SÍNTESE E DETERMINAÇÃO DA ESTEREOQUÍMICA RELATIVA DE UM NOVO EPÓXIDO ALDEÍDO CICLOPENTANO MONOTERPENÓIDE

In this study, we report the preparation of a new tetra-substituted epoxide aldehyde cyclopentane, which acts as a starting material for the synthesis of plinol, from (R)-(+)-epoxy-limonene. The synthesis was performed in three steps and resulted in a good yield. The structural determination was performed by 1H and 13C NMR, and the relative stereochemistry was defined by nuclear Overhauser effect (NOE) experiments with computer calculations of molecular modeling, particularly with respect to indirect coupling constant calculations.

Spectroscopic analysis of C80 doping with group III and group V elements using semiempirical PM3 molecular modelling technique

Semiempirical calculations at the level of PM3 of theory were carried out to study the structural and electronic properties of C80 and some of its doped derivatives with the elements of group III and V at the level of PM3 of theory. We have selected these elements to be substituted in the fullerene-C80 cage in order to show the effect of such structural change on the electronic properties of the molecules studied. The theoretical IR spectra, some of physical and chemical properties of the molecules studied are obtained and discussed.

Cuticular and Suberin Polymers of Edible Plants. Analysis by Gas Chromatographic-Mass Spectrometric and Solid State Spectroscopic Methods

Cutin and suberin are structural and protective polymers of plant surfaces. The epidermal cells of the aerial parts of plants are covered with an extracellular cuticular layer, which consists of polyester cutin, highly resistant cutan, cuticular waxes and polysaccharides which link the layer to the epidermal cells. A similar protective layer is formed by a polyaromatic-polyaliphatic biopolymer suberin, which is present particularly in the cell walls of the phellem layer of periderm of the underground parts of plants (e.g. roots and tubers) and the bark of trees. In addition, suberization is also a major factor in wound healing and wound periderm formation regardless of the plants’ tissue. Knowledge of the composition and functions of cuticular and suberin polymers is important for understanding the physiological properties for the plants and for nutritional quality when these plants are consumed as foods. The aims of the practical work were to assess the chemical composition of cuticular polymers of several northern berries and seeds and suberin of two varieties of potatoes. Cutin and suberin were studied as isolated polymers and further after depolymerization as soluble monomers and solid residues. Chemical and enzymatic depolymerization techniques were compared and a new chemical depolymerization method was developed. Gas chromatographic analysis with mass spectrometric detection (GC-MS) was used to assess the monomer compositions. Polymer investigations were conducted with solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (13C CP-MAS NMR), Fourier transform infrared spectroscopy (FTIR) and microscopic analysis. Furthermore, the development of suberin over one year of post-harvest storage was investigated and the cuticular layers from berries grown in the North and South of Finland were compared. The results show that the amounts of isolated cuticular layers and cutin monomers, as well as monomeric compositions vary greatly between the berries. The monomer composition of seeds was found to differ from the corresponding berry peel monomers. The berry cutin monomers were composed mostly of long-chain aliphatic ω-hydroxy acids, with various mid-chain functionalities (double-bonds, epoxy, hydroxy and keto groups). Substituted α,ω-diacids predominated over ω-hydroxy acids in potato suberin monomers and slight differences were found between the varieties. The newly-developed closed tube chemical method was found to be suitable for cutin and suberin analysis and preferred over the solvent-consuming and laborious reflux method. Enzymatic hydrolysis with cutinase was less effective than chemical methanolysis and showed specificity towards α,ω-diacid bonds. According to ₁₃C CP-MAS NMR and FTIR, the depolymerization residues contained significant amounts of aromatic structures, polysaccharides and possible cutan-type aliphatic moieties. Cultivation location seems to have effect on cuticular composition. The materials studied contained significant amounts of different types of biopolymers that could be utilized for several purposes with or without further processing. The importance of the so-called waste material from industrial processes of berries and potatoes as a source of either dietary fiber or specialty chemicals should be further investigated in detail. The evident impact of cuticular and suberin polymers, among other fiber components, on human health should be investigated in clinical trials. These by-product materials may be used as value-added fiber fractions in the food industry and as raw materials for specialty chemicals such as lubricants and emulsifiers, or as building blocks for novel polymers.

Competência de Juízo Moral entre Estudantes de Odontologia

Esta pesquisa objetivou avaliar a competência moral de estudantes de Odontologia no Estado do Ceará. O estudo foi do tipo observacional transversal descritivo. Aplicou-se o Moral Judgement Test (MJT) com os alunos regularmente matriculados no primeiro e último semestres dos cursos de Odontologia do Estado. Para a análise do ambiente de aprendizagem, realizou-se a coleta dos conteúdos das disciplinas e estágios de todas as IES envolvidas para consolidação das cargas horárias. Avaliou-se como variável dependente o aspecto cognitivo – competência de juízo moral calculada a partir do MJT e expressa pelo escore C. As variáveis independentes foram: (a) tipo de instituição; (b) tempo de aprendizagem; (c) gênero; (d) idade. Para análise da diferença estatística significante entre gênero, semestre e tipo de instituição, calculou-se a diferença de médias através do teste t.O teste de Anova foi utilizado para análise das diferenças entre grupos etários por semestre.Os resultados apontam que a média de competência de juízo moral (escore C)dos entrevistados foi de 18,3, não havendo diferença significativa entre os sexos. Analisando-se a média de escore C dos estudantes do primeiro e último semestre, observou-se uma tendência de perda de competência do primeiro (19,0) para o último semestre (17,6) e uma diferença significativa entre alunos de instituições públicas (21,0) e privadas (16,5). Observou-se também que as disciplinas com conteúdo de Ciências Humanas não ultrapassaram20% dos projetos pedagógicos dos cursos, condicionando os futuros cirurgiões-dentistas a desenvolver uma competência moral limitada.

Caution and necessity

In this paper I examine Crispin Wright's modal anti-realism as based on the availability of a certain attitude of Caution towards judgements of necessity. I think that Wright's account should be attractive in several ways for modal theorists with an anti-realist bend. However, the attitude of Caution to which it appeals has attracted some controversy. Wright himself has later come to doubt whether Caution is ultimately coherent. Here I first address Wright's worries concerning the coherence of Caution and show that they are unfounded. But then I argue that although the attitude of Caution is coherent, it cannot provide a suitable basis for a non-eliminativist account of necessity. I offer two different objections against Caution. (1) I argue that Wright's appeal to Caution, if successful, would show not only that modal judgement is non-objective but also that it is dispensable. Thus, I claim that appeal to Caution would seem to serve more as a threat against a non-eliminativist account of necessity, rather than as a potential adequate basis for it. However, (2) I argue that Wright's appeal to Caution is unsuccessful, for there is no genuine Caution: Caution is a mere verbal attitude.

Upconverting Phosphor Technology: Exceptional Photoluminescent Properties Light Up Homogeneous Bioanalytical Assays

The aim of the present study was to demonstrate the wide applicability of the novel photoluminescent labels called upconverting phosphors (UCPs) in proximity-based bioanalytical assays. The exceptional features of the lanthanide-doped inorganic UCP compounds stem from their capability for photon upconversion resulting in anti-Stokes photoluminescence at visible wavelengths under near-infrared (NIR) excitation. Major limitations related to conventional photoluminescent labels are avoided, rendering the UCPs a competitive next-generation label technology. First, the background luminescence is minimized due to total elimination of autofluorescence. Consequently, improvements in detectability are expected. Second, at the long wavelengths (>600 nm) used for exciting and detecting the UCPs, the transmittance of sample matrixes is significantly greater in comparison with shorter wavelengths. Colored samples are no longer an obstacle to the luminescence measurement, and more flexibility is allowed even in homogeneous assay concepts, where the sample matrix remains present during the entire analysis procedure, including label detection. To transform a UCP particle into a biocompatible label suitable for bioanalytical assays, it must be colloidal in an aqueous environment and covered with biomolecules capable of recognizing the analyte molecule. At the beginning of this study, only UCP bulk material was available, and it was necessary to process the material to submicrometer-sized particles prior to use. Later, the ground UCPs, with irregular shape, wide size-distribution and heterogeneous luminescence properties, were substituted by a smaller-sized spherical UCP material. The surface functionalization of the UCPs was realized by producing a thin hydrophilic coating. Polymer adsorption on the UCP surface is a simple way to introduce functional groups for bioconjugation purposes, but possible stability issues encouraged us to optimize an optional silica-encapsulation method which produces a coating that is not detached in storage or assay conditions. An extremely thin monolayer around the UCPs was pursued due to their intended use as short-distance energy donors, and much attention was paid to controlling the thickness of the coating. The performance of the UCP technology was evaluated in three different homogeneous resonance energy transfer-based bioanalytical assays: a competitive ligand binding assay, a hybridization assay for nucleic acid detection and an enzyme activity assay. To complete the list, a competitive immunoassay has been published previously. Our systematic investigation showed that a nonradiative energy transfer mechanism is indeed involved, when a UCP and an acceptor fluorophore are brought into close proximity in aqueous suspension. This process is the basis for the above-mentioned homogeneous assays, in which the distance between the fluorescent species depends on a specific biomolecular binding event. According to the studies, the submicrometer-sized UCP labels allow versatile proximity-based bioanalysis with low detection limits (a low-nanomolar concentration for biotin, 0.01 U for benzonase enzyme, 0.35 nM for target DNA sequence).

En gestaltning av individens erfarenhetsbaserade kunskap inom diabetesvården

The aim of this study is to form the experience-based knowledge of diabetics. The broader intent is to be able to transform this experience-based knowledge as an asset within caring. In this study, a theoretical contact for the empirical data is presented through phronesis, i.e. practical wisdom. Phronesis can be seen as the most suitable form of knowledge to be able to deepen the individual's understanding of experiencebased knowledge. For this research, hermeneutic phenomenology was chosen. Abductive reasoning was the method chosen to approach the data collected through repeated deep interviews with individuals with personal experience of diabetes and the use of insulin pumps. The abductive approach fascilitates a broader interpretation of the primary empirical results via a theory of philosophy of science, such as phronesis, the life-world and the negativity of the experience. The latent message of the empirical data is thereby also additionally highlighted. The synthesis reveals that experience-based knowledge arrives with time, it is personified and praxis-oriented, and before this time, the knowledge and security must be provided by the established care, by people close to the individual or by other external sources. The experience-based knowledge has strenghts and weaknesses. The knowledge is further categorized by the individual's ability to discern and make judgement. Additionally, the experience-based kowledge is a reflecting and action-based knowledge striving to improve the care provided. The experience-based knowledge held by the individual is potentially a great instrument towards improving general knowledge with possible practical applications within the diabetic care. Furthermost, in practical suggestions to fascilitate care. In generally applying knowledge gathered from the individual's experiental point of view, there are inherent risks. These risks could potentially be eliminated through the adoption of a concept where the established care could function as a quality guarantor. A concept taking into account the experiencebased knowledge as a source of information and knowledge in the care for diabetics. Co-created knowledge and understanding is a position found in both self-care and pump-treatment. It is also found through the optimal application of the experience-based knowledge of the individual as well as the knowledge found within the established care, in order to fascilitate well-being. This as expressed by the individual's phronesis-based knowledge.

Accidental and experimental salinomycin poisoning in rabbits

An outbreak of salinomycin poisoning in rabbits is described. At least 27 out of 2,000 rabbits reared on a farm died after the coccidiostatic drug sulfaquinoxaline was substituted by salinomycin in the feed. An average of 26.9ppm salinomycin was detected in the ration given to the rabbits. Clinical signs included anorexia, apathy and bradykinesia, which progressed to incoordination and recumbency. Gross lesions consisted of pale areas in the skeletal muscles. The histopathological findings showed severe necrotic degenerative myopathy in association with infiltration of neutrophils and macrophages. One rabbit exhibited similar alterations in the myocardium. Mineralization was observed in the affected skeletal muscles in some cases. In order to verify if the poisoning was due to salinomycin, 20 rabbits were divided into five groups and a ration containing the drug at doses of 10, 25, 50, 75 and 100ppm was given. The administration of doses higher than 50ppm resulted in manifestation of the clinical signs seen in the outbreak of poisoning. It was concluded, that probably an error related to the mixture of salinomycin in the feed was the cause of deaths in the spontaneous outbreak of poisoning on the rabbit farm.

Modulaarisen tuotteen mallivalikoiman ja tuoterakenteen keventäminen

Työn päätavoitteena on analysoida Konecranesin nosturiohjaamoperheitä ja tehdä analyysin pohjalta ehdotuksia liiketoimintayksiköiden käyttämän ohjaamovalikoiman ja modulaarisen tuoterakenteen keventämisestä. Ohjaamovalikoiman ja ohjaamojen tuoterakenteen keventämiselle on tarvetta koska laajan ohjaamovalikoiman ja monimutkaisen tuoterakenteen myötä tuotehallinta on vaikeutunut hankaloittaen myyntiprosessia ja lisäten samalla myös tuotteen tilaus-toimitusprosessin virhealttiutta ja kustannuksia. Suuren valikoiman ja monimutkaisen tuoterakenteen takia tuotekonfiguroinnissa tarvittavia teknisiä lausekkeita ei voida myöskään soveltaa kaikkiin ohjaamomalleihin ja ne ovatkin sen takia jääneet vajaakäyttöön Työn tuloksena ehdotetaan elinkaarensa päähän tulleiden ja/tai duplikaateiksi luokiteltavien mallien poistamista valikoimasta ja vain vähäistä myyntipotentiaalia omaavien tuotteiden siirtämistä erikoistuotteiden valikoimaan tarjottavaksi suunnittelua vaativina, projektiluonteisina tuotteina. Työn tuloksena ehdotetaan myös ohjaamoperheiden tuoterakenteen yhtenäistämistä ja tuotealustojen vari-oituvuuden vähentämisestä siirtämällä pienen myyntipotentiaalin omaavia alustoja projektituotteiksi.

Printed platforms for paper-based analytical applications

Paper-based analytical technologies enable quantitative and rapid analysis of analytes from various application areas including healthcare, environmental monitoring and food safety. Because paper is a planar, flexible and light weight substrate, the devices can be transported and disposed easily. Diagnostic devices are especially valuable in resourcelimited environments where diagnosis as well as monitoring of therapy can be made even without electricity by using e.g. colorimetric assays. On the other hand, platforms including printed electrodes can be coupled with hand-held readers. They enable electrochemical detection with improved reliability, sensitivity and selectivity compared with colorimetric assays. In this thesis, different roll-to-roll compatible printing technologies were utilized for the fabrication of low-cost paper-based sensor platforms. The platforms intended for colorimetric assays and microfluidics were fabricated by patterning the paper substrates with hydrophobic vinyl substituted polydimethylsiloxane (PDMS) -based ink. Depending on the barrier properties of the substrate, the ink either penetrates into the paper structure creating e.g. microfluidic channel structures or remains on the surface creating a 2D analog of a microplate. The printed PDMS can be cured by a roll-ro-roll compatible infrared (IR) sintering method. The performance of these platforms was studied by printing glucose oxidase-based ink on the PDMS-free reaction areas. The subsequent application of the glucose analyte changed the colour of the white reaction area to purple with the colour density and intensity depending on the concentration of the glucose solution. Printed electrochemical cell platforms were fabricated on paper substrates with appropriate barrier properties by inkjet-printing metal nanoparticle based inks and by IR sintering them into conducting electrodes. Printed PDMS arrays were used for directing the liquid analyte onto the predetermined spots on the electrodes. Various electrochemical measurements were carried out both with the bare electrodes and electrodes functionalized with e.g. self assembled monolayers. Electrochemical glucose sensor was selected as a proof-of-concept device to demonstrate the potential of the printed electronic platforms.

Savings Calculator for Centrifugal Pumps

Centrifugal pumps are one of the major energy consuming end-devices in developed coun-tries both in industrial and services sectors. According to recent studies, even 30 % of the energy used in pumping systems could be saved by more careful choosing of devices and system design. One of the most efficient and affordable ways to decrease the energy con-sumption of the pumping system is to substitute traditionally used flow control methods, like valve control, with modern variable speed drive (VSD) control. In this thesis, Microsoft Excel based program, Savings Calculator for Centrifugal Pumps (SCCP), is designed. SCCP calculates the achievable energy and financial savings when throttle control is substituted by VSD control in the pumping system. Compared to the sim-ilar existing programs, the goal is to make SCCP calculations more accurate and require less input information. Also some useful additional features are added to the designed program to make it more user friendly. The reliability of the calculations of designed program seem to vary depending on case. The results are corresponding accurately to the laboratory measurements, but there occurs high deviations in some cases, when the results are compared to the pump information specified by manufacturer. On the basis of verification in this thesis, SCCP seems to be at least as accurate as similar existing programs and it can be used as help in investment decision whether to have VSD or not.

One-winged Drosophila subobscura: a phenotype with an obscure genetic basis

A line of one-winged Drosophila subobscura was studied. The absent wing is substituted by a bulky structure with macro and microchaetes, showing a thoracic appearance. Genetic crosses showed that there is no way to select for the trait by simple crossing. The number of one-winged flies in the various generations was always low. In one case a wingless fly was also obtained. The trait presents an unknown genetic pattern.

Thyroid function in post-weaning rats whose dams were fed a low-protein diet during suckling

This study was designed to evaluate the thyroid and pituitary hormone levels in post-weaning rats whose dams were fed a low-protein diet during suckling (21 days). The dams and pups were divided into 2 groups: a control group fed a diet containing 22% protein that supplies the necessary amount of protein for the rat and is the usual content of protein in most commercial rat chow, and a diet group fed a low-protein (8%) diet in which the protein was substituted by an isocaloric amount of starch. After weaning all dams and pups received the 22% protein diet. Two hours before sacrifice of pups aged 21, 30 and 60 days, a tracer dose (0.6 µCi) of 125I was injected (ip) into each animal. Blood and thyroid glands of pups were collected for the determination of serum T4, T3 and TSH and radioiodine uptake. Low protein diet caused a slight decrease in radioiodine uptake at 21 days, and a significant decrease in T3 levels (128 ± 14 vs 74 ± 9 ng/dl, P<0.05), while T4 levels did not change and TSH was increased slightly. At 30 days, T3 and TSH did not change while there was a significant increase in both T4 levels (4.8 ± 0.3 vs 6.1 ± 0.2 µg/dl, P<0.05) and in radioiodine uptake levels (0.34 ± 0.02 vs 0.50 ± 0.03%/mg thyroid, P<0.05). At 60 days serum T3, T4 and TSH levels were normal, but radioiodine uptake was still significantly increased (0.33 ± 0.02 vs 0.41 ± 0.03%/mg thyroid, P<0.05). Thus, it seems that protein malnutrition of the dams during suckling causes hypothyroidism in the pups at 21 days that has a compensatory mechanism increasing thyroid function after refeeding with a 22% protein diet. The radioiodine uptake still remained altered at 60 days, when all the hormonal serum levels returned to the normal values, suggesting a permanent change in the thyroid function

The regulation of apoptotic cell death

Apoptosis is a fundamental biological phenomenon in which the death of a cell is genetically and biochemically regulated. Different molecules are involved in the regulation of the apoptotic process. Death receptors, coupled to distinct members of the caspases as well as other adapter molecules, are involved in the initiation of the stress signals (The Indictment). Members of the Bcl-2 family control at the mitochondrial level the decision between life and death (The Judgement). The effector caspases are responsible for all morphological and biochemical changes related to apoptosis including the "eat-me" signals perceived by phagocytes and neighboring cells (The Execution). Finally, apoptosis would have little biological significance without the recognition and removal of the dying cells (The Burial).

New families of highly efficient, halogen-free flame retardants for polypropylene (PP)

The driving forces for current research of flame retardants are increased fire safety in combination with flame retardant formulations that fulfill the criteria of sustainable production and products. In recent years, important questions about the environmental safety of antimony, and in particular, brominated flame retardants have been raised. As a consequence of this, the current doctoral thesis work describes efforts to develop new halogen-free flame retardants that are based on various radical generators and phosphorous compounds. The investigation was first focused on compounds that are capable of generating alkyl radicals in order to study their role on flame retardancy of polypropylene. The family of azoalkanes was selected as the cleanest and most convenient source of free alkyl radicals. Therefore, a number of symmetrical and unsymmetrical azoalkanes of the general formula R-N=N-R’ were prepared. The experimental results show that in the series of different sized azocycloalkanes the flame retardant efficacy decreased in the following order: R = R´= cyclohexyl > cyclopentyl > cyclobutyl > cyclooctanyl > cyclododecanyl. However, in the series of aliphatic azoalkanes compounds, the efficacy decreased as followed: R = R´= n-alkyl > tert-butyl > tert-octyl. The most striking difference in flame retardant efficacy was observed in thick polypropylene plaques of 1 mm, e.g. azocyclohexane (AZO) had a much better flame retardant performance than did the commercial reference FR (Flamestab® NOR116) in thick PP sections. In addition, some of the prepared azoalkane flame retardants e.g. 4’4- bis(cyclohexylazocyclohexyl) methane (BISAZO) exhibited non-burning dripping behavior. Extrusion coating experiments of flame retarded low density polyethylene (LDPE) onto a standard machine finished Kraft paper were carried out in order to investigate the potential of azoalkanes in multilayer facings. The results show that azocyclohexane (AZO) and 4’4-bis (cyclohexylazocyclohexyl) methane (BISAZO) can significantly improve the flame retardant properties of low density polyethylene coated paper already at 0.5 wt.% loadings, provided that the maximum extrusion temperature of 260 oC is not exceeded and coating weight is kept low at 13 g/m2. In addition, various triazene-based flame retardants (RN1=N2-N3R’R’’) were prepared. For example, polypropylene samples containing a very low concentration of only 0.5 wt.% of bis- 4’4’-(3’3’-dimethyltriazene) diphenyl ether and other triazenes passed the DIN 4102-1 test with B2 classification. It is noteworthy that no burning dripping could be detected and the average burning times were very short with exceptionally low weight losses. Therefore, triazene compounds constitute a new and interesting family of radical generators for flame retarding of polymeric materials. The high flame retardant potential of triazenes can be attributed to their ability to generate various types of radicals during their thermal decomposition. According to thermogravimetric analysis/Fourier transform infrared spectroscopy/MS analysis, triazene units are homolytically cleaved into various aminyl, resonance-stabilized aryl radicals, and different CH fragments with simultaneous evolution of elemental nitrogen. Furthermore, the potential of thirteen aliphatic, aromatic, thiuram and heterocyclic substituted organic disulfide derivatives of the general formula R-S-S-R’ as a new group of halogen-free flame retardants for polypropylene films have been investigated. According to the DIN 4102- 1 standard ignitibility test, for the first time it has been demonstrated that many of the disulfides alone can effectively provide flame retardancy and self-extinguishing properties to polypropylene films at already very low concentrations of 0.5 wt.%. For the disulfide family, the highest FR activity was recorded for 5’5’-dithiobis (2-nitrobenzoic acid). Very low values for burning length (53 mm) and burning time (10 s) reflect significantly increased fire retardant performance of this disulfide compared to other compounds in this series as well as to Flamestab® NOR116. Finally, two new, phosphorus-based flame retardants were synthesized: P’P-diphenyl phosphinic hydrazide (PAH) and melamine phenyl phosphonate (MPhP). The DIN 4102-1 test and the more stringent UL94 vertical burning test (UL94 V) were used to assess the formulations ability to extinguish a flame once ignited. A very strong synergistic effect with azoalkanes was found, i.e. in combination with these radical generators even UL94 V0 rate could be obtained.