Extração sortiva em barra de agitação para análise de fármacos em fluidos biológicos

A novel solventless sample preparation, stir-bar sorptive extraction (SBSE), for extraction, and sample enrichment of organic compounds from biological fluids, is described in this manuscript from principle to applications. The SBSE is based on sorptive extraction, whereby the compounds are extracted into a polymer coating, polydimethylsiloxane (PDMS), on a magnetic stirring rod. The extraction is controlled by the partitioning coefficient of drugs between the PDMS and sample matrix, and upon the sample-extraction medium phase ratio. The SBSE technique has been applied successfully, with high sensitivities, to biomedical analysis of volatiles and for semi-volatiles drugs from biological sample, including urine, plasma, and saliva. SBSE combined with in situ derivatization, drugs quite more polar (e.g. metabolites) also can be analyzed.

Aplicações de enzimas na síntese e na modificação de polímeros

Enzymes are biological catalysts that offer great potential for use in the synthesis and modification of polymers, being more specific and greener than chemical catalysts. In this work, enzymes from the classes of hydrolases (lipase, cutinase and protease) and of oxidoreductases (horseradish peroxidase, manganese peroxidase and laccase) were identified as the main biocatalysts responsible for the synthesis of polymers. Biocatalysis can potentially be part of the life cycle of several polymers, including polyesters, polyurethanes, polycarbonates, polyamides, functionalized polysaccharides and polystyrene, allowing the synthesis of specialty macromolecules for fine applications and with higher added-value than commodity polymers.

Buying behavior of public organizations and its influence on export partner governance

Public organizations form a significant part of any economy, yet their buying behavior has received very little attention. Operating with complex public sector is further complicated when sales and marketing activities are done by foreign export partners. This thesis explores the buying behavior of public organizations and how partnership governance is influenced by it. The theoretical part focuses on two subjects. Firstly the strictly regulated purchase process, rigid decision making and other special characteristics of public organizations are examined. Secondly the thesis examines partnership governance forms and how coordination is arranged in the relationships. The empirical part investigates the subjects of public organization buying behavior and partnership governance using a case study of a Finnish SME and their two export partners. The findings suggest high degree of uniformity between public organizations enables the use of unilateral governance forms. By creating mutual dependence through training the possibility of adopting a purely bilateral governance form exists as well.

Cytopathology of callus cells infected with grapevine leafroll-associated virus 3

The cytopathology of grapevine (Vitis spp.) callus tissue infected with Grapevine leafroll-associated virus 3 (GLRaV-3), genus Vitivirus was studied in order to investigate the usefulness of callus cultures to study grapevine leafroll-associated viruses. Ultrathin sections were made from in vitro callus obtained from stems and shoots of GLRaV-3 infected grapevine plants. Callus was composed of two types of tissue. Translucent, soft callus was formed and composed of large loosely arranged cells, containing big vacuoles and a thin layer of cytoplasm. Other parts of the callus were brown-coloured and composed of small compactly arranged cells, which showed flexuous and rod-shaped closterovirus-like particles, with 10-12 nm in diameter, at higher magnifications. Groups of vesicles formed by a single membrane were also observed, with sizes ranging from 50-200 nm, containing fine fibrillar material, also typical of closterovirus infections. Virus concentration was monitored by Immunosorbent electron microscopy (ISEM) tests, which showed that in vitro culture of callus tissue from grapevine infected plants, could be used to study the GLRaV viruses through many successive generations, despite the decline in virus concentration after repeated transfers. No virus particles were observed in callus tissue obtained from healthy grapevines.

Optimization of the power cable for low voltage direct current system

The demand for electricity is constantly growing in contemporary world and, in the same time, quality and reliability requirements are becoming more rigid. In addition, renewable sources of energy have been widely introduced for power generation, and they create specific challenges for the network. Consequently, new solution for distribution system is required, and Low Voltage Direct Current (LVDC) system is the proposed one. This thesis focuses on the investigation of specific cable features for low voltage direct current (LVDC) distribution system. The LVDC system is public ±750 VDC distribution system, which is currently being developed at Lappeen-ranta University of Technology. The aspects, considered in the thesis, are reliable and economic power transmission in distribution networks and possible power line communication in the LVDC cable.

Suitability of foam coating on application of thin liquid films

This work aimed to find out the suitability of foam as medium in application of thin liquid films. This consists of research over phenomena related to foam physics and behaviour. Solutions and mixtures to be foamed, foaming agents, foam generation and application methods were evaluated. Over the evaluated solutions and mixtures coating paste and CMC did not foam well. Latex and PVA solutions were foamable and the best solution for foam use was starch. PVA and casein can be used as foaming agents, but the best results were achieved with sodium dodecyl sulphate (SDS). SDS works well with starch solutions producing fine and stable foam. Foaming was done with simple mixers where pressurized air was fed to the solution. The foaming works fine when enough shear force is used together with sufficient foaming agent concentration. Foam application with curtain, rod and cylinder methods with a gap between the application device and paper were not usable because of high coating amount. Coating amounts were smallest with the blade method which achieved 0.9 g/m2 starch layer. Although some strength decrease was expected because of the foaming agent, it dit not have significant effect. The targeted coating amount of 0.5 g/m2 was not achieved due to the limitations with the methods. More precise foam application methods are needed. Continuous foam generation and feed to the paper surface with controllable device such as application teeth could improve the results.

Phase voltage control and filtering in a converter-fed single-phase customer-end system of the LVDC distribution network

In recent years, the network vulnerability to natural hazards has been noticed. Moreover, operating on the limits of the network transmission capabilities have resulted in major outages during the past decade. One of the reasons for operating on these limits is that the network has become outdated. Therefore, new technical solutions are studied that could provide more reliable and more energy efficient power distributionand also a better profitability for the network owner. It is the development and price of power electronics that have made the DC distribution an attractive alternative again. In this doctoral thesis, one type of a low-voltage DC distribution system is investigated. Morespecifically, it is studied which current technological solutions, used at the customer-end, could provide better power quality for the customer when compared with the current system. To study the effect of a DC network on the customer-end power quality, a bipolar DC network model is derived. The model can also be used to identify the supply parameters when the V/kW ratio is approximately known. Although the model provides knowledge of the average behavior, it is shown that the instantaneous DC voltage ripple should be limited. The guidelines to choose an appropriate capacitance value for the capacitor located at the input DC terminals of the customer-end are given. Also the structure of the customer-end is considered. A comparison between the most common solutions is made based on their cost, energy efficiency, and reliability. In the comparison, special attention is paid to the passive filtering solutions since the filter is considered a crucial element when the lifetime expenses are determined. It is found out that the filter topology most commonly used today, namely the LC filter, does not provide economical advantage over the hybrid filter structure. Finally, some of the typical control system solutions are introduced and their shortcomings are presented. As a solution to the customer-end voltage regulation problem, an observer-based control scheme is proposed. It is shown how different control system structures affect the performance. The performance meeting the requirements is achieved by using only one output measurement, when operating in a rigid network. Similar performance can be achieved in a weak grid by DC voltage measurement. An additional improvement can be achieved when an adaptive gain scheduling-based control is introduced. As a conclusion, the final power quality is determined by a sum of various factors, and the thesis provides the guidelines for designing the system that improves the power quality experienced by the customer.

Magnetic and transport properties of LaMnO3+δ, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1-xSrxMn1-yFeyO3

Interest to hole-doped mixed-valence manganite perovskites is connected to the ‘colossal’ magnetoresistance. This effect or huge drop of the resistivity, ρ, in external magnetic field, B, attains usually the maximum value near the ferromagnetic Curie temperature, TC. In this thesis are investigated conductivity mechanisms and magnetic properties of the manganite perovskite compounds LaMnO3+, La1-xCaxMnO3, La1-xCaxMn1-yFeyO3 and La1- xSrxMn1-yFeyO3. When the present work was started the key role of the phase separation and its influence on the properties of the colossal magnetoresistive materials were not clear. Our main results are based on temperature dependencies of the magnetoresistance and magnetothermopower, investigated in the temperature interval of 4.2 - 300 K in magnetic fields up to 10 T. The magnetization was studied in the same temperature range in weak (up to 0.1 T) magnetic fields. LaMnO3+δ is the parent compound for preparation of the hole-doped CMR materials. The dependences of such parameters as the Curie temperature, TC, the Coulomb gap, Δ, the rigid gap, γ, and the localization radius, a, on pressure, p, are observed in LaMnO3+δ. It has been established that the dependences above can be interpreted by increase of the electron bandwidth and decrease of the polaron potential well when p is increased. Generally, pressure stimulates delocalization of the electrons in LaMnO3+δ. Doping of LaMnO3 with Ca, leading to La1-xCaxMnO3, changes the Mn3+/Mn4+ ratio significantly and brings an additional disorder to the crystal lattice. Phase separation in a form of mixture of the ferromagnetic and the spin glass phases was observed and investigated in La1- xCaxMnO3 at x between 0 and 0.4. Influence of the replacement of Mn by Fe is studied in La0.7Ca0.3Mn1−yFeyO3 and La0.7Sr0.3Mn1−yFeyO3. Asymmetry of the soft Coulomb gap and of the rigid gap in the density of localized states, small shift of the centre of the gaps with respect to the Fermi level and cubic asymmetry of the density of states are obtained in La0.7Ca0.3Mn1−yFeyO3. Damping of TC with y is connected to breaking of the double-exchange interaction by doping with Fe, whereas the irreversibility and the critical behavior of the magnetic susceptibility are determined by the phase separation and the frustrated magnetic state of La0.7Sr0.3Mn1−yFeyO3.

Vårdande och icke-vårdande tröst

The aim of the thesis is, from a caring science perspective including a caring theology perspective, to illustrate the meaning of the phenomenon consolation and howconsolation relates to suffering and care. Two studies were completed where staff and elderly care receivers were interviewed and a third study focused on an analysis of consolation as it is presented in the Book of Job in the Old Testament. These studies deal with carers' experiences of consolation and consoling, elderly care receivers' experiences of consolation, and Job's experience of consolation. Phenomenology and hermeneutics form the basis for the methodological approach. A phenomenological- hermeneutic method, inspired by Paul Ricoeur, has been used for the text analyses. The thesis also covers significant aspects of poetical and religious texts. The metaphors that occur in the interview studies with the carers and the elderly are analysed in order to take care of the excess of meaning that, according to Ricoeur, can be expressed in metaphors. The result showfive overall meanings: The contradictory consolation, The bonding consolation, The mute and rigid consolation, The uncontrolled consolation and The restful consolation. A caring consolation is contradictory in the sense that it entails that the sufferer on the one hand passes on his or her suffering to someone else and on the other hand that the suffering can be returned to be suffered. Consolation can thus entail suffering. The bonding consolation is present, i.e. is with the sufferer and is based on that person's suffering. This consolation is characterised by a close fellowship, a feeling of being understood at a deeper level. The results also reveal a consolation that is mute and rigid. This consolation does not respond to the sufferer's experience of his or her suffering, is shapeless and therefore unable to follow the suffering. An example of a mute, rigid and non-caring consolation is the consolation of the friends in the Book of Job. This consolation is not capable of consoling because it does not correspond to where Job is, i.e. in his experience of his suffering. A caring consolation is also uncontrolled because it is on the one hand spontaneous and on the other hand helps the sufferer to lose control over the suffering. To lose control entails, amongst other things, the sufferer giving up trying to understand suffering and instead lets that which is incomprehensible be incomprehensible. A consoling and health-bringing rest in or from the struggle with suffering presents itself by giving up what in various ways is tied to the suffering. The result as a whole is interpreted from a caring science perspective with the following important concepts: caring relationship, faith, health and sacrifice. Consolation as health is considered on the basis of a theoretical model inspired by Katie Eriksson's ontological health model. The research is also illustrated from a philosophical-ethical perspective, mainly based on the work of Emmanuel Levinas. The findings are discussed in relation to previous research and also to caring science, society and care.

General terms and rigidity: another solution to the trivialization problem

In this paper I am concerned with the problem of applying the notion of rigidity to general terms. In Naming and Necessity, Kripke has clearly suggested that we should include some general terms among the rigid ones, namely, those common nouns semantically correlated with natural substances, species and phenomena, in general, natural kinds -'water', 'tiger', 'heat'- and some adjectives -'red', 'hot', 'loud'. However, the notion of rigidity has been defined for singular terms; after all, the notion that Kripke has provided us with is the notion of a rigid designator. But general terms do not designate single individuals: rather, they apply to many of them. In sum, the original concept of rigidity cannot be straightforwardly applied to general terms: it has to be somehow redefined in order to make it cover them. As is known, two main positions have been put forward to accomplish that task: the identity of designation conception, according to which a rigid general term is one that designates the same property or kind in all possible worlds, and the essentialist conception, which conceives of a rigid general term as an essentialist one, namely, a term that expresses an essential property of an object. My purpose in the present paper is to defend a particular version of the identity of designation conception: on the proposed approach, a rigid general term will be one that expresses the same property in all possible worlds and names the property it expresses. In my opinion, the position can be established on the basis of an inference to the best explanation of our intuitive interpretation and evaluation, relative to counterfactual circumstances, of statements containing different kinds of general terms, which is strictly analogous to our intuitive interpretation and evaluation, relative to such circumstances, of statements containing different kinds of singular ones. I will argue that it is possible to offer a new solution to the trivialization problem that is thought to threaten all versions of the identity of designation conception of rigidity. Finally, I will also sketch a solution to the so-called 'over-generalization and under-generalization problems', both closely related to the above-mentioned one.

Influence of stiffness in bolted connections in wooden plane structure of truss type

Trusses are structural systems commonly used in projects, being employed mainly in roof structures, present in most rural buildings. The design of trusses, as well as other structural systems, requires the determination of displacements, strains and stresses. However, the project is developed from an ideal model of calculation, considering free rotation between the elements of a connection. This paper presents a computer program for the analysis of bidimensional wooden trusses with connections formed with two screws per node. The formulation is based on the flexibility method, taking into account the influence of the effect of semi-rigid connections formed by two screws. An example of a structure is presented and analyzed by the program developed here, highlighting the importance of behavior analysis on semi-rigid connections.

Wet bulbs from the subsurface drip irrigation with water supply and treated sewage effluent

The use of treated sewage effluent (TSE) combined with the subsurface drip irrigation (SDI) method in agriculture can decrease the costs of agricultural production, in attempts to fertigate crops more efficiently. In this study it was compared the dimensions of the wet bulb formed by the application of TSE and municipal water supply (MWS) in an Oxisoil. We have evaluated the effect of water quality and discharge between drippers used in sugarcane crop. Three trenches were opened and 21 three-rod TDR probes were setup in a mesh and a dripper was buried at 0.30 m, for each constant discharge of 1.0 L h-1and 1.6 L h-1. Comparing results from different wetted soil profiles it was observed that the vertical and horizontal dimensions of the wet bulb are similar for both MWS and TSE, being peculiars according to the discharges used and volume applied. Regardless the water quality, an increase of 60% in discharge decreased the deepest infiltration.

Extração de fitobezoar gástrico por videolaparoscopia: considerações técnicas originais

Videolaparoscopic surgery has been used for treatment of almost all surgical abdominal diseases, mainly where there are no large ressections, or operative field is limited. In these situations, laparoscopic surgery has the advantages of less morbidity, quick recovery and good cosmetic results. Bezoars removal, or its mobilization, is probably included in these possible proceedings. Three non-laparotomic procedures were described: 1. endoscopic-laparoscopic; 2. videolaparoscopy and mobilization of intestinal bezoar to the cecum; 3. laparoscopy and gastrotomy for bezoar removal, through suprapubic incision or the umbilical punction. There have been only two publications describing the videolaparoscopic method for bezoar removal, and the methods applied can be complications or morbidity related. We describe one case where the applied technique is simple and easy to perform, time saving and probably less complications-related. This technique, with four trocars, utilized a plastic bag besides the stomach to be opened, followed by gastrotomy, bezoar removal and immediate introduction in the plastic bag, suture of gastrotomy and removal through the left subcostal trocar. This technique was feasible and easy to perform, with short operative time, and there were no intra or post-operative complications; the patient was discharged in the second post-operative day, and is without further problems after one year follow-up. We believe that this could be an adequate technique to perform laparoscopic gastric bezoar removal, and the rigid sequence of operative events allows a quick procedure, with minimal contamination. The videolaparoscopy seems to be an adequate access to surgical treatment of gastro-intestinal bezoars, with or without obstruction, and should be the ellected the procedure of choice to begin the surgical treatment, with convertion to laparotomy in case of any intra-operative adversity.