Ion selective electrodes for determination of low and ultra low concentrations of lead (II) in natural waters

Att övervaka förekomsten av giftiga komponenter i naturliga vattendrag är nödvändigt för människans välmående. Eftersom halten av föroreningar i naturens ekosystem bör hållas möjligast låg, pågår en ständig jakt efter kemiska analysmetoder med allt lägre detektionsgränser. I dagens läge görs miljöanalyser med dyr och sofistikerad instrumentering som kräver mycket underhåll. Jonselektiva elektroder har flera goda egenskaper som t.ex. bärbarhet, låg energiförbrukning, och dessutom är de relativt kostnadseffektiva. Att använda jonselektiva elektroder vid miljöanalyser är möjligt om deras känslighetsområde kan utvidgas genom att sänka deras detektionsgränser. För att sänka detektionsgränsen för Pb(II)-selektiva elektroder undersöktes olika typer av jonselektiva membran som baserades på polyakrylat-kopolymerer, PVC och PbS/Ag2S. Fast-fas elektroder med membran av PbS/Ag2S är i allmänhet enklare och mer robusta än konventionella elektroder vid spårämnesanalys av joniska föroreningar. Fast-fas elektrodernas detektionsgräns sänktes i detta arbete med en nyutvecklad galvanostatisk polariseringsmetod och de kunde sedan framgångsrikt användas för kvantitativa bestämningar av bly(II)-halter i miljöprov som hade samlats in i den finska skärgården nära tidigare industriområden. Analysresultaten som erhölls med jonselektiva elektroder bekräftades med andra analytiska metoder. Att sänka detektionsgränsen m.hj.a. den nyutvecklade polariseringsmetoden möjliggör bestämning av låga och ultra-låga blyhalter som inte kunde nås med klassisk potentiometri. Den verkliga fördelen med att använda dessa blyselektiva elektroder är möjligheten att utföra mätningar i obehandlade miljöprov trots närvaron av fasta partiklar vilket inte är möjligt att göra med andra analysmetoder. Jag väntar mig att den nyutvecklade polariseringsmetoden kommer att sätta en trend i spårämnesanalys med jonselektiva elektroder.

Modeling and Control of the Power Conversion Unit in a Solid Oxide Fuel Cell Environment

In this doctoral thesis, a power conversion unit for a 10 kWsolid oxide fuel cell is modeled, and a suitable control system is designed. The need for research was identified based on an observation that there was no information available about the characteristics of the solid oxide fuel cell from the perspective of power electronics and the control system, and suitable control methods had not previously been studied in the literature. In addition, because of the digital implementation of the control system, the inherent characteristics of the digital system had to be taken into account in the characteristics of the solid oxide fuel cell (SOFC). The characteristics of the solid oxide fuel cell as well the methods for the modeling and control of the DC/DC converter and the grid converter are studied by a literature survey. Based on the survey, the characteristics of the SOFC as an electrical power source are identified, and a solution to the interfacing of the SOFC in distributed generation is proposed. A mathematical model of the power conversion unit is provided, and the control design for the DC/DC converter and the grid converter is made based on the proposed interfacing solution. The limit cycling phenomenon is identified as a source of low-frequency current ripple, which is found to be insignificant when connected to a grid-tied converter. A method to mitigate a second harmonic originating from the grid interface is proposed, and practical considerations of the operation with the solid oxide fuel cell plant are presented. At the theoretical level, the thesis discusses and summarizes the methods to successfully derive a model for a DC/DC converter, a grid converter, and a power conversion unit. The results of this doctoral thesis can also be used in other applications, and the models and methods can be adopted to similar applications such as photovoltaic systems. When comparing the results with the objectives of the doctoral thesis, we may conclude that the objectives set for the work are met. In this doctoral thesis, theoretical and practical guidelines are presented for the successful control design to connect a SOFC-based distributed generation plant to the utility grid.

Histopathological and histomicrobiological study of root canal therapy medication, comparison of calcium hydroxide versus gutta-percha with zinc oxide/eugenol in the teeth of dogs

The presence of microorganisms in dental structures with experimentally induced necrosis was evaluated. The materials were tested to evaluate their antimicrobial activity and tissue repair efficacy. Four dogs were used in this experiment, with a total of 64 roots of premolar teeth, divided into three groups. The root canals of Group I were filled with gutta-percha and zinc oxide/eugenol cement; Group II were filled with calcium hydroxide, and Group III were not filled. All animals were clinically and radiographically examined 15 days after surgery andthen again every subsequent 15 days until 120 days, when the teeth were extracted en bloc.Histopathological analysis showed inflammatory infiltration, cement and bone resorption andnecrotic tissue in the apical delta in different proportions. Histomicrobiological analysis showedthe presence of microorganisms inside the teeth structures, with different concentrationsaccording to the treatment used. There was statistical significance between the groups(p>0.05). Gutta-percha with zinc oxide/eugenol demonstrated good antimicrobial activity;calcium hydroxide was not efficient. The conclusion of this study is that gutta-percha withzinc oxide/eugenol is the better protocol for filling root canals in dogs.

Evidence of mixed persistent infections in calves born to cows challenged with a pool of bovine viral diarrhea virus isolates

Pregnant cows infected with noncytopathic (NCP) isolates of bovine viral diarrhea virus (BVDV) between days 40 and 120 days of gestation frequently deliver immunotolerant, persistently infected (PI) calves. We herein report the characterization of PI calves produced experimentally through inoculation of pregnant cows with a pool of Brazilian BVDV-1 (n=2) and BVDV-2 isolates (n=2) between days 60 and 90 of gestation. Two calves were born virus positive, lacked BVDV antibodies, but died 7 and 15 days after birth, respectively. Six other calves were born healthy, seronegative to BVDV, harbored and shed virus in secretions for up to 210 days. Analysis of the antigenic profile of viruses infecting these calves at birth and 30 days later with a panel of monoclonal antibodies indicated two patterns of infection. Whereas three calves apparently harbored only one isolate (either a BVDV-1 or BVDV-2), co-infection by two antigenically distinct challenge viruses was demonstrated in three PI calves. Moreover, testing the viruses obtained from the blood of PI calves by an RT-PCR able to differentiate between BVDV-1 and BVDV-2 confirmed the presence/persistence of two co-infecting viruses of different genotypes (BVDV-1 and BVDV-2) in these animals. These findings indicate that persistent infection of fetuses/calves - a well characterized consequence of fetal infection by BVDV - may be established concomitantly by more than one isolate, upon experimental inoculation. In this sense, mixed persistent infections with antigenically distinct isolates may help in understanding the immunological and molecular basis of BVDV immunotolerance and persistence.

Carbon Nanotubes as Material for Supercapacitor Electrodes

Electrochemical double-layer supercapacitors have an intermediate position between rechargeable batteries, which can store high amounts of energy, and dielectric capacitors, which have high output power. Supercapacitors are widely suggested to be used in automobiles (recuperation during braking, facilitate engine starting, electric stabilization of the system), industry (forklifts, elevators), hybrid off-road machinery and also in consumer electronics. Supercapacitor electrodes require highly porous material. Typically, activated carbon is used. Specific surface area of activated carbon is approximately 1000 m2 per gram. Carbon nanotubes represent one of prospective materials. According to numerous studies this material allows to improve the properties of supercapacitors. The task of this Master‘s Thesis was to test multiwalled carbon nanotubes and become confident with the testing methods.

Kelvin Probe Force Microscopy (KPFM) characterization of lanthanum lutetium oxide high-k dielectric thin films

Lanthanum lutetium oxide (LaLuO3) thin films were investigated considering their perspective application for industrial microelectronics. Scanning probe microscopy (SPM) techniques permitted to visualize the surface topography and study the electric properties. This work compared both the material properties (charge behavior for samples of 6 nm and 25 nm width) and the applied SPM modes. Particularly, Kelvin probe force microscopy (KPFM) was applied to characterize local potential difference with high lateral resolution. Measurements showed the difference in morphology, chargeability and charge dissipation time for both samples. The polarity effect was detected for this material for the first time. Lateral spreading of the charged spots indicate the diffusive mechanism to be predominant in charge dissipation. This allowed to estimate the diffusion coefficient and mobility. Using simple electrostatic model it was found that charge is partly leaking into the interface oxide layer.

Diarrhea outbreaks in suckling piglets due to rotavirus group C single and mixed (rotavirus groups A and B) infections

Porcine group A rotavirus (PoRVA) is a major cause of neonatal diarrhea in suckling and recently weaned piglets worldwide. The involvement of non-group A rotavirus in cases of neonatal diarrhea in piglets are sporadic. In Brazil there are no reports of the porcine rotavirus group C (PoRVC) as etiologic agent of the diarrhea outbreaks in piglets. The aim of this study was to describe the identification of rotavirus group C in single and in mixed infection with rotavirus groups A and B in three neonatal diarrhea outbreaks in suckling (<21-day-old) piglets, with 70% to 80% and 20% to 25% of morbidity and lethality rates, respectively, in three pig herds located in the state of Santa Catarina, Brazil. The diagnosis of PoRV in the diarrheic fecal samples was performed using polyacrylamide gel electrophoresis (PAGE) to identify the presence of porcine rotavirus groups A, B (PoRVB), and C, and by RT-PCR (PoRVA and PoRVC) and semi-nested (SN)-PCR (PoRVB) to partially amplify the VP4 (VP8*)-VP7, NSP2, and VP6 genes of PoRVA, PoRVB, and PoRVC, respectively. One RT-PCR (PoRVA and PoRVC) and SN-PCR (PoRVB) product of each group of rotavirus of each diarrhea outbreak was submitted to nucleotide (nt) sequence analysis. Based on the PAGE technique, 4 (25%) and 1 (6.25%) of the 16 diarrheic fecal samples evaluated in the first outbreak presented PoRVA and PoRVC electropherotype, respectively, and 11 (68.75%) were negative. In the second outbreak, 3 (42.85%) of the 7 fecal samples evaluated presented PoRVA electropherotype, and in 3 (42.85%) and in 1 (14.3%) fecal samples were detected inconclusive and negative results, respectively. Three (30%) of the 10 fecal samples of the third outbreak presented PoRVC electropherotype; 5 (50%) and 2 (20%) samples showed negative and inconclusive results, respectively. Based on the RT-PCR and SN-PCR assays in the first neonatal diarrhea outbreak, PoRVC was detected in 13 (81.2%) of the 16 diarrheic fecal samples evaluated. PoRVC single infection was identified in 4 (25%) of these samples and mixed infections with PoRVA and PoRVB in 9 (56.2%) fecal samples. All of the seven diarrheic fecal samples evaluated from the second neonatal diarrhea outbreak were positive for PoRVC, whereas its mixed infection with other PoRV groups was detected in 4 (57.2%) samples. In the third outbreak, PoRVC in single infection was detected in all of the 10 diarrheic fecal samples analyzed. In the nt sequence analysis, the PoRVA strains of the first and second outbreaks demonstrated higher nt identity with G4P[6] and G9P[23] genotypes, respectively. The PoRVB strains (first and second outbreaks) and the PoRVC strains (first, second, and third outbreaks) showed higher nt identity and clustered in the phylogenetic tree with PoRVB and PoRVC strains that belong to the N4 and I1 genotypes, respectively. This is the first description in Brazil of the involvement of PoRVC in the etiology of diarrhea outbreaks in suckling piglets. The results of this study demonstrated that PoRVC, in both single and mixed infections, is an important enteropathogen involved in neonatal diarrhea outbreaks in piglets and that the use of more sensitive diagnostic techniques allows the identification of mixed infections involving two or even three groups of PoRV, which may be more common than previously reported.

Numerical study on mixed convection in a horizontal flow past a square porous cavity using UNIFAES scheme

Mixed convection on the flow past a heated length and past a porous cavity located in a horizontal wall bounding a saturated porous medium is numerically simulated. The cavity is heated from below. The steady-state regime is studied for several intensities of the buoyancy effects due to temperature variations. The influences of Péclet and Rayleigh numbers on the flow pattern and the temperature distributions are examined. Local and global Nusselt numbers are reported for the heated surface. The convective-diffusive fluxes at the volume boundaries are represented using the UNIFAES, Unified Finite Approach Exponential-type Scheme, with the Power-Law approximation to reduce the computing time. The conditions established by Rivas for the quadratic order of accuracy of the central differencing to be maintained in irregular grids are shown to be extensible to other quadratic schemes, including UNIFAES, so that accuracy estimates could be obtained.

Young Registered Nurses’ Intent to Leave the Profession in Finland - A Mixed-Method Study

The purpose of this study was to examine and expand understanding concerning young Finnish registered nurses (RN) with an intention to leave the profession and the related variables, specifically when that intention has emerged before the age of 30. The overall goal of the study was to develop a conceptual model in relation to young RNs’ intention to leave the profession. Suggestions for policymakers, nurse leaders and nurse managers are presented for how to retain more young RNs in the nursing workforce. Suggestions for future nursing research are also provided. Phase I consists of two sequential integrative literature reviews of 75 empirical articles concerning nurses’ intention to leave the profession. In phase II, data had been collected as part of the Nurses’ Early Exit (NEXT) study, using the BQ-12 structured postal questionnaire. A total of 147 young RNs participated in the study. The data were analysed with statistical methods. In phase III, firstly, an in-depth interpretive case study was conducted in order to understand how young RNs explain and make sense of their intention to leave the profession. The data in this study consisted of longitudinal career stories by three young RNs. The data was analysed by using narrative holistic-content and thematic methods. Secondly, a total of 15 young RNs were interviewed in order to explore in-depth their experiences concerning organizational turnover and their intent to leave the profession. The data was analysed using conventional content analysis. Based on earlier research, empirical research on the young RNs intention to leave the profession is scarce. Nurses’ intention to leave the profession has mainly been studied with quantitative descriptive studies, conducted with survey questionnaires. Furthermore, the quality of previous studies varies considerably. Moreover, nurses’ intention to leave the profession seems to be driven by a number of variables. According to the survey study, 26% of young RNs had often considered giving up nursing completely and starting a different kind of job during the course of the previous year. Many different variables were associated with an intention to leave the profession (e.g. personal burnout, job dissatisfaction). According to the in-depth inquiries, poor nursing practice environments and a nursing career as a ‘second-best’ or serendipitous career choice were themes associated with young RNs’ intention to leave the profession. In summary, young RNs intention to leave the profession is a complex phenomenon with multiple associated variables. These findings suggest that policymakers, nurse leaders and nurse managers should enable improvements in nursing practice environments in order to retain more young RNs. These improvements can include, for example, adequate staffing levels, balanced nursing workloads, measures to reduce work-related stress as well as possibilities for advancement and development. Young RNs’ requirements to provide high-quality and ethical nursing care must be recognized in society and health-care organizations. Moreover, sufficient mentoring and orientation programmes should be provided for all graduate RNs. Future research is needed into whether the motive for choosing a nursing career affects the length of the tenure in the profession. Both quantitative and in-depth research is needed for the comprehensive development of nursing-turnover research.

Modeling light interception and distribution in mixed canopy of common cocklebur (Xanthium stramarium) in competition with corn

The aim of this study was to model light interception and distribution in the mixed canopy of Common cocklebur (Xanthium stramarium) with corn. An experiment was conducted in factorial arrangement on the basis of randomized complete blocks design with three replications in Gonabad in 2006-2007 and 2007-2008 seasons. The factors used in this experiment include corn density of 7.5, 8.5 and 9.5 plants per meter of row and density of Common cocklebur of zero, 2, 4, 6 and 8 plants per meter of row. INTERCOM model was used through replacing parabolic function with triangular function of leaf area density. Vertical distribution of the species' leaf area showed that corn has concentrated the most leaf area in layer of 80 to 100 cm while Common cocklebur has concentrated in 35-50 cm of canopy height. Model sensitivity analysis showed that leaf area index, species' height, height where maximum leaf area is seen (hm), and extinction coefficient have influence on light interception rate of any species. In both species, the distribution density of leaf area at the canopy length fit a triangular function, and the height in which maximum leaf area was observed was changed by change in density. There was a correlation between percentage of the radiation absorbed by the weed and percentage of corn seed yield loss (r² = 0.89). Ideal type of corn was determined until the stage of tasseling in competition with weed. This determination indicates that the corn needs more height and leaf area, as well as less extinction coefficient to successfully fight against the weed.

Morphological and physiological alterations induced by lactofen in soybean leaves are reduced with nitric oxide

Lactofen is a diphenylether herbicide recommended to control broad-leaved weeds in soybean (Glycine max) fields and its mechanism of action is the inhibition of protoporphyrinogen-IX oxidase (Protox), which acts in the chlorophyll biosynthesis. This inhibition results in an accumulation of protoporphyrin-IX, which leads to the production of reactive oxygen species (ROS) that cause oxidative stress. Consequently, spots, wrinkling and leaf burn may occur, resulting in a transitory crop growth interruption. However, nitric oxide (NO) acts as an antioxidant in direct ROS scavenging. Thus, the aim of this work was to verify, through phytometric and biochemical evaluations, the protective effect of NO in soybean plants treated with the herbicide lactofen. Soybean plants were pre-treated with different levels of sodium nitroprusside (SNP), a NO-donor substance, and then sprayed with 168 g a.i. ha-1 lactofen. Pre-treatment with SNP was beneficial because NO decreased the injury symptoms caused by lactofen in young leaflets and kept low the soluble sugar levels. Nevertheless, NO caused slower plant growth, which indicates that further studies are needed in order to elucidate the action mechanisms of NO in signaling the stress caused by lactofen in soybean crop.

Application of cerium oxide thin films grown by atomic layer deposition for soot removal

The objective of the thesis is to study cerium oxide thin films grown by the atomic layer deposition (ALD) for soot removal. Cerium oxide is one of the most important heterogeneous catalysts and can be used in particulate filters and sensors in a diesel exhaust pipe. Its redox/oxidation properties are a key factor in soot oxidation. Thus, the cerium oxide coating can help to keep particulate filters and sensors clean permanently. The literature part of the thesis focuses on the soot removal, introducing the origin and structure of soot, reviewing emissions standards for diesel particulate matter, and presenting methods and catalysts for soot removal. In the experimental part the optimal ALD conditions for cerium oxide were found, the structural properties of cerium oxide thin films were analyzed, and the catalytic activity of the cerium oxide for soot oxidation was investigated. Studying ALD growth conditions of cerium oxide films and determining their critical thickness range are important to maximize the catalytic performance operating at comparatively low temperature. It was found that the cerium oxide film deposited at 300 °C with 2000 ALD cycles had the highest catalytic activity. Although the activity was still moderate and did not decrease the soot oxidation temperature enough for a real-life application. The cerium oxide thin film deposited at 300 °C has a different crystal structure, surface morphology and elemental composition with a higher Ce3+ concentration compared to the films deposited at lower temperatures. The different properties of the cerium oxide thin film deposited at 300 °C increase the catalytic activity most likely due to higher surface area and addition of the oxygen vacancies.

Mixed reproduction systems in Opuntia monacantha (Cactaceae) in Southern Brazil

The Cactaceae have morphological and physiological adaptations associated with their life histories that are reflected in different modes of reproduction and multiplication. The reproductive phenology, preferential reproductive mode, and the sexual and asexual multiplication of Opuntia monacantha were investigated between 2003 and 2006 in two restinga (sandy coastal) environment in Southern Brazil to determine the adaptive values of its reproduction modes. Flowering was annual and occurred continuous for approximately 100 days between the months of September and January, with a few flowers opening per day per individual (but many in the whole population). Facultative xenogamy was identified as the preferential sexual system, with the highest levels of fruit and seed formation following natural pollination. The seeds are recalcitrant and have high germinative capacities under laboratory conditions. Seedling recruitment and establishment in the field was extremely reduced. The skins of the fruits and the cladodes have high capacities for regeneration and clonal multiplication because of their areolas.

A simple model for the estimation of congenital malformation frequency in racially mixed populations

A simple model is proposed, using the method of maximum likelihood to estimate malformation frequencies in racial groups based on data obtained from hospital services. This model uses the proportions of racial admixture, and the observed malformation frequency. It was applied to two defects: postaxial polydactyly and cleft lip, the frequencies of which are recognizedly heterogeneous among racial groups. The frequencies estimated in each racial group were those expected for these malformations, which proves the applicability of the method.