Hemes férricos pentacoordenados e hexacoordenados dos monômeros d nativo e reconstituído da hemoglobina extracelular de Glossoscolex paulistus: estudos espectroscópicos em meio ácido

UV-Vis and fluorescence spectroscopic studies of the native and reconstituted d monomers of Glossoscolex paulistus were performed in acid medium. The coexistence of distinct species shows the complexity of the equilibria. Besides the hexacoordinate low spin hemichrome, with bands at 535 and 565 nm, a pentacoordinate high spin hemichrome is identified by the blue-shifted low intensity Soret band (371 nm) and the LMCT band (643 nm). The pentacoordinate hemichrome must be related to the partial unfolding of the polypeptide.

Pankkien rahoitusinstrumenttien arvostus menetelmät IFRS siirtymässä empiirinen tarkastelu

IFRS standardit pyrkivät yhdenmukaistamaan yritysten taloudellisen informaation esittämistapaa ja lisäämään tilinpäätöksen läpinäkyvyyttä sijoittajien näkökulmasta. Tässä tutkielmassa tarkastellaan pankkien rahoitusomaisuuserien läpinäkyvyysvaatimusten toteutumista tutkimalla, kuinka rahoitusinstrumenttien arvostusmenetelmät ovat muuttuneet IFRS:n käyttöönoton myötä. Tutkimusmenetelmäksi valittiin monitapaustutkimus, jossa selvitettiin kuinka aineistoon valitut neljä pohjoismaista pankkia oust menetelleet rahoitusinstrumenttien arvostamisessa IFRS standardien käyttöönoton siirtymävaiheessa vuosina 2003 2007. Aineistona käytettiin pankkien julkisia tilinpäätöstietoja ja vuosikertomuksia. Tulosten perusteella rahoitusinstrumenttien läpinäkyvyyden voidaan sanoa jonkin verran lisääntyneen, sillä pankit olivat yleisesti ottaen siirtyneet käyvän arvon käyttämiseen aikaisemmasta hankintamenopohjaisesta menetelmästä. Käyvän arvon kaikki pankit oust määrittäneet markkinahintanoteerausten perusteella tai niiden puuttuessa erilaistenarvostusmenetelmien avulla. Pankin koko näytti olevan sidoksissa käytettavien arvostusmenetelmien monimutkaisuuteen.

Estudo espectroscópico do equilíbrio entre espécies hexacoordenada e pentacoordenada dos monômero d nativo e reconstituído da hemoglobina extracelular gigante de Glossoscolex paulistus em meio alcalino

UV-Vis and fluorescence spectroscopic studies of native and reconstituted d monomers from Glossoscolex paulistus were performed in alkaline pH. In addition to the presence of aquomet and hemichrome hexacoordinated species, a pentacoordinated species occurs. This latter species, which presents an imidazolate group of axial histidine as fifth ligand, is identified by the blue-shifted low-intensity Soret band and LMCT band. The pentacoordinated species must occur due to partial polypeptide unfolding.

Determinação das propriedades catalíticas em meio aquoso e orgânico da lipase de Candida rugosa imobilizada em celulignina quimicamente modificada por carbonildiimidazol

Microbial lipase from Candida rugosa was immobilized by covalent binding on wood cellulignin (Eucaliptus grandis) chemically modified with carbonyldiimidazole. The immobilized system was fully evaluated in aqueous (olive oil hydrolysis) and organic (ester synthesis) media. A comparative study between free and immobilized lipase was carried out in terms of pH, temperature and thermal stability. A higher pH value (8.0) was found optimal for the immobilized lipase. The optimal reaction temperature shifted from 37 °C for the free lipase to 45 °C for the immobilized lipase. The pattern of heat stability indicated that the immobilization process tends to stabilize the enzyme. Kinetics tests at 37 °C following the hydrolysis of olive oil obeyed the Michaelis-Menten rate equation. Values for Km = 924.9 mM and Vmax = 198.3 U/mg were lower than for free lipase, suggesting that the affinity towards the substrate changed and the activity of the immobilized lipase decreased during the course of immobilization. The immobilized derivative was also tested in the ester synthesis from several alcohols and carboxylic acids.

Percutaneous access versus standard femoral exposure for endovascular abdominal aortic aneurysm repair: a randomized, controlled trial

The treatment of abdominal aortic aneurysm (AAA) has shifted from the exposure of the aorta artery in an open repair technique to a small groin cut in an endovascular repair. Recently, a percutaneous access for endovascular repair has appeared. This new technique aims to minimize the complications of the common femoral artery exposure, the patient discomfort and the length of hospitalizationObjectives: To compare the proportion of discharged patients within the first 48 postoperative hours of two common femoral artery accesses for endovascular repair of AAA: the open exposure technique and the percutaneous technique. Secondary objectives include to evaluate the total procedure time, the femoral access complications, the need for extra analgesia and the patient satisfaction and groin discomfort of the two techniquesDesign: Randomized controlled trial conducted between 2014 and 2017Participants: Patients diagnosed with abdominal aortic aneurysm with elective endovascular repair indication

Desempenho da matriz híbrida SiO2-quitosana na imobilização da lipase microbiana de Candida rugosa

Lipase from Candida rugosa was immobilized by covalent attachment on hybrid SiO2-chitosan obtained by sol-gel technique. A comparative study between free and immobilized lipase was provided in terms of pH, temperature, kinetic parameters and thermal stability on the olive oil hydrolysis. The pH and temperature for maximum activity shifted from 7.0 and 45 ºC for the free lipase to 7.5 and wide range of temperature (40-50 ºC) after immobilization. Kinetics parameters were found to obey Michaelis-Menten equation and K M values indicated that immobilization process reduced the affinity of enzyme-substrate; however Kd values revealed an increase of thermal stability of lipase.

Conversioni al cattolicesimo a Roma tra Sei e Settecento. La presenza degli scandinavi nell’Ospizio dei Convertendi.

In my PhD dissertation, I have examined a group of people of Scandinavian origin received by Ospizio dei Convertendi. This group has been hitherto largely unknown to historical research. The Ospizio was an institute founded by the Oratorian Congregation in Rome in 1673 to provide religious instruction and material aid to both recent and aspirant converts to Roman Catholicism. My research traces the profile of converts and a typology of motives, examining different factors which influenced the conversion process. I show that the key factors were often of a social rather than a religious nature. Moreover, I have analyzed the hospice in the context of Counter-Reformation charity as well. In terms of numbers, the Scandinavians formed a somewhat marginal yet not insignificant group within the Roman hospice. Out of a total of 2203 guests received between 1673 and 1706, 4.6 % were Scandinavians: 74 Swedes (including Finland and Livonia) and 27 Danes (including Norway). They came from a rigorously Protestant region which reacted to Catholicism with severe legislative measures. Converts to Catholicism risked confiscation of their goods, expulsion or even capital punishment. Since both Sweden and Denmark were practically impenetrable to Catholicism at the time and clandestine missionary attempts often failed before they had even properly started, the Roman Catholic Church shifted its interest towards Northerners arriving in Rome, a preferred destination for young noblemen, artists and migrant craftsmen. The material related to Ospizio dei Convertendi, conserved in the Vatican archives, is a scarcely known yet unusually rich source, not only for the religious history of our continent, but also for social history and the study of migration in early modern Europe. It contains a wealth of information about members of the subordinate classes, of their travels and lives in Europe. The profile delineated in these documents is of individuals who had a wide range of different professions and different aspirations. These documents encompass a vast social spectrum that was highly mobile on a continent which by that time had become pluriconfessional. Therefore, these migrants faced the complex religious reality in their everyday life. The principal corpus of my research consists of two types of manuscript sources created for administrative and in a way also for apologetic purposes of the Roman Catholic Church. My starting point is the Primo registro generale of Ospizio dei Convertendi. This is a volume in which the following information about each guest was registered: name, nationality, city of origin, age, sex, profession, confession professed before converting, date of arrival, departure, abjuration and baptism. Typically, the convert was male, originating from Stockholm or Copenhagen, from 21 to 30 years of age. The biggest occupational groups in descending order were soldiers, noblemen, craftsmen and sailors. Thus the data reflects a multiform reality of interurban and long distance migration, ideals regarding the education of young noblemen and gentry as well as the need of European armies to hire foreign mercenaries in their various campaigns. Against this background the almost total absence of women is hardly surprising: there is only one woman in the material I have studied. The second main source, Nota degl’ospiti ricevuti e spese fatte per essi, sheds more light on the choices of the converts, their motivations and their lives outside Scandinavia before reaching Rome. This narrative material permits an analysis which completes but also goes far beyond the columns of the Institute’s general register. This material consists of reports written by Catholic priests based on an interview conducted upon each guest’s arrival. The material frequently includes information on what the converts would do following their departure from the Institute as well. These sources have a specific narrative form and contain short biographies, list reasons for converting and information about the journey from the North to the Mediterranean - a journey which in many cases took several years. Moreover, they show that certain unorthodox practices such as calling on the saints and pleading for help from them were not uncommon in the Protestant popular religion. The recording of information on conversions from Protestantism to Catholicism reflects both religious and social interest on the part of the receiving institute. The information obtained was used for the purposes of religious teaching, for finding adequate ways of inserting the convert into Italian society so that he could earn a living, and to find effective methods to convert others with a similar cultural and geographical background. The stories recorded were based on interviews with the newly-arrived, information obtained from a travel companion or fellow countrymen, or from written documents the aspirant converts carried with them. These sources illustrate, although sometimes in rather simplified ways, the circumstances and motivations which were relevant to the choice of changing one’s confession. In addition, I have examined petitions addressed to the hospice and other Roman authorities in order to get financial aid. These petitions were written by Italian scrittori, and they contain certain conventions and topoi of presenting the conversion with the purpose of improving the chances of obtaining financial aid. It is through these filters, which may seem initially almost invisible, that the remote voice of the converts reaches us. The results of the analysis are particularly interesting because they disagree with some of the principal conclusions of previous work on the subject. First, earlier research has focused almost exclusively on the conversions of noblemen, and has argued, second, that the Queen Christina of Sweden was the driving force behind their change of confession. The sources examined for this dissertation present a profile of long-distance migrants, many of them members of the subordinate classes, who were looking for ways to make their living in Europe. These people had in many cases left their country of origin several years earlier and not for religious reasons, so, crucially, we are not dealing with confessional migration in these cases. Rather, conversion was a complex process, intricately tied up with strategies of survival, integration and upward social mobility. At the same time, while these components are significant on their own right, they do not necessarily point to the absence of motivations of a more clearly religious nature.

INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

Resorcinol-formaldehyde (RF) organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C) molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.

Finnish Critical Industries, Maritime Transport Vulnerabilities and societal Implications

Maritime transports are very essential for Finland as over 80% of the foreign trade in the country is seaborne and possibilities to carry out these transports by are limited. Any disruption in maritime transports has negative consequences to many sectors in the Finnish economy. Maritime transport thus represents critical infrastructure for Finland. This report focuses on the importance of maritime transports on security of supply in Finland and for the so called critical industries in particular. The report summarizes the results of the Work Package 2 of the research project STOCA – “Study of cargo flows in the Gulf of Finland in emergency situations”. The aim of the research was to analyze the cargo flows and infrastructure that are vital for maintaining security of supply in Finland, as well as the consequences of disruptions in the maritime traffic for the Finnish critical industries and for the Finnish society. In the report we give a presentation of the infrastructure and transport routes which are critical for maintaining security of supply in Finland. We discuss import dependency of the critical industries, and the importance of the Gulf of Finland ports for Finland. We assess vulnerabilities associated with the critical material flows of the critical industries, and possibilities for alternative routings in case either one or several of the ports in Finland would be closed. As a concrete example of a transport disruption we analyze the consequences of the Finnish stevedore strike at public ports (4.3.–19.3.2010). The strike stopped approximately 80% of the Finnish foreign trade. As a result of the strike Finnish companies could not export their products and/or import raw materials, components and spare parts, or other essential supplies. We carried out personal interviews with representatives of the companies in Finnish critical industries to find out about the problems caused by the strike, how companies carried out they transports and how they managed to continue their operations during the strike. Discussions with the representatives of the companies gave us very practical insights about companies’ preparedness towards transport disruptions in general. Companies in the modern world are very vulnerable to transport disruptions because companies regardless of industries have tried to improve their performance by optimizing their resources and e.g. by reducing their inventory levels. At the same time they have become more and more dependent on continuous transports. Most companies involved in foreign trade have global operations and global supply chains, so any disruption anywhere in the world can have an impact on the operations of the company causing considerable financial loss. The volcanic eruption in Iceland in April 2010 stopping air traffic in the whole Northern Europe and most recently the earth quake causing a tsunami in Japan in March 2011 are examples of severe disruptions causing considerable negative impacts to companies’ supply chains. Even though the Finnish stevedore strike was a minor disruption compared to the natural catastrophes mentioned above, it showed the companies’ vulnerability to transport disruptions very concretely. The Finnish stevedore strike gave a concrete learning experience of the importance of preventive planning for all Finnish companies: it made them re-think their practical preparedness towards transport risks and how they can continue with their daily operations despite the problems. Many companies realized they need to adapt their long-term countermeasures against transport disruptions. During the strike companies did various actions to secure their supply chains. The companies raised their inventory levels before the strike began, they re-scheduled or postponed their deliveries, shifted customer orders between production plants among their company’s production network or in the extreme case bought finished products from their competitor to fulfil their customers’ order. Our results also show that possibilities to prepare against transport disruptions differ between industries. The Finnish society as a whole is very dependent on imports of energy, various raw materials and other supplies needed by the different industries. For many of the Finnish companies in the export industries and e.g. in energy production maritime transport is the only transport mode the companies can use due to large volumes of materials transported or due to other characteristics of the goods. Therefore maritime transport cannot be replaced by any other transport mode. In addition, a significant amount of transports are concentrated in certain ports. From a security of supply perspective attention should be paid to finding ways to decrease import dependency and ensuring that companies in the critical industries can ensure the continuity of their operations.

Hankintatoimen suorituskyvyn mittaaminen

Hankintatoimen merkitys yritysten kannattavuudelle on huomioitu viime vuosina aiempaa enemmän. Hankintatoimen rooli on muuttunut strategi-sen toiminnon suuntaan. Myös hankintatoimen suorituskyvyn johtamiseen on alettu kiinnittää enemmän huomiota. Tutkimuksen tavoitteena on suunnitella ja valita sopivat mittarit hankintatoimen suorituskyvyn mittaamista varten. Tutkimuksen toisena tavoitteena on arvioida sitä, mitkä valituista mittareista mittaavat organisaation aineetonta pääomaa. Tutkimus toteutetaan case-tutkimuksena. Aineiston keräämiseen ja ratkaisun toteuttamiseen käytetään kvalitatiivista tutkimusmenetelmää ja konstruktiivista tutkimus-otetta. Tutkimuksessa sovellettiin Balanced Scorecard -mittariston toteutuspro-sessia. Valitut mittarit ryhmiteltiin neljän näkökulman mukaisesti. Mittaris-toa ja näkökulmien soveltuvuutta tulee arvioida säännöllisesti käyttöönoton jälkeen. Aineettoman pääoman merkityksestä hankintatoimessa tarvitaan edelleen lisätutkimusta.

Vuokamallisten kartonkipakkausten laadunvarmistuslaitteiston kehittäminen

Diplomityön tavoitteena oli kehittää vuokamallisille kartonkipakkauksille laadunvarmistuslaitteisto. Kirjallisen osan alussa esiteltiin vuokamallisten kartonkipakkausten valmistusprosessia. Tästä siirryttiin laatuasioihin, jossa tärkeimmät asiat olivat kartonkivuokien valmistuksessa esiintyvät laatupoikkeamat ja konenäkö. Tutkimusosan alussa esitellään Lappeenrannan teknillisessä yliopistossa kehitetty kartonkivuokien valmistuslinjasto. Tämän jälkeen vaatimuslistan pohjalta suunnitellaan kyseiseen linjastoon sopiva automaattinen laadunvalvontalaite, johon sisältyy myös kartonkivuokien siirtolaite. Suunnitteluprosessi aloitettiin koekuvaamalla kartonkivuokia erilaisilla kameroilla ja valaistusmenetelmillä. Koekuvausten perusteella valittiin konenäkölaitteisto. Tämän jälkeen toiminnoista luotiin periaatepiirroksia, joista kehitettiin varsinainen suunnitelma. Työn tuloksena saatiin suunnitelma konenäköön perustuvan automaattisen laadunvalvontalaitteen rakentamiselle.

Rukoile ja työtä tee. Onni Puhakan kehitys innovaattorista oman tien kulkijaksi

Pray and work. The development of Onni Puhakka: from innovator to nonconformist This ethnological biographical study examines the modernization which began in the mid-1800s, continued into the mid-1900s, and has changed Finnish society in many ways. This era has been studied on a general level quite extensively, but this work explores the life and everyday experiences of Onni Puhakka (1870−1955), a farmer who spent most of his life in the town of Liperi. The goal is to find new perspectives on the development of the modernization process in society through the experiences of an individual. In this study, a central theme is the rural co-operative movement represented in Finland by Pellervo as well as its development in this country and as a significant undertaking in Onni Puhakka’s life. The co-operative movement was one of the most significant sectors affecting modernization in rural communities. The main character in the study is the grandfather of the present author, and thus this research belongs to the newly accepted ethnological research tradition of studying one’s own community. Written documents, mainly collected and preserved by Onni Puhakka himself during his lifetime, form the research material. The material consists mainly of Puhakka’s extensive correspondence, personal notes and diaries, documents related to his farm, and photographs taken by him. Earlier research and other written material examining the general development of the period were used to provide a background for the study. The co-operative movement formed a comprehensive ideology for Onni Puhakka, in which the possibilities for the development of both individuals and the community were combined. His life was based on a religious conviction, and he felt that the co-operative movement was the application of Christian love for one’s neighbour in practice. At the beginning of his active working career, Puhakka was an innovator, a reformer at the forefront of progress, but quite soon he became a sworn critic of the development of the co-operative movement in particular. One of Puhakka’s criticisms of the co-operative movement was the shifting of decision-making power to professional managers and central organizations, far from the reach of local actors. A fundamental reason for his dissatisfaction was the development within the co-operative movement in which the ideological background was forgotten, and economic goals and making a profit took an excessive significance. This assessment of the co-operative movement made by Onni Puhakka and his predictions about its development were not unfounded. This has been shown by several studies examining the development of both the Pellervo and working class cooperative movements. The professionalization of management, managerialism, as well as the direct links between professional managers of local co-operatives and central organizations have lead to the situation in which fewer and fewer people make the decisions, and management has as its goal economic success and growth. Co-operative enterprises that have grown in size have become estranged from the everyday life of their members. Instead of taking care of relations with the membership of the co-op, competitive ability and the market share have become the most important concerns of the management. As the membership has become alienated, their interest in large-scale co-ops has also become largely economic. A significant change among the membership of the Pellervo movement occurred at the stage when the co-operative movement shifted from rural areas to urban centres. This meant that the commitment of the membership became much looser than it had been in the farmers’ production and consumer co-ops. From the point of view of its members, the nature of the co-operative movement has become diametrically opposed to its point of departure: the active members who previously formed the subject of the co-operative movement have become the object of the economic activities of that same movement. The co-operative movement has been transformed from the progressive agent of change of its early years into a business activity which no longer has any significant task as a social reformer. This study confirms the observations of the latest research on modernization which states that modernization has not been a straightforward and inevitable development that has lead to the present situation. For example, the criticism directed by Puhakka toward the co-operative movement includes information that shows that a few others who were initially actively involved also criticized the development of the movement. Despite his occasional frustration, Onni Puhakka continued his criticism and attempts to get the co-operative movement to change its course and return to its ‘roots’. In the early years of the cooperative movement he probably did not differ much from the other pioneers in the sense that many of them had adopted and internalized the same values and motive for being involved that he had. However, Puhakka differed from his colleagues in the sense that he was able to believe in what he called the “fundamental values” of the co-operative movement longer than many of them.

Episodes in carbohydrate chemistry : from β-linked mannosides to glycoconjugates

Carbohydrates are one of the most abundant classes of biomolecules on earth. In the initial stages of research on carbohydrates much effort was focused on investigation and determination of the structural aspects and complex nature of individual monosaccharides. Later on, development of protective group strategies and methods for oligosaccharide synthesis became the main topics of research. Today, the methodologies developed early on are being utilized in the production of carbohydrates for biological screening events. This multidisciplinary approach has generated the new discipline of glycobiology which focuses on research related to the appearance and biological significance of carbohydrates. In more detail, studies in glycobiology have revealed the essential roles of carbohydrates in cell-cell interactions, biological recognition events, protein folding, cell growth and tumor cell metastasis. As a result of these studies, carbohydrate derived diagnostic and therapeutic agents are likely to be of growing interest in the future. In this doctoral thesis, a journey through the fundamentals of carbohydrate synthesis is presented. The research conducted on this journey was neither limited to the study of any particular phenomena nor to the addressing of a single synthetic challenge. Instead, the focus was deliberately shifted from time to time in order to broaden the scope of the thesis, to continue the learning process and to explore new areas of carbohydrate research. Throughout the work, several previously reported synthetic protocols, especially procedures related to glycosylation reactions and protective group manipulations, were evaluated, modified and utilized or rejected. The synthetic molecules targeted within this thesis were either required for biological evaluations or utilized to study phenomena occuring in larger molecules. In addition, much effort was invested in the complete structural characterization of the synthesized compounds by a combination of NMR spectroscopic techniques and spectral simulations with the PERCH-software. This thesis provides the basics of working with carbohydrate chemistry. In more detail, synthetic strategies and experimental procedures for many different reactions and guidelines for the NMR-spectroscopic characterization of oligosaccharides and glycoconjugates are provided. Therefore, the thesis should prove valuable to researchers starting their own journeys in the ever expanding field of carbohydrate chemistry.

The Evolution of Securities Lending and Risk Mitigation: A Finnish Market Case Study

Although securities lending is an important function of the financial markets, it has not received that much academic attention. This study examines the evolution of European securities lending and risk management with an emphasis on the development of collateral management, the function responsible for reducing credit risk. The effects of the recent financial instabilities are also considered. The evolution of the Finnish securities lending market is examined in more detail through a case-study. This study can be classified as a constructive qualitative case study. The initial practical knowledge comes from the author's own experience and additional insight and theoretical background is acquired through a literature review. The case study is based on research, semi-structured interviews and a brief analysis of numerical data. The main observation of this study was that securities lending is now recognized as more of an investment management discipline than an operational support function. The recent financial instabilities have resulted in an increased focus on risk and transparency. In securities lending this is directly reflected in collateral management guidelines and procedures. Collateral management has become increasingly technologically developed and automated. Collateral optimization initiatives have been started to make the process more efficient, liquid, and cost effective. Although securities lending is generally an OTC-market with no standard market place, centralized exchange-like models have been introduced. Finnish securities lending has now shifted towards the more common global OTC model. Although the Finnish securities lending industry has developed, and the main laws governing it (tax legislation) have changed, there is still need for development. There are still not many Finnish participants involved and due to legal issues most securities loans are collateralized with cash and not securities (e.g. government bonds).

O papel atual do cirurgião no tratamento do GIST

Recent progress in gastrointestinal stromal tumor's (GIST) treatment were responsible for changing GIST's natural history. Knowlegde acquirement of molecular mechanism-based systemic therapy gave rise to the development of targeted antineoplastic drugs capable of reaching outcomes that had never been reached before. The introduction of imatinib in the clinical practice not only changed GIST's patients survival but also shifted paradigms. However, besides all these new advances and the improved results with imatinib, the surgeon still plays a pivotal role in the management of the primary GIST tumor and even in the metastatic setting.