Coordenação local do Eu(III) em híbridos orgânicos/inorgânicos emissores de luz branca

Eu3+ luminescence and EXAFS (Extended X-ray Absorption Fine Structure) results are presented for organic-inorganic hybrid gel hosts composed of a siliceous network to which small chains of oxyethylene units are covalently grafted by means of urea bridges. Coordination numbers for Eu3+ ions range from 12.8 to 9.7 with increasing Eu3+ concentration while the Eu3+-first neighbours mean distance is found to be constant at 2.48-2.49 Å in the same concentration range. Emission spectra display a broad band in the green/blue spectral region superposed to narrow lines appearing in the yellow/red region in such a way that for the eyes emission appears white. The broad band is assigned to intrinsic NH groups emission and also to electron-hole recombination in the nanosised siliceous domains. The narrow lines are assigned to intra-4f6, 5D0->7F0-4 Eu3+ transitions and from the energy position of the 7F0-4 levels a mean distance could be calculated for the Eu3+-first neighbours. The calculated results are in good agreement with the experimental ones obtained from EXAFS analysis.

DDT (dicloro difenil tricloroetano): toxicidade e contaminação ambiental - uma revisão

DDT and others organochlorine insecticides are very persistent substances. Clinical symptoms of intoxication have been reported in humans, although the main problem concerning such substances is bioaccumulation and biomagnification along throphic chains, leading to contamination of top predators and humans after them. In this review these characteristics are described, as well as some aspects of the control of vector borne diseases, like leishmaniasis and malaria, which were until recently, controlled by the health authorities using DDT.

Small but powerful: Top predator local extinction affects ecosystem structure and function in an intermittent stream.

Top predator loss is a major global problem, with a current trend in biodiversity loss towards high trophic levels that modifies most ecosystems worldwide. Most research in this area is focused on large-bodied predators, despite the high extinction risk of small-bodied freshwater fish that often act as apex consumers. Consequently, it remains unknown if intermittent streams are affected by the consequences of top-predators' extirpations. The aim of our research was to determine how this global problem affects intermittent streams and, in particular, if the loss of a small-bodied top predator (1) leads to a 'mesopredator release', affects primary consumers and changes whole community structures, and (2) triggers a cascade effect modifying the ecosystem function. To address these questions, we studied the topdown effects of a small endangered fish species, Barbus meridionalis (the Mediterranean barbel), conducting an enclosure/exclosure mesocosm experiment in an intermittent stream where B. meridionalis became locally extinct following a wildfire.We found that top predator absence led to 'mesopredator release', and also to 'prey release' despite intraguild predation, which contrasts with traditional food web theory. In addition, B. meridionalis extirpation changed whole macroinvertebrate community composition and increased total macroinvertebrate density. Regarding ecosystem function, periphyton primary production decreased in apex consumer absence. In this study, the apex consumer was functionally irreplaceable; its local extinction led to the loss of an important functional role that resulted in major changes to the ecosystem's structure and function. This study evidences that intermittent streams can be affected by the consequences of apex consumers' extinctions, and that the loss of small-bodied top predators can lead to large ecosystem changes. We recommend the reintroduction of small-bodied apex consumers to systems where they have been extirpated, to restore ecosystem structure and function.

Tailored Jeffamine molecular tools for ordering mesoporous Silica

Herein, we report the formation of organized mesoporous silica materials prepared from a novel nonionic gemini surfactant, myristoyl-end capped Jeffamine, synthesized from a polyoxyalkyleneamine (ED900). The behavior of the modified Jeffamine in water was first investigated. A direct micellar phase (L1) and a hexagonal (H1) liquid crystal were found. The structure of the micelles was investigated from the SAXS and the analysis by Generalized Indirect Fourier Transformation (GIFT), which show that the particles are globular of coreshell type. The myristoyl chains, located at the ends of the amphiphile molecule are assembled to form the core of the micelles and, as a consequence, the molecules are folded over on themselves. Mesoporous materials were then synthesized from the self-assembly mechanism. The recovered materials were characterized by SAXS measurements, nitrogen adsorptiondesorption analysis, transmission and scanning electron microscopy. The results clearly evidence that by modifying the synthesis parameters, such as the surfactant/silica precursor molar ratio and the hydrothermal conditions, one can control the size and the nanostructuring of the resulting material. It was observed that, the lower the temperature of the hydrothermal treatment, the better the mesopore ordering.

Euroopan unionin kestävyyskriteerien soveltuvuus liikenteen biopolttoaineiden kasvihuonekaasuvaikutusten arviointiin

Euroopan unioni on niin sanotussa RES-direktiivissä asettanut tavoitteet uusiutuvan energian käytön lisäämiseksi 10 %:iin liikenteen energian kulutuksesta kaikissa jäsenmaissa vuoteen 2020 mennessä. Eräs näistä uusiutuvan energian muodoista on biopolttoaineet. Tässä työssä testataan RES-direktiivissä esitettyä laskentamenetelmää biopolttoaineiden tuotannon ja käytön kasvihuonekaasupäästöjen arviointiin. Esimerkkitapauksena on yhdyskuntien ja teollisuuden jätemateriaalia raaka-aineena käyttävän jäte-etanoliprosessin ja siihen yhdistetyn sähköä ja lämpöä tuottavan CHP-laitoksen päästölaskenta. Laskennan yhteydessä käy ilmi RES-direktiivin laskentamenetelmän tulkinnanvaraisuus. Laskentamenetelmän perusteella järjestelmäraja voidaan asettaa usealla eri tavalla, jolloin saadut päästövähennystulokset vaihtelevat huomattavasti eri tulkintavaihtoehtojen välillä. Jäte-etanolin tapauksessa tulokset ovat myös hyvin riippuvaisia jätemateriaalille määritellystä päästökertoimesta. Laskennan perusteella voidaankin sanoa, että RES-direktiivin laskentamenetelmällä saadut päästövähennystulokset biopolttoaineille ovat hyvin epävarmoja ja riippuvat sekä laskennan lähtöoletuksista että direktiivin tulkintatavasta. RES-direktiivin laskentamenetelmää voidaan myös pitää hyvin suppeana lähestymistapana biopolttoaineiden kasvihuonekaasuvaikutusten arviointiin. Tarkastelua tehdään suppealla järjestelmärajalla ja esimerkiksi biopolttoaineketjujen aiheuttamat epäsuorat ilmastovaikutukset jäävät huomioimatta. RES-direktiivin laskentamenetelmä perustuu perinteiseen staattiseen elinkaariarviointiin eli syytarkasteluun eikä sovellu arvioimaan muutosta. Ilmastomuutoksen hillinnän haastavuuden ja kiireellisyyden vuoksi biopolttoaineiden ilmastovaikutuksia tulisi kuitenkin arvioida myös laajemmin muutostarkasteluna, ja verrata biopolttoaineiden avulla saatuja päästövähennyksiä muilla keinoin saavutettuihin päästövähennyksiin. Näin voitaisiin paremmin arvioida sitä, mitkä keinot soveltuvat parhaiten nopeiden päästövähennysten saavuttamiseen.

Anestésicos locais: interação com membranas de eritrócitos de sangue humano, estudada por ressonância magnética nuclear de ¹H e 31P

The literature carries many theories about the mechanism of action of local anesthetics (LA). We can highlight those focusing the direct effect of LA on the sodium channel protein and the ones that consider the interaction of anesthetic molecules with the lipid membrane phase. The interaction between local anesthetics and human erythrocyte membranes has been studied by ¹H and 31P nuclear magnetic resonance spectroscopy. It was found that lidocaine (LDC) and benzocaine (BZC) bind to the membranes, increase the mobility of the protons of the phospholipid's acyl chains, and decrease the mobility and/or change the structure of the polar head groups. The results indicate that lidocaine molecules are inserted across the polar and liquid interface of the membrane, establishing both electrostatic (charged form) and hydrophobic (neutral form) interactions. Benzocaine locates itself a little deeper in the bilayer, between the interfacial glycerol region and the hydrophobic core. These changes in mobility or conformation of membrane lipids could affect the Na+-channel protein insertion in the bilayer, stabilizing it in the inactivated state, thus causing anesthesia.

Entrenamiento de la fuerza orientado a la mejora de la velocidad de golpeo en tenis

El golpeo de la bola a velocidades elevadas, es un factor determinante para el rendimiento en el tenis moderno. Durante los últimos 20 años se ha producido una gran evolución del juego y los cambios en el juego moderno se han traducido en el uso de poderosos servicios y golpes de fondo. Aunque la fuerza es una capacidad determinante desde la perspectiva de la condición física, ha habido poca investigación para fundamentar la eficacia de los programas de entrenamiento de fuerza para los jugadores de tenis. El objetivo de este estudio es realizar una revisión sobre los criterios básicos para dirigir correctamente el entrenamiento de la fuerza orientado a la mejora de la de la velocidad de golpeo de la pelota. Aunque las necesidades de fuerza dinámica máxima (FDM) en los golpeos son bajas, la literatura científica parece apuntar que unos adecuados niveles de FDM ejercen efectos positivos sobre el aumento de velocidad de golpeo en el tenis. La mejora y mantenimiento de esta manifestación de fuerza se busca a expensas de factores neurales. Los entrenamientos de fuerza útil deben utilizar medios que permitan ejecutar el gesto técnico, implicar las mismas cadenas musculares, rango de movimiento o velocidades de ejecución. En este sentido, se han propuesto la utilización de pelotas medicinales, mancuernas de peso ligero, gomas elásticas, máquinas multifuncionales de resistencia neumática o poleas.

Fotoquímica de alfa,alfa-dimetilvalerofenona adsorvida em celulose microcristalina

Irradiation of a,a-dimethylvalerophenone (1) adsorbed on microcrystalline cellulose employing methanol as the solvent shows a Norrish Type II/Type I ratio of 1.0±0.1. In solution, values of 2.3±0.3 in benzene and 8.7±2.0 in terc-butanol were obtained. The cyclization/elimination ratio for the Norrish Type II reaction of 1 shows values of 1.2±0.3 in cellulose, 17.9±2.7 in benzene and 3.2±03 in terc-butanol. When samples of 1/microcrystalline cellulose were prepared employing n-hexane, the Type II/Type I (29.5±2.9) and the cycl/elim (113.3±12.1) ratios were dramatically modified. These results demonstrate the difference in the behavior of 1 when entrapped in the cellulose chains or adsorbed on the cellulose surface.

Competitive flexibility in systems supplier companies in mechanical engineering industry

Systems suppliers are focal actors in mechanical engineering supply chains, in between general contractors and component suppliers. This research concentrates on the systems suppliers’ competitive flexibility, as a competitive advantage that the systems supplier gains from independence from the competitive forces of the market. The aim is to study the roles that power, dependence relations, social capital, and interorganizational learning have on the competitive flexibility. Research on this particular theme is scarce thus far. The research method applied here is the inductive multiple case study. Interviews from four case companies were used as main source of the qualitative data. The literature review presents previous literature on subcontracting, supply chain flexibility, supply chain relationships, social capital and interorganizational learning. The result of this study are seven propositions and consequently a model on the effects that the dominance of sales of few customers, power of competitors, significance of the manufactured system in the end product, professionalism in procurement and the significance of brand products in the business have on the competitive flexibility. These relationships are moderated by either social capital or interorganizational learning. The main results obtained from this study revolve around social capital and interorganizational learning, which have beneficial effects on systems suppliers’ competitive flexibility, by moderating the effects of other constructs of the model. Further research on this topic should include quantitative research to provide the extent to which the results can be reliably generalized. Also each construct of the model gives possible focus for more thorough research.

Logistisen tiedon hallita toimitusprojektissa

Distributed supply chains, tight delivery times and tailor made products are typical for international project business. This type of environment sets great challenges for logistics management. The scope of this work was to study logistics and information management in delivery projects. The logistic information of delivery project is divided into four categories: The information used to plan, execute and follow up the material flow and the information directly embedded into material flow. On the practical study the operations of the target company are dived into main processes supporting project execution. Logistic information is studied by modelling information flows between the processes. The aim was to identify the information crucial for project materials management and describe the flow of information between the processes. Results of the study show that the information related to execution of material flow is usually emphasized when it comes to operations and tools for data management. The traditional system tools poorly support the planning of material flow in project environment. In addition the significance of clearly defined and documented practices is highlighted.

Supply Risk Management in Pharmaceutical

Fast development in the operating environment and fierce competition have driven companies to pursue efficiency and success through lean and global supply chains. At the same time overall uncertainty has increased in the business environment and supply chains have become a priority in risk management since their vulnerability may endanger business continuity. Although risk management should start at procurement strategy development phase, proactive contingency planning is also essential because it enables correct reaction and fast changes in process execution in the case of risk realization. This thesis is a case study conducted in the pharmaceutical industry where purchasing and materials management organizations face a number of challenges and limitations that have to be considered in supply risk management. The goal of the study was to discuss the operating environment, and identify and analyze supply risks and potential risk management practices. The study was concluded with suggestions for purchasing strategy development that take risk management considerations into account. This copy is the public version of the thesis.

Theoretical background for market emergence framework : Case: Electricity Distribution Industry

Both the competitive environment and the internal structure of an industrial organization are typically included in the processes which describe the strategic management processes of the firm, but less attention has been paid to the interdependence between these views. Therefore, this research focuses on explaining the particular conditions of an industry change, which lead managers to realign the firm in respect of its environment for generating competitive advantage. The research question that directs the development of the theoretical framework is: Why do firms outsource some of their functions? The three general stages of the analysis are related to the following research topics: (i) understanding forces that shape the industry, (ii) estimating the impacts of transforming customer preferences, rivalry, and changing capability bases on the relevance of existing assets and activities, and emergence of new business models, and (iii) developing optional structures for future value chains and understanding general boundaries for market emergence. The defined research setting contributes to the managerial research questions “Why do firms reorganize their value chains?”, “Why and how are decisions made?” Combining Transaction Cost Economics (TCE) and Resource-Based View (RBV) within an integrated framework makes it possible to evaluate the two dimensions of a company’s resources, namely the strategic value and transferability. The final decision of restructuring will be made based on an analysis of the actual business potential of the outsourcing, where benefits and risks are evaluated. The firm focuses on the risk of opportunism, hold-up problems, pricing, and opportunities to reach a complete contract, and finally on the direct benefits and risks for financial performance. The supplier analyzes the business potential of an activity outside the specific customer, the amount of customer-specific investments, the service provider’s competitive position, abilities to revenue gains in generic segments, and long-term dependence on the customer.

Electrical and magnetic properties of new compounds of the conductor anion [Ni(dmit)2]- and nitronyl nitroxide magnetic radicals

Three compounds have been synthesized with formulae [3-MeRad][Ni(dmit)2] (1), [4-MeRad][Ni(dmit)2] (2) and [4-PrRad][Ni(dmit)2] (3) where [Ni(dmit)2]- is an anionic pi-radical (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) and [3-MeRad]+ is 3-N-methylpyridinium alpha-nitronyl nitroxide, [4-MeRad]+ is 4-N-methylpyridinium alpha-nitronyl nitroxide and [4-PrRad]+ is 4-N-propylpyridinium alpha-nitronyl nitroxide. The temperature-dependent magnetic susceptibility of 1 revealed that an antiferromagnetic interaction operates between the 3-MeRad+ radical cations with exchange coupling constants of J1 = - 1.72 cm-1 and antiferromagnetism assigned to the spin ladder chains of the Ni(dmit)2 radical anions. Compound 1 exhibits semiconducting behavior and 3 presents capacitor behavior in the temperature range studied (4 - 300 K).

Resistência mecânica de hidrogéis termo-sensíveis constituídos de Alginato-Ca2+ / PNIPAAm, tipo Semi-IPN

Thermosensitive hydrogels were synthesized using alginate-Ca2+ in association with a thermosensitive polymer, such as PNIPAAm. The mechanical properties of the hydrogels were determined measuring the maximum tension of deformation. With the increase of the temperature by 25 to 40 ºC above the LCST the chains of PNIPAAm collapsed, dragging the alginate net and diminishing the size of the pores. The decrease in the size of the pores of the hydrogel was followed by an increase in the mechanicals resistance of the material.

Programa de gestió per la Boutique Shahrazad

Per tal d'iniciar el meu TFC, vaig decidir començar a desenvolupar un programa que contempla la gestió diària del comerç, així com la dels productes, clients, proveïdors, vendes i compres, d’un negoci que es tracta d’una botiga de roba, sabates,bosses i complements, per tal de convertir-ho en un sistema de gestió més complert. Actualment, l’entorn de negoci en el petit comerç està cada cop més desplaçat degut al gran creixement de les grans superfícies per part de franquícies de cadenes molt potents. A més, els clients són cada cop més exigents i el mercat està cada vegada més saturat. És per això que voldrem incloure un valor afegit al sistema, per poder donar un nou punt de vista al negoci, de tal manera que permeti nodrir la nostra relació amb el client, de manera que la col·laboració sigui satisfactòria per ambdues parts. I per acabar s’elabora una pàgina web per tal de fer promoció i publicitat per la botiga, ja que avui en dia és molt important existir en el món virtual.