while the proNPY immunoreactivity was prominent in the [p.L7]+[p.L7] genotype cells. In the proliferation experiments there was a difference in the [p.L7]+[p.L7] genotype cells between early and late passage (aged) cells; the proliferation was raised in the aged cells. NPY increased the growth of the cells with the [p.L7]+[p.P7] genotype. Apoptosis did not seem to differ between the genotypes, but in the aged cells with the [p.L7]+[p.L7] genotype, LDL uptake was found to be elevated. Furthermore, the genotype seemed to have a strong effect on the nitric oxide metabolism. The results indicated that the mobility of NPY protein inside the cells was increased within the P7 containing constructs. The existence of the mitochondria targeted NPY fragment was verified, and translational preferences were proved to be due to the origin of the cells. Cell of neuronal origin preferred the translation of mature NPY (NPY1-36) when compared to the non neuronal cells that translated both, NPY and the mitochondrial fragment of NPY. The mobility of the mitochondrial fragment was found to be minimal. The functionality of the mitochondrial NPY fragment remains to be investigated. L7P polymorphism in the preproNPY causes a series of intracellular changes. These changes may contribute to the state of cellular senescence, vascular tone and lead to endothelial dysfunction and even to increased susceptibility to diseases, like atherosclerosis and T2 diabetes.

Equivalent representation form of oscillators with elastic and damping nonlinear terms

In this work we consider the nonlinear equivalent representation form of oscillators that exhibit nonlinearities in both the elastic and the damping terms. The nonlinear damping effects are considered to be described by fractional power velocity terms which provide better predictions of the dissipative effects observed in some physical systems. It is shown that their effects on the system dynamics response are equivalent to a shift in the coefficient of the linear damping term of a Duffing oscillator. Then, its numerical integration predictions, based on its equivalent representation form given by the well-known forced, damped Duffing equation, are compared to the numerical integration values of its original equations of motion. The applicability of the proposed procedure is evaluated by studying the dynamics response of four nonlinear oscillators that arise in some engineering applications such as nanoresonators, microresonators, human wrist movements, structural engineering design, and chain dynamics of polymeric materials at high extensibility, among others

Calculation of the critical crack size for cold form rectangular hollow section tube (CRHS) under bending load at -40º C temperature

To predict the capacity of the structure or the point which is followed by instability, calculation of the critical crack size is important. Structures usually contain several cracks but not necessarily all of these cracks lead to failure or reach the critical size. So, defining the harmful cracks or the crack size which is the most leading one to failure provides criteria for structure’s capacity at elevated temperature. The scope of this thesis was to calculate fracture parameters like stress intensity factor, the J integral and plastic and ultimate capacity of the structure to estimate critical crack size for this specific structure. Several three dimensional (3D) simulations using finite element method by Ansys program and boundary element method by Frank 3D program were carried out to calculate fracture parameters and results with the aid of laboratory tests (loaddisplacement curve, the J resistance curve and yield or ultimate stress) leaded to extract critical size of the crack. Two types of the fracture which is usually affected by temperature, Elastic and Elasti-Plastic fractures were simulated by performing several linear elastic and nonlinear elastic analyses. Geometry details of the weldment; flank angle and toe radius were also studied independently to estimate the location of crack initiation and simulate stress field in early stages of crack extension in structure. In this work also overview of the structure’s capacity in room temperature (20 ºC) was studied. Comparison of the results in different temperature (20 ºC and -40 ºC) provides a threshold of the structure’s behavior within the defined range.

Constantes de acidez de ácidos dipróticos a partir de titulações potenciométricas: ilustração dos princípios do cálculo através da construção de um algoritmo muito simples

This work describes the creation of an very simple calculation algorithm, based in basic chemical and mathematic principles, for the calculation of weak diprotic acid dissociation constants as, for example, amino acids, from potentiometric titrations. For an easier understanding of the algorithm the logical reasoning of this calculus is schematized in a diagram of blocks. In the second part of the work the algorithm is applied to an Excel calculation sheet to determine the dissociation constants of Nicotinic Acid and Glycine, from the respective potentiometric titration curves. The values obtained using this algorithm are compared with those estimated by Hyperquad2008 (program generally used for this type of calculus) and also with the values of a stability constants database.

Spectrophotometric method for determination of atazanavir sulfate in capsule dosage form

Two sensitive and simple spectrophotmetric methods were developed for determination of Atazanavir Sulfate in capsule dosage form. The first method was based on the oxidative coupling of ATV with 3-Methyl Benzothiazolin-2-one hydrazone (MBTH). The resulting green product had Λmax of 627.3 nm and was stable for 2 h. The second method was based on the reaction between diazotized drug with N-(1-napthyl)ethylenediamine dihydrochloride (NEDA) in neutral medium to yield yellowish orange product which had Λmax of 517.1 nm. The product was stable for 4 h. Both methods were highly reproducible and had been applied to pharmaceutical preparations.

Desenvolvimento de um algoritmo para identificação e correção de spikes em espectroscopia Raman de imagem

Raman imaging spectroscopy is a highly useful analytical tool that provides spatial and spectral information on a sample. However, CCD detectors used in dispersive instruments present the drawback of being sensitive to cosmic rays, giving rise to spikes in Raman spectra. Spikes influence variance structures and must be removed prior to the use of multivariate techniques. A new algorithm for correction of spikes in Raman imaging was developed using an approach based on comparison of nearest neighbor pixels. The algorithm showed characteristics including simplicity, rapidity, selectivity and high quality in spike removal from hyperspectral images.

Makeovermani - ny form av magi?

Kirjallisuusarvostelu

Use of modified silica gel for concentrating Pb (II) and Cd (II) occurring in form of complex anions

The performance of silica gel, modified by the impregnation with a high molecular weight quaternary amine (triethyl octadecyl ammonium iodide), used for the concentration of heavy metals occurring in water is studied. The material under study captures Cd, Pb, which are capable of forming stable complexes with I- ions.The results obtained about the metal capture, under dynamic conditions, are described and metal ions are removed by desorption with EDTA and quantified by AAS.

Metaheurística algoritmo genético para solução de problemas de planejamento florestal com restrições de integridade

Os objetivos deste trabalho foram desenvolver e testar um algoritmo genético (AG) para a solução de problemas de gerenciamento florestal com restrições de integridade. O AG foi testado em quatro problemas, contendo entre 93 e 423 variáveis de decisão, sujeitos às restrições de singularidade, produção mínima e produção máxima, periodicamente. Todos os problemas tiveram como objetivo a maximização do valor presente líquido. O AG foi codificado em ambiente delphi 5.0 e os testes foram realizados em um microcomputador AMD K6II 500 MHZ, com memória RAM de 64 MB e disco rígido de 15GB. O desempenho do AG foi avaliado de acordo com as medidas de eficácia e eficiência. Os valores ou categorias dos parâmetros do AG foram testados e comparados quanto aos seus efeitos na eficácia do algoritmo. A seleção da melhor configuração de parâmetros foi feita com o teste L&O, a 1% de probabilidade, e as análises foram realizadas através de estatísticas descritivas. A melhor configuração de parâmetros propiciou ao AG eficácia média de 94,28%, valor mínimo de 90,01%, valor máximo de 98,48%, com coeficiente de variação de 2,08% do ótimo matemático, obtido pelo algoritmo exato branch and bound. Para o problema de maior porte, a eficiência do AG foi cinco vezes superior à eficiência do algoritmo exato branch and bound. O AG apresentou-se como uma abordagem bastante atrativa para solução de importantes problemas de gerenciamento florestal.

Estimativa dos componentes do balanço de energia e da evapotranspiração em plantios de eucalipto utilizando o algoritmo sebal e imagem landsat 5 - TM

Variáveis climáticas são essenciais para a compreensão das condições ambientais que influenciam o crescimento e o desenvolvimento vegetal. Nos últimos anos, as pesquisas que utilizam dados climáticos e técnicas de sensoriamento remoto em análises espaço-temporais da demanda por água e energia das plantas têm-se intensificado. O SEBAL (Surface Energy Balance Algorithms for Land) é um dos algoritmos mais destacados em estudos que envolvem estimativas dos fluxos de energia em grandes áreas, e pode ser aplicado com poucas medições de campo. Este trabalho, realizado no Município de Santa Bárbara, Minas Gerais, objetivou estimar os componentes do balanço de energia e, por conseguinte, a evapotranspiração em plantios de eucalipto com aplicação do algoritmo SEBAL e de imagem do sensor TM do satélite Landsat 5. As estimativas foram realizadas para cena do dia 20/06/2003. Considerando apenas as áreas referentes aos plantios de eucalipto (sete anos de idade), foram obtidos valores médios de saldo de radiação (Rn), fluxo de calor no solo (G), fluxo de calor sensível (H), fluxo de calor latente (LE) de 420,12 W m-2, 81,80 W m-2, 149,93 W m-2, 188,39 W m-2, respectivamente. Para a evapotranspiração real horária (ETr h), o valor médio obtido foi de 0,28 mm h-1. As estimativas mostraram-se condizentes com dados da literatura, no entanto pesquisas com maior controle experimental devem ser realizadas.

Variabilidade local e regional da evapotranspiração estimada pelo algoritmo SEBAL

Em face da importância em conhecer a evapotranspiração (ET) para uso racional da água na irrigação no contexto atual de escassez desse recurso, algoritmos de estimativa da ET a nível regional foram desenvolvidos utilizando-se de ferramentas de sensoriamento remoto. Este estudo objetivou aplicar o algoritmo SEBAL (Surface Energy Balance Algorithms for Land) em três imagens do satélite Landsat 5, do segundo semestre de 2006. As imagens correspondem a áreas irrigadas, floresta nativa densa e a Caatinga do Estado do Ceará (Baixo Acaraú, Chapada do Apodi e Chapada do Araripe). Este algoritmo calcula a evapotranspiração horária a partir do fluxo de calor latente, estimado como resíduo do balanço de energia na superfície. Os valores de ET obtidos nas três regiões foram superiores a 0,60 mm h-1 nas áreas irrigadas ou de vegetação nativa densa. As áreas de vegetação nativa menos densa apresentaram taxa da ET horária de 0,35 a 0,60 mm h-1, e valores quase nulos em áreas degradadas. A análise das médias de evapotranspiração horária pelo teste de Tukey a 5% de probabilidade permitiu evidenciar uma variabilidade significativa local, bem como regional no Estado do Ceará.