Aluminophosphate-based mesoporous molecular sieves: Synthesis and characterization of TAPOs

Mesoporous Ti-substituted aluminophosphates (AlPOs) with a hexagonal, cubic and lamellar pore structure, characteristic of MCM-41, MCM-48, and MCM-50, respectively, were synthesized. The stability of these mesophases upon template removal was studied. The pore structures, surface properties, and local atom environments of Al, P, and Ti of the hexagonal and cubic Ti-containing mesoporous products were extensively characterized using X-ray diffraction, magic angle spinning nuclear magnetic resonance, AAS, XPS, ultraviolet–visible, and adsorption of nitrogen and water vapor techniques while the lamellar mesophase was not further characterized due to its very poor thermal stability. Ti-containing mesoporous AlPO materials show a reasonable thermal stability upon template removal, a hydrophilic surface property, and high porosity showing application potentials in catalytic oxidation of hydrocarbons.

Molecular motion in nanocomposites of poly(ethylene oxide) and montmorillonite

Motion of chains of poly(ethylene oxide) within the interlayer spacing of 2:1 phyllosilicate/montmorillonite was studied with H-1 and C-13 NMR spectroscopy. Measurements of the H-1 NMR line widths and relaxation times across a large temperature range were used to determine the effect of bulk thermal transitions on polymer chain motion within the nanocomposites. The results were consistent with previous reports of low apparent activation energies of motion. Details of the frequency and geometry of motion were obtained from a comparison of the C-13 cross-polarity/magic-angle spinning spectra and relaxation times of the nanocomposite with those of the pure polymer. (C) 2001 John Wiley & Sons, Inc.

High-speed MAS F-19 NMR analysis of an irradiated fluoropolymer

The effect of gamma-radiation on a perfluoroalkoxy (PFA) resin was examined using solid-state high-speed magic angle spinning (MAS) F-19 NMR spectroscopy. Samples were prepared for analysis by subjecting them to gamma-radiation in the dose range 0.5-3 MGy at either 303, 473, or 573 K. New structures identified include new saturated chain ends, short and long branches, and unsaturated groups. The formation of branched structures was found to increase with increasing irradiation temperature; however, at all temperatures the radiation chemical yield (G value) of new chain ends was greater than the G value of long branch points, suggesting that chain scission is the net process.

Hydrofluoric acid pre-treatment for improving 13C CPMAS NMR spectral quality of forest soils in south-east Queensland, Australia

Hydrofluoric acid (HF) was used to pre-treat forest soils of south-east Queensland for assessing the effectiveness of iron (Fe) removal, carbon (C) composition using C-13 cross-polarisation (CP) with magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) before and after the HF pre-treatment, and the improvement of C-13 CPMAS NMR spectra. Soil samples were collected from 4 experimental sites of different soil types, harvest residue management or prescribed burning, and tree species. More than 86% of Fe was in all soil types removed by the HF treatment. The C-13 NMR spectral quality was improved with increased resolution, especially in the alkyl C and O-alkyl C regions, and reduced NMR run-time (1-5 h per sample compared with >20 h per sample without the pre-treatment). The C composition appeared to alter slightly after the pre-treatment, but this might be largely due to improved spectrometer conditions and increased resolution leading to more accurate NMR spectral integration. Organic C recovery after HF pre-treatment varied with soil types and forest management, and soluble soil organic matter (SOM) could be lost during the pre-treatment. The Fourier Transform-Infrared (FT-IR) spectra of HF extracts indicated the preferential removal of carboxylic C groups during the pre-treatment, but this could also be due to adsorbed water on the mineral matter. The NMR spectra revealed some changes in C composition and quality due to residue management and decomposition. Overall, the HF treatment was a useful pre-treatment for obtaining semi-quantitative C-13 CPMAS NMR spectra of subtropical Australian forest soils.

Composition and quality of harvest residues and soil organic matter under windrow residue management in young hoop pine plantations as revealed by solid-state C-13 NMR spectroscopy

Solid-state C-13 nuclear magnetic resonance (NMR) with cross-polarisation (CP) and magic-angle-spinning (MAS) was used to: (a) examine the changes in carbon (C) composition of windrowed harvest residues during the first 3 years of hoop pine plantations in subtropical Australia; (b) assess the impacts of windrowed harvest residues on soil organic matter (SOM) composition and quality in the 0-10 cm soil layer. Harvest residues were collected from 0-, 1-, 2- and 3-year-old windrows of ca. 2.5 m width (15 m apart for 0-, 1- and 2-year-old sites and 10 m apart for 3-year-old site). Soils from the 0 to 10 cm soil layer were collected from the 1-, 2- and 3-year-old sites. The 13C NMR spectra of the harvest residues indicated the presence of lignin in the hoop pine wood, foliage and newly incorporated organic matter (NIOM). Condensed tannin structures were found in the decay-resistant bark, small wood and foliage, but were absent in other residue components and SOM. The NMR spectra of small wood samples contained condensed tannin structures because the outer layer of bark was not removed. NIOM showed a shift from foliage-like structures (celluloses) to lignin-type structures, indicating an incorporation of woody residues from the decomposing harvest residues. Suberins were also present in the small wood, foliage and bark. The 13C CP NMR spectra of SOM indicated that in areas where windrows were present, SOM did not show compositional changes. However, an increase in SOM quality under the windrows in the second year after their formation as characterised by the alkyl C/O-alkyl C (A/O-A) ratio was mainly due to inputs from the decomposition of the labile, readily available components of the windrowed harvest residues. (C) 2002 Published by Elsevier Science B.V.

How does residue management impact soil organic matter composition and quality under Eucalyptus globulus plantations in southwestern Australia?

This study investigated the influence of harvest residue management practices on soil organic matter (SOM) composition and quality from two second-rotation Eucalyptus globulus plantations in southwestern Australia, using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy with cross-polarisation and magic-angle-spinning (CPMAS). Soil samples (0–5 cm) were collected every 12 months for 5 years from two sites that had contrasting soil types and fertility. Harvest residue management treatments established at both sites were (a) no harvest residues; and (b) double harvest residues. The use of 13C CPMAS and DD NMR spectroscopy enabled the successful non-destructive detection of SOM quality changes in the two E. globulus plantations. Relative intensities of 13C CPMAS NMR spectral regions were similar at both sites, and for both harvest residue treatments, indicating that SOM composition was also similar. Dipolar dephasing (DD) NMR spectra revealed resonances in SOM assigned to lignin and tannin structures, with larger resonances in the carbonyl and alkyl C regions that were indicative of cuticular material, enabling detection of changes in SOM quality. Retention of double harvest residues on the soil surface increased the soil quality compared with removal of all harvest residues at both sites as indicated by the NMR aromaticities, but this was most noticeable at Manjimup, which had greater initial soil fertility.

Cross-linking of PFA by electron beam irradiation

The effect of electron beam radiation on a perfluoroalkoxy (PFA) resin was examined using solid-state high-speed magic angle spinning F-19 NMR spectroscopy and FT-IR spectroscopy. Samples were prepared for analysis by subjecting them to electron beam radiation in the dose range 0.5-2.0 MGy at 633 K, which is above the crystalline melting temperature. The new structures were identified and include new saturated chain ends, short and long branches, unsaturated groups, and cross-links. The radiation chemical yield (G value) of new long branch points was greater than the G value of new chain ends, suggesting that cross-linking is the net radiolytic process. This conclusion was supported by an observed decrease in the crystallinity and an increase in the optical clarity of the polymer.

Quadrados mágicos para todos os gostos

Voltamos ao tema dos quadrados mágicos. (...) Vejamos alguns exemplos curiosos. Começamos pelo Quadrado Mágico do Aniversariante (figura A). Se o leitor fizer as contas, verificará que a soma dos números de cada linha, de cada coluna e de cada uma das duas diagonais do quadrado é sempre 22 (figura B). Este é, portanto, um quadrado mágico ideal para quem tem 22 anos. Contudo, a sua utilização é muito mais flexível do que à primeira vista se possa pensar. Isto porque também é possível utilizar este quadrado mágico para felicitar qualquer amigo com mais de 22 anos. Se quisermos que o quadrado da figura A tenha constante mágica igual a x, com x>22, basta adicionar a cada um dos números das quatro casas brancas o valor x-22. (...) Na figura D, apresenta-se um Quadrado Mágico Reversível. Este quadrado aparece no livro "Self-working Number Magic", de Karl Fulves, publicado em 1983. Para começar, uma observação atenta a cada linha, coluna ou diagonal do quadrado permite concluir que, em cada uma dessas filas, são utilizados os mesmos algarismos: 1, 6, 8 e 9. Um olhar ainda mais atento permite detetar duas ocorrências de cada um desses algarismos por fila. (...)

Circunferências mágicas

(...) A ideia original das circunferências mágicas remonta pelo menos à segunda edição do livro “Magic Squares and Cubes”, de W. S. Andrews. A publicação data de 1917, há quase um século, e conta com contributos de diferentes autores. A secção dedicada às circunferências mágicas é da autoria de Harry A. Sayles. (...) O leitor provavelmente já encontrou um padrão: quando usamos números de 1 a n, a soma dos números dos pontos de intersecção de duas quaisquer circunferências deve ser n+1. No desafio apresentado na Fig. A usamos os números de 1 a 40, logo a soma dos números dos pontos de intersecção de duas quaisquer circunferências deve ser igual a 41! Além disso, 205=5x41 (cada circunferência tem dez números e 5 é metade de 10). A descoberta da solução do desafio da Fig. A é, agora, imediata. Esta é a grande vantagem da Matemática. Depois de descoberto um padrão, tudo se torna mais claro. O sentimento é o mesmo de um míope quando coloca os óculos na cara: passa a ver a realidade com outra nitidez. (...)

Marketing: estratégias de sucesso em tempos de crise económica

Mestrado em Gestão e Empreendedorismo

La médecine indigène comme instrument normatif social: l’exemple du corps malade navajo

La médecine traditionnelle indigène peut parfois se poser comme un instrument normatif désignant le malade comme celui qui transgresse l‘ordre établi par les ancêtres sacrés et permet à la maladie d‘advenir. Un tiers malveillant ou un sorcier peuvent également être les causes du désordre physiologique et moral du corps social communautaire. L‘étiologie navajo repose sur deux phénomènes : l‘existence de sociosomas (troubles liés à une mauvaise relation à l‘entourage) et de mouvements d‘exclusion ou d‘inclusion du corps étranger, de la conduite déviante. L‘étude de la figure du malade dans les mythes soulignera l‘aspect normatif des thérapeutiques navajo. Enfin, une réflexion sur la justification idéologique de l‘intégration des pratiques ancestrales au protocole de soin montrera dans quelle mesure la collaboration entre praticiens traditionnels et personnels de santé contribue à stigmatiser le malade comme l‘épitome de toutes les déviances : par rapport à la tradition mais aussi au modèle social dominant.

Electron driven reactions in complexes embedded in superfluid helium droplets

A thesis submitted to the University of Innsbruck for the doctor degree in Natural Sciences, Physics and New University of Lisbon for the doctor degree in Physics, Atomic and Molecular Physics

Teaching mathematics using Massive Open Online Courses

Distance learning - where students take courses (attend classes, get activities and other sort of learning materials) while being physically separated from their instructors, for larger part of the course duration - is far from being a “new event”. Since the middle of the nineteenth century, this has been done through Radio, Mail and TV, taking advantage of the full educational potential that these media resources had to offer at the time. However, in recent times we have, at our complete disposal, the “magic wonder” of communication and globalization - the Internet. Taking advantage of a whole new set of educational opportunities, with a more or less unselfish “look” to economic interests, focusing its concern on a larger and collective “welfare”, contributing to the development of a more “equitable” world, with regard to educational opportunities, the Massive Open Online Courses (MOOCs) were born and have become an important feature of the higher education in recent years. Many people have been talking about MOOCs as a potential educational revolution, which has arrived from North America, still growing and spreading, referring to its benefits and/or disadvantages. The Polytechnic Institute of Porto, also known as IPP, is a Higher Education Portuguese institution providing undergraduate and graduate studies, which has a solid history of online education and innovation through the use of technology, and it has been particularly interested and focused on MOOC developments, based on an open educational policy in order to try to implement some differentiated learning strategies to its actual students and as a way to attract future ones. Therefore, in July 2014, IPP launched the first Math MOOC on its own platform. This paper describes the requirements, the resulting design and implementation of a mathematics MOOC, which was essentially addressed to three target populations: - pre-college students or individuals wishing to update their Math skills or that need to prepare for the National Exam of Mathematics; - Higher Education students who have not attended in High School, this subject, and who feel the need to acquire basic knowledge about some of the topics covered; - High School Teachers who may use these resources with their students allowing them to develop teaching methodologies like "Flipped Classroom” (available at http://www.opened.ipp.pt/). The MOOC was developed in partnership with several professors from several schools from IPP, gathering different math competences and backgrounds to create and put to work different activities such video lectures and quizzes. We will also try to briefly discuss the advertising strategy being developed to promote this MOOC, since it is not offered through a main MOOC portal, such as Coursera or Udacity.

Viva@Matemática project: a different way to see math

Viva@Mat is a project developed by four Math teachers from the School of Industrial Studies and Management (ESEIG) that was born with the fundamental objective of engaging ESEIG students with different math backgrounds in Math challenging activities. Some of these activities were transformed into real palpable materials and others into small interactive ones, being the great majority of them proposed by ESEIG’ students themselves. This small project rapidly grew into something we didn’t expect – it did flow over the walls of our institution to the general involving community – specifically to pre-university schools through the Viva@Math Exhibits – Orange, Blue and Green (the fourth, the Purple one is still in development). Nowadays, Viva@Math Exhibits – the public face of the Project – are itinerant and have been travelling between several, and different institutions (pre-university schools, preparatory schools, libraries, among others), around ESEIG and IPP area of influence and having registered visitors/participants of all ages. In this article we will describe the Viva@Math Project, its different activities that are categorized in some “great groups” like Numerical Trivia, Logic Activities and Mental Calculation, Puzzles, Geometric Curiosities, Magic Tricks, among others, designed to challenge students to use the underlying logical-mathematical reasoning to any ordinary and everyday activity. We will give specific and concrete examples of some of the activities developed and, also, reproduce of the general stimulating feedback the Project receives from the enrolled “actors” (teachers, students and their relatives, institutions, among others). We feel that this Project has become a small “bridge” between the pre-university schools and Higher Education Institutions (HEI), in trying to shorten the “gap” between the institutions of different levels of education and bring them to work together.

Characterization of sol-gel matrices with entrapped cutinase

Dissertação para obtenção do Grau de Doutor em Engenharia Química e Bioquímica