Um aparato para monitorar reações rápidas: um "stopped-flow" artesanal de baixo custo

The modern stopped-flow reaction analyzer has shown high efficiency and flexibility, which provides outstanding sample economy with a dead-time of less than 1 ms. However the cost of the equipment imposes a serious restriction to many Brazilian scientists and teachers. In this work we describe the construction of a low-cost stopped-flow system coupled to a UV-Vis spectrophotometer. The performance of the system was checked by monitoring the kinetics of two reactions: the fading of phenolphthalein in aqueous alkaline solution and the chlorophyll a demetallation in acid medium. The apparatus showed reasonable efficiency with a dead-time of 0.3 to 0.5 s. The very good results obtained in these two illustrative processes show that the system is satisfactory for determining rate constants with mean reaction times ranging from seconds to minutes.

Influência do sulfato de condroitina na formação de filmes isolados de polimetacrilato: avaliação do índice de intumescimento e permeabilidade ao vapor d'água

Natural or modified chondroitin sulfate was incorporated in to polymethacrylate to obtain isolated films. The addition of polysaccharide to synthetic polymers occurred at different rates. Isolated films were micro and macroscopically characterized and swelling index and water vapor transmission were determined. Results indicated changed transparency and flexibility, coupled to their dependence on increase in polysaccharide concentration. A similar occurrence was reported in the permeability to water vapor and swelling degree. Films composed of modified chondroitin sulfate, 90:10 concentration, showed hydration levels, permeability and morphological properties which allow them to be applied as excipients in the development of new drug delivery systems.

Síntese de copolímeros em bloco com propriedades líquido cristalinas

The principal techniques for the synthesis of liquid crystalline block copolymers are reviewed. The syntheses are done by living/controlled free radical chain polymerization. The copolymers display an amorphous continuous phase and a discontinuous liquid crystalline phase (LC). The presence of oxypropylenic segments disturbs the range of mesophase transitions at lower temperatures. This behavior is not observed when styrenic segments are employed and suggests that the liquid crystalline behavior can be modified in block copolymers to show mesophases at higher and lower temperatures according to the flexibility of the chain segment that is present.

Pienen ja keskisuuren osakeyhtiön pääoma uudessa osakeyhtiölaissa

Tämä Pro Gradu tutkielman tavoitteena on selvittää, miten 1.9.2007 voimaan tullut uusi osakeyhtiölaki vaikuttaa pienten ja keskisuurten osakeyhtiöiden pääomanhallintaan. Vastausta etsitään myös siihen, toteutuivatko lakimuutoksessa asetetut tavoitteet pienen ja keskisuuren yrityksen näkökulmasta. Tutkimusmetodologiana käytetään käsiteanalyyttistä lähestymistapaa. Tutkielma on havainnoiva ja selittävä. Tutkimuksen analyysin lähteenä käytettävät yritystilanteet ovat kirjoittajan tilitoimistotyössä esiin tulleita. Lain kokonaisuudistuksessa eräs tavoite oli tehdä laista pienille osakeyhtiöille selkeä ja toimintaa helpottava. Lain teksti on helppolukuisempaa ja lain rakenne on selkeä. Etua monelle perustettavalle pienelle osakeyhtiölle on siitä, että perustaminen on yksinkertaistunut ja minimipääoma pienentynyt. Velkojien aseman parantamiseksi lakiin otetun maksukykyisyystestin ja joustavan rahoitusratkaisun tarjoavan sijoitetun vapaan pääoman rahaston voidaan myös katsoa auttavan pientä ja keskisuurta osakeyhtiötä toiminnassaan. Maksukykyisyystesti on hyödyllinen muistutus varovaisesta varojen jaosta ja SVOP rahasto on vaihtoehto pääomalainalle. Verolakien uudistamatta jääminen osakeyhtiölain muuttuessa on vaikeuttanut joidenkin OYL:n mahdollistamien uusien menettelytapojen käyttöönottoa.

Sistema per gestionar les incidències d'un servei d'informàtica amb una arquitectura J2EE distribuïda en tres nivells

Tant en la meva etapa d’estudiant com en la meva curta vida laboral, he participat en el desenvolupament de varies aplicacions de gestió, tant d’escriptori com web, que majoritàriament sempre estaven dividides en tres capes però en dos nivells: la base de dades i l’aplicació, que contenia tant la lògica de negoci com la vista. Des de fa temps he tingut la curiositat i la necessitat d’intentar desenvolupar una aplicació de gestió que estigui distribuïda en tres o més nivells, separant el model de dades i la lògica de negoci de la vista. Crec que el treball de fi de carrera és idoni per desenvolupar-la. L’aplicació a desenvolupar anirà destinada a la gestió d’un servei d’informàtica, que s’encarrega de resoldre les incidències, inventariar i realitzar el manteniment preventiu dels equips informàtics d’una o de varies empreses. Es crearà una aplicació que contindrà el model de dades i la lògica de negoci. També es crearan dues aplicacions clients: una aplicació d’escriptori que donarà accés a totes i cadascuna de les funcionalitats del sistema i una aplicació web que oferirà un accés lleuger i des de qualsevol ubicació a les funcionalitats d’explotació del sistema. Per últim, també es crearà una altre aplicació web que s’encarregarà de generar els llistats sol•licitats per les dues aplicacions clients. D’aquesta manera també es centralitzarà la gestió dels llistats de les aplicacions del sistema. Per desenvolupar el sistema, s’utilitzarà la plataforma J2EE de Java, i es comptarà amb l’ajuda de marcs de treball com, per exemple, Oracle ADF o JasperReports. Com a conclusió general, puc assegurar que si es distribueixen les tres capes d’un sistema en tres nivells s’obtenen beneficis en l’administració, en el manteniment, en l’escalabilitat, en la flexibilitat i en la reutilització de les aplicacions. El principal inconvenient és el possible augment de lentitud en les aplicacions clients.

Implementació de la metodologia Scrum en una empresa de desenvolupament de Software

L’organització de la producció és sempre un factor clau en qualsevol empresa. No hi ha cap fórmula magistral que pugui servir per a tothom, perquè aquesta és molt depenent del sector i de la mida. Softvic S.A., l’empresa on treballo, em va demanar que implantés un sistema d’organització adequat a una empresa de desenvolupament de Software. Les empreses d’aquesta tipologia tenen dues característiques diferenciadores respecte una empresa de fabricació: les feines es fan una única vegada i es redefineixen freqüentment els projectes a fer al futur. És a dir, els requisits són inestables i requereixen rapidesa i flexibilitat. Actualment, Softvic S.A. ja té la ISO 9001:2008 al departament de programació. Aquesta ISO contempla com es creen les ordres de programació (OP) i ordres d’incidència (OI) i com es registra i avalua la feina realitzada. L’objectiu és implantar una metodologia que s’encarregui de la part anterior a aquesta, és a dir, definir les feines a fer en un període. Això s’ha d’integrar perfectament amb la part ja recolzada per la ISO. Per aquest fet es va escollir la metodologia Scrum que complia tots els requisits esmentats i estava contrastada per diferents empreses del món del Software. Primerament es van fer proves en les quals es guardava la informació en un Excel i s’imprimien manualment les feines a realitzar. Un cop es va haver decidit quina informació era útil i quina no en el cas de Softvic, es va crear una base de dades amb les taules i camps necessaris. Per treballar de forma més còmoda es va fer posteriorment un programa per a mantenir les dades i un formulari per imprimir etiquetes. A mesura que hem anat utilitzant la metodologia Scrum, hem anat ajustant aspectes cap on hem cregut convenient pel nostre cas en particular.

Design and manufacture of a microdistillation column

Aim of this thesis was to design and manufacture a microdistillation column. The literature review part of this thesis covers stainless steels, material processing and basics about engineering design and distillation. The main focus, however, is on the experimental part. Experimental part is divided into five distinct sections: First part is where the device is introduced and separated into three parts. Secondly the device is designed part by part. It consists mostly of detail problem solving, since the first drawings had already been drawn and the critical dimensions decided. Third part is the manufacture, which was not fully completed since the final assembly was left out of this thesis. Fourth part is the test welding for the device, and its analysis. Finally some ideas for further studies are presented. The main goal of this thesis was accomplished. The device only lacks some final assembly but otherwise it is complete. One thing that became clear during the process was how difficult it is to produce small and precise steel parts with conventional manufacturing methods. Internal stresses within steel plates and thermal distortions can easily ruin small steel structures. Designing appropriate welding jigs is an important task for even simple devices. Laser material processing is a promising tool for this kind of steel processing because of the flexibility, good cutting quality and also precise and low heat input when welding. Next step in this project is the final assembly and the actual distillation tests. The tests will be carried out at Helsinki University of Technology.

Conservation Genetics of Exploited Finnish Salmonid Fishes

Genetic diversity is one of the levels of biodiversity that the World Conservation Union (IUCN) has recognized as being important to preserve. This is because genetic diversity is fundamental to the future evolution and to the adaptive flexibility of a species to respond to the inherently dynamic nature of the natural world. Therefore, the key to maintaining biodiversity and healthy ecosystems is to identify, monitor and maintain locally-adapted populations, along with their unique gene pools, upon which future adaptation depends. Thus, conservation genetics deals with the genetic factors that affect extinction risk and the genetic management regimes required to minimize the risk. The conservation of exploited species, such as salmonid fishes, is particularly challenging due to the conflicts between different interest groups. In this thesis, I conduct a series of conservation genetic studies on primarily Finnish populations of two salmonid fish species (European grayling, Thymallus thymallus, and lake-run brown trout, Salmo trutta) which are popular recreational game fishes in Finland. The general aim of these studies was to apply and develop population genetic approaches to assist conservation and sustainable harvest of these populations. The approaches applied included: i) the characterization of population genetic structure at national and local scales; ii) the identification of management units and the prioritization of populations for conservation based on evolutionary forces shaping indigenous gene pools; iii) the detection of population declines and the testing of the assumptions underlying these tests; and iv) the evaluation of the contribution of natural populations to a mixed stock fishery. Based on microsatellite analyses, clear genetic structuring of exploited Finnish grayling and brown trout populations was detected at both national and local scales. Finnish grayling were clustered into three genetically distinct groups, corresponding to northern, Baltic and south-eastern geographic areas of Finland. The genetic differentiation among and within population groups of grayling ranged from moderate to high levels. Such strong genetic structuring combined with low genetic diversity strongly indicates that genetic drift plays a major role in the evolution of grayling populations. Further analyses of European grayling covering the majority of the species’ distribution range indicated a strong global footprint of population decline. Using a coalescent approach the beginning of population reduction was dated back to 1 000-10 000 years ago (ca. 200-2 000 generations). Forward simulations demonstrated that the bottleneck footprints measured using the M ratio can persist within small populations much longer than previously anticipated in the face of low levels of gene flow. In contrast to the M ratio, two alternative methods for genetic bottleneck detection identified recent bottlenecks in six grayling populations that warrant future monitoring. Consistent with the predominant role of random genetic drift, the effective population size (N_e) estimates of all grayling populations were very low with the majority of N_e estimates below 50. Taken together, highly structured local populations, limited gene flow and the small N_e of grayling populations indicates that grayling populations are vulnerable to overexploitation and, hence, monitoring and careful management using the precautionary principles is required not only in Finland but throughout Europe. Population genetic analyses of lake-run brown trout populations in the Inari basin (northernmost Finland) revealed hierarchical population structure where individual populations were clustered into three population groups largely corresponding to different geographic regions of the basin. Similar to my earlier work with European grayling, the genetic differentiation among and within population groups of lake-run brown trout was relatively high. Such strong differentiation indicated that the power to determine the relative contribution of populations in mixed fisheries should be relatively high. Consistent with these expectations, high accuracy and precision in mixed stock analysis (MSA) simulations were observed. Application of MSA to indigenous fish caught in the Inari basin identified altogether twelve populations that contributed significantly to mixed stock fisheries with the Ivalojoki river system being the major contributor (70%) to the total catch. When the contribution of wild trout populations to the fisheries was evaluated regionally, geographically nearby populations were the main contributors to the local catches. MSA also revealed a clear separation between the lower and upper reaches of Ivalojoki river system – in contrast to lower reaches of the Ivalojoki river that contributed considerably to the catch, populations from the upper reaches of the Ivalojoki river system (>140 km from the river mouth) did not contribute significantly to the fishery. This could be related to the available habitat size but also associated with a resident type life history and increased cost of migration. The studies in my thesis highlight the importance of dense sampling and wide population coverage at the scale being studied and also demonstrate the importance of critical evaluation of the underlying assumptions of the population genetic models and methods used. These results have important implications for conservation and sustainable fisheries management of Finnish populations of European grayling and brown trout in the Inari basin.

Use of neural networks in robot positioning of large flexible redundant manipulators

Deflection compensation of flexible boom structures in robot positioning is usually done using tables containing the magnitude of the deflection with inverse kinematics solutions of a rigid structure. The number of table values increases greatly if the working area of the boom is large and the required positioning accuracy is high. The inverse kinematics problems are very nonlinear, and if the structure is redundant, in some cases it cannot be solved in a closed form. If the structural flexibility of the manipulator arms is taken into account, the problem is almost impossible to solve using analytical methods. Neural networks offer a possibility to approximate any linear or nonlinear function. This study presents four different methods of using neural networks in the static deflection compensation and inverse kinematics solution of a flexible hydraulically driven manipulator. The training information required for training neural networks is obtained by employing a simulation model that includes elasticity characteristics. The functionality of the presented methods is tested based on the simulated and measured results of positioning accuracy. The simulated positioning accuracy is tested in 25 separate coordinate points. For each point, the positioning is tested with five different mass loads. The mean positioning error of a manipulator decreased from 31.9 mm to 4.1 mm in the test points. This accuracy enables the use of flexible manipulators in the positioning of larger objects. The measured positioning accuracy is tested in 9 separate points using three different mass loads. The mean positioning error decreased from 10.6 mm to 4.7 mm and the maximum error from 27.5 mm to 11.0 mm.

Ikääntyvät työelämässä. Päihittääkö nuoruus ja koulutus aikuisuuden ja kokemuksen?

The Ageing in Working Life. Do Adolescence and Schooling Beat Adulthood and Experience? This study examines the changes in the work and the work organisations of employees in the fields of health care and retail trade who have turned 45 and their experience of change. In addition, the question of how ageing employees experience their status in post-modern working life is explored. Attention is also focused on the choices and decisions connected with staying at work and retiring. These views are examined in relation to professions and professional cultures. Thematic interviews (N=98) were used to gather the material. The effects of the market liberalistic turn in welfare policy are clearly seen in the everyday work of the health care professions. These changes were examined from the point of view of managing by outcomes and quality assurance, multi-professional cooperation, flexibility in the division of labour, and the spread of market-like procedures. The discourse of those in involved retail trade was dominated by extremely tight global market competition and control of outcomes, and by the structural changes taking place in the retail trade sector. This change discourse was to a large extent a reaction to those changes in the functional environment which were experienced as negative and to the conflict between their own professional identity and professional ethics on the one hand, and their functional environment on the other. There were also obstacles connected with professional culture: defending one's own station and power, guarding the 'frontier', showed up in attitudes towards new management and organisation models or towards structural and functional reforms. The deep structures of professional culture and the mindset of the actors change much more slowly than the functional practices of organisations. For those in a supervisory position, the loss of power due to becoming part of a chain or because of the introduction of a team organisation model was not an easy thing to accept. The nurses and others in related fields felt that they were forced to do work that was below their level of training and professional skill. For sales personnel and those who did assisting work in health care, power and the possibility of having an influence were not so important, as long as they were able to do their work in their own way and were trusted. This view is often completely forgotten, for example, in various organisation models in which power and the possibility of having an influence entwined with power are taken for granted as being clearly positive and desired aspects of job satisfaction. Up to date professional skills were experienced as being important from the point of view of professional identity and self-worth. Thus, training can be understood as a moral obligation, which in turn is intertwined with professional ideology. In the rhetoric of adult education, an adult is expected to be an active player who will seek training again and again if working life so requires. The dark side of this ideology, which leads to feelings of guilt, was apparent in the thoughts of the respondents. Am I never good enough at my job; why must I continually strive for better, additional qualifications? The majority of the respondents evaluated their expertise as being at quite a high level. This self-confidence did not extend to applying for a job. Job recruitment was seen as a situation in which age discrimination reached its peak. The interviewees were unanimous about the idea that society favours the young. Especially among those in the retail trade sector, there was a feeling that it would be difficult, if not impossible, to find a new job of the same level or a permanent post if they were made redundant. Age discrimination was also apparent in the retail trade field in the form of older employees being retired against their will or transferred to other tasks. It was felt that ruthless forced retirement of older workers was part of the personnel policy of some organisations. The importance of one's outward appearance was connected with the theme of discrimination. This phenomenon is described using the concept of the double standard of ageing in feminist research. An ageing woman is relegated to an inferior position due to both her age and her sex. A culture that would both make possible and allow various types of choices regardless of age, which is described as being characteristic of the post-modern era, does not seem to be very topical in the practice of working life. It is important for employees that the management and the personnel policy that is being implemented makes them feel like both their contribution and they as individuals are appreciated, that their opinions are listened to and that they are noticed as persons. The interviewees hoped for gratitude and a concern for the well-being of employees that shows in everyday life. They valued training and activities aimed at maintaining their work ability, but thought that better coping at work and a pleasant working environment cannot be achieved through such measures as along as the foundation is 'in a mess'. Development of the quality of working life is the only thing that can improve job satisfaction and get people to remain in the work force longer than at present. There should be a sufficient number of properly trained employees at the work place. It was important to the respondents that they be able to stay on their job to the end with honour, since compromising with their own quality standards or acting contrary to their ideal self-image in terms of professional ethics would strike a blow to their professional self-esteem. They called for the development of various types of workplace flexibility, and felt that they have the right to a lightened workload and to early retirement. Early retirement was even seen as an altruistic deed: it would free up a place for younger workers. Thoughts of retirements were explained by familiar factors such as health and finances, life situation, the enticement of free-time, as well as by various factors related to work. It is very important to ageing employees that their work has meaningful content. The values related to self-fulfilment are felt to be of great importance, and if they cannot be realised at work, the respondents wanted more free time, either through retirement or in the form of flexibility in working life.

Brain size and evolutionary diversification in birds

The role of behavior in evolution remains controversial, despite that some ideas are over 100 years old. Changes in behavior are generally believed to enhance evolution by exposing individuals to new selective pressures and by facilitating range expansions. However, this hypothesis lacks firm empirical evidence. Moreover, behavioral changes can also inhibit evolution by hiding heritable variation from natural selection. Taking advantage of the complete phylogeny of extant birds, a new species-level measure of past diversification rate and the best existing measures of brain size (n = 1326 species), I show here that relative brain size is associated (albeit weakly) with diversification rates. Assuming that brain relative size reflects behavioral flexibility, an assumption well-supported by evidence, this finding supports the idea that behavior can enhance evolutionary diversification. This view is further supported by the discovery that the most important factor influencing diversification rates is ecological generalism, which is believed to require behavioral flexibility. Thus, behavioral changes that expose animals to a variety of environments can have played an important role in the evolution of birds.

Propriedades físicas de filmes biodegradáveis à base de amido de mandioca, álcool polivinílico e montmorilonita

The objective of this work was to manufacture biodegradable films based on cassava starch, polyvinyl alcohol (PVA) and sodium montmorillonite (Na-MMT), using glycerol as a plasticizer. These films were characterized according to their microstructure, optical, mechanical, and barrier properties. The combination of starch-PVA-MMT resulted in films with a more homogeneous surface than starch films. The introduction of PVA into the starch matrix led to the formation of films with lower water vapor permeability (WVP), higher tensile strength and greater elongation. MMT was exfoliated in the films, resulting in greater stability for different relative humidities, lower WVP, higher resistance and lower flexibility.

Kirjallisuutta

Kirjallisuusarvostelu

EFEITO DOS TRATAMENTOS SUPERFICIAIS NAS PROPRIEDADES DO BAGAÇO DA FIBRA DE PIAÇAVA Attalea funifera Martius

The aim of this study was to investigate the effect of surface treatment on the properties of waste piassava fiber with the goal of aggregating additional business value. The fiber surface was subjected to four different treatments. In the present work, it was found that washing the fibers with water partially removed impurities from the surface rendering it rougher. Alkaline treatment removed impurities from the surface, hemicellulose and lignin, improving the flexibility of the fibers. Increasing the concentration of washing agents, times and temperature of treatment promoted intense defibrillation on the fiber surface, reducing its strength.

APLICAÇÃO DE ÓXIDOS DE FERRO NANOESTRUTURADOS COMO ADSORVENTES E FOTOCATALISADORES NA REMOÇÃO DE POLUENTES DE ÁGUAS RESIDUAIS

New techniques for treating wastewater, particularly the removal or degradation of organic pollutants and heavy metals, among other pollutants, have been extensively studied. The use of nanostructured iron oxides as adsorbent and photocatalyst for the removal of these contaminants has proved a promising approach, not only because of their high treatment efficiency, but also for their cost-effectiveness, having the flexibility for in situ and ex situ applications. In this review, we briefly introduced the most used kinds of iron oxide nanoparticles, some synthesis techniques for iron oxide nanostructure formation, their potential benefits in environmental clean-up, and their recent advances and applications in wastewater treatment. These advances range from the direct applications of synthesized nanoparticles as adsorbents for removing toxic contaminants or as catalysts to oxidize and break down noxious contaminants (including bacteria and viruses) in wastewater, to integrating nanoparticles into conventional treatment technologies, such as composite photocatalytic filters (membranes, sand and ceramic) that combine separation technology with photocatalytic activity. Finally, the impact of nanoparticles on the environment and human health is briefly discussed.