Ligandless cloud point extraction of trace amounts of palladium and rhodium in road dust samples using Span 80 prior to their determination by flame atomic absorption spectrometry

In this study, a procedure is developed for cloud point extraction of Pd(II) and Rh(III) ions in aqueous solution using Span 80 (non-ionic surfactant) prior to their determination by flame atomic absorption spectroscopy. This method is based on the extraction of Pd(II) and Rh(III) ions at a pH of 10 using Span 80 with no chelating agent. We investigated the effect of various parameters on the recovery of the analyte ions, including pH, equilibration temperature and time, concentration of Span 80, and ionic strength. Under the best experimental conditions, the limits of detection based on 3Sb for Pd(II) and Rh(III) ions were 1.3 and 1.2 ng mL-1, respectively. Seven replicate determinations of a mixture of 0.5 µg mL-1 palladium and rhodium ions gave a mean absorbance of 0.058 and 0.053 with relative standard deviations of 1.8 and 1.6%, respectively. The developed method was successfully applied to the extraction and determination of the palladium and rhodium ions in road dust and standard samples and satisfactory results were obtained.

Final chlorine dioxide stage at near-neutral pH for bleaching eucalypt pulp

It is well known that pH is an important parameter for controlling the eucalyptus pulp bleaching when using the final chlorine dioxide stage, since it affects the effectiveness of the process. Recommendations found in the literature for operating are in the 3.5 to 4.0 range. However, in this paper it was shown that final chlorine dioxide has better performance, with significant brightness gain while also preserving pulp quality, when it is operated at near neutral pH. This result can be explained by the generation of sodium bicarbonate in situ upon adding carbon dioxide at this stage.

PREDICTING THE BOILING POINT OF PCDD/Fs BY THE QSPR METHOD BASED ON THE MOLECULAR DISTANCE-EDGE VECTOR INDEX

The quantitative structure property relationship (QSPR) for the boiling point (Tb) of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was investigated. The molecular distance-edge vector (MDEV) index was used as the structural descriptor. The quantitative relationship between the MDEV index and Tb was modeled by using multivariate linear regression (MLR) and artificial neural network (ANN), respectively. Leave-one-out cross validation and external validation were carried out to assess the prediction performance of the models developed. For the MLR method, the prediction root mean square relative error (RMSRE) of leave-one-out cross validation and external validation was 1.77 and 1.23, respectively. For the ANN method, the prediction RMSRE of leave-one-out cross validation and external validation was 1.65 and 1.16, respectively. A quantitative relationship between the MDEV index and Tb of PCDD/Fs was demonstrated. Both MLR and ANN are practicable for modeling this relationship. The MLR model and ANN model developed can be used to predict the Tb of PCDD/Fs. Thus, the Tb of each PCDD/F was predicted by the developed models.

Earnings Management Shareholders point of view

This paper studies the relationship of earnings management and investors. Analysis of incentives reveals that most of them are opportunistic in nature. Unfortunately the investor would need insider information to distinguish between different forms of earnings management. Investors in some countries seem to devalue earnings when government body has signaled that earnings management might be involved, unfortunately without a clear signal the behavior seems reverse among non-institutional investors.

Critical-point yield model to estimate yield damage caused by Cercospora zea-maydis in corn

A model to estimate damage caused by gray leaf spot of corn (Cercospora zea-maydis) was developed from experimental field data gathered during the summer seasons of 2000/01 and during the second crop season [January-seedtime] of 2001, in the southwest of Goiás state. Three corn hybrids were grown over two seasons and on two sites, resulting in 12 experimental plots. A disease intensity gradient (lesions per leaf) was generated through application, three times over the season, of five different doses of the fungicide propiconazol. From tasseling onward, disease intensity on the ear leaf (El), and El - 1, El - 2, El + 1, and El + 2, was evaluated weekly. A manual harvest at the physiological ripening stage was followed by grain drying and cleaning. Finally, grain yield in kg.ha-1 was estimated. Regression analysis, performed between grain yield and all combinations of the number of lesions on each leaf type, generated thirty linear equations representing the damage function. To estimate losses caused by different disease intensities at different corn growth stages, these models should first be validated. Damage coefficients may be used in determining the economic damage threshold.

Multilevel converter modulation: implementation and analysis

Multilevel converters provide an attractive solution to bring the benefits of speed-controlled rotational movement to high-power applications. Therefore, multilevel inverters have attracted wide interest in both the academic community and in the industry for the past two decades. In this doctoral thesis, modulation methods suitable especially for series connected H-bridge multilevel inverters are discussed. A concept of duty cycle modulation is presented and its modification is proposed. These methods are compared with other well-known modulation schemes, such as space-vector pulse width modulation and carrier-based modulation schemes. The advantage of the modified duty-cycle modulation is its algorithmic simplicity. A similar mathematical formulation for the original duty cycle modulation is proposed. The modified duty cycle modulation is shown to produce well-formed phase-to-neutral voltages that have lower total harmonic distortion than the space-vector pulse width modulation and the duty cycle modulation. The space-vector-based solution and the duty cycle modulation, on the other hand, result in a better-quality line-to-line voltage and current waveform. The voltage of the DC links in the modules of the series-connected H-bridge inverter are shown to fluctuate while they are under load. The fluctuation causes inaccuracies in the voltage production, which may result in a failure of the flux estimator in the controller. An extension for upper-level modulation schemes, which changes the switching instants of the inverter so that the output voltage meets the reference voltage accurately regardless of the DC link voltages, is proposed. The method is shown to reduce the error to a very low level when a sufficient switching frequency is used. An appropriate way to organize the switching instants of the multilevel inverter is to make only one-level steps at a time. This causes restrictions on the dynamical features of the modulation schemes. The produced voltage vector cannot be rotated several tens of degrees in a single switching period without violating the above-mentioned one-level-step rule. The dynamical capabilities of multilevel inverters are analyzed in this doctoral thesis, and it is shown that the multilevel inverters are capable of operating even in dynamically demanding metal industry applications. In addition to the discussion on modulation schemes, an overvoltage in multilevel converter drives caused by cable reflection is addressed. The voltage reflection phenomenon in drives with long feeder cables causes premature insulation deterioration and also affects the commonmode voltage, which is one of the main reasons for bearing currents. Bearing currents, on the other hand, cause fluting in the bearings, which results in premature bearing failure. The reflection phenomenon is traditionally prevented by filtering, but in this thesis, a modulationbased filterless method to mitigate the overvoltage in multilevel drives is proposed. Moreover, the mitigation method can be implemented as an extension for upper-level modulation schemes. The method exploits the oscillations caused by two consecutive voltage edges so that the sum of the oscillations results in a mitigated peak of the overvoltage. The applicability of the method is verified by simulations together with experiments with a full-scale prototype.

Vähempiarvoisen kalan käsittelyketjut ja hiilijalanjälki

The condition of Baltic Sea has weakened considerably because of eutrophication which has caused massive increase of devalued fish. The condition of Baltic Sea can be helped by fishing these fish. This study handles three different ways to approach those fish utilizations and counts carbon footprint for those three chains. Environmental point of views are also examined. There are three different fish processing chains. Every processing chain begins with fishing the fish in Baltic Sea. After that the fishes are prepared by crushing and some formic acid is added to ensure preservation. In the first processing chain the fishes are processed as biodiesel. The waste from the biodiesel process is taken to the anaerobic digestion and the forming methane is used as energy. In the second chain the fishes are taken straight to the anaerobic digestion after preparing. In the third chain, the fish will be first prepared and then taken to fur farms as forage. The carbon footprint has been calculated for 1000 kg fish. The carbon footprint in the first chain is 164-178 kg CO2e, in the second chain 313 – 333 kg CO2e and in the third chain 363 kg CO2e. In the processing chains the bioenergy is produced from the biodiesel, anaerobic digestion and from the glycerol, which is by-product of the biodiesel. The energy produced from the biodiesel is so-called emission neutral, which is not taken into account when calculating emissions. The energy is used to compensate the emissions caused by fossil fuels. The PAS 2050 was used to calculate the carbon footprint. Only carbon dioxide and methane were used when calculating the carbon footprint.

Mobile system for pump working point estimation

In the current economy situation companies try to reduce their expenses. One of the solutions is to improve the energy efficiency of the processes. It is known that the energy consumption of pumping applications range from 20 up to 50% of the energy usage in the certain industrial plants operations. Some studies have shown that 30% to 50% of energy consumed by pump systems could be saved by changing the pump or the flow control method. The aim of this thesis is to create a mobile measurement system that can calculate a working point position of a pump drive. This information can be used to determine the efficiency of the pump drive operation and to develop a solution to bring pump’s efficiency to a maximum possible value. This can allow a great reduction in the pump drive’s life cycle cost. In the first part of the thesis, a brief introduction in the details of pump drive operation is given. Methods that can be used in the project are presented. Later, the review of available platforms for the project implementation is given. In the second part of the thesis, components of the project are presented. Detailed description for each created component is given. Finally, results of laboratory tests are presented. Acquired results are compared and analyzed. In addition, the operation of created system is analyzed and suggestions for the future development are given.

Yritysverojärjestelmän hyvyys, merkitys ja verosuunnittelun painopistealueet yrittäjien sekä asiantuntijoiden näkökulmista

Tämän tutkielman tavoitteena on kuvata hyvän verojärjestelmän ominaisuuksien toteutumista nykyisessä pienten osakeyhtiöiden yritysverojärjestelmässä. Lisäksi tavoitteena on selvittää yritysverotuksen painoarvo yritystoimintaa säätelevässä lainsäädännössä sekä yritysverotuksen keskeiset teemat asiantuntijakirjoitusten perusteella. Verosuunnittelun ja verotuksen merkitystä yrityskentässä selvitetään myös yrittäjien näkökulmasta ja verrataan asiantuntijakirjoituksiin. Tutkimuksen teoriassa käydään läpi hyvän verojärjestelmän periaatteet sekä pienen osakeyhtiön verosuunnittelukeinot. Empiirisessä osassa tutkimuksen kyselyaineistoa käsiteltiin varianssianalyysilla (ANOVA) sekä asiantuntija-artikkelit jaettiin suhteellisiin pää- ja alaryhmiin. Tutkimuksen perusteella voidaan todeta, että nykyinen yritysverojärjestelmä ei ole tarpeeksi yksinkertainen ja se luo epätasa-arvoa verovelvollisten joukossa. Muuten oikeudenmukaisuus toteutuu melko hyvin nykyisessä yritysverojärjestelmässä. Veroilla halutaan myös jonkin verran ohjata verovelvollisen käyttäytymistä ja näin ollen täysin neutraaliinkaan verojärjestelmään ei päästä. Kansainvälisen kilpailukyvyn näkökulmasta Suomen nimellinen verotus on EU-maiden keskiarvoa hieman korkeampi, mutta verotuksella ei karkoteta tuotannontekijöitä. Oikeusvarmuus ja ennakoitavuus toteutuvat hyvin. Yritysverotus on ollut esillä alan lehdissä runsaasti ja erityisesti kansainvälinen yritysverotus on saanut painoarvoa. Asiantuntijat näkevät verosuunnittelun monimuotoisempana kuin yrittäjät, jotka pitävät suunnittelua lähinnä palkan ja osingon edullisuuden vertailuna.

La cuestión del poder neutral en Schmitt

El artículo busca mostrar la importancia que la teoría del pouvoir neutre de B. Constant/ tuvo en la interpretación que Carl Schmitt hace de las funciones del Reichspräsident, en los años veinte hasta el nazismo. Aun cuando Schmitt critica al romanticismo, del cual al autor de Adolphe es una figura clave, igualmente reconoce que Constant teorizó la institución constitucional más adecuada para enfrentar las situaciones críticas, cuando la constitución debe autodefenderse mediante poderes legales pero excepcionales.

Nollapistekiinnittimen hyödyntäminen työkalun valmistuksessa ja muovausprosessissa

Tämä diplomityö tehtiin Lappeenrannan teknillisen yliopiston konetekniikan osastolle. Työn tavoitteena oli kartoittaa nollapistekiinnittimien tyyppejä ja toimintaperiaatteita sekä luoda muistilista liittyen nollapistekiinnittimen käyttöönottoon kiinnitysratkaisuna. Nollapistekiinnitin on konepajatekniikan kappaleenkiinnitin, joka tarjoaa tarkan paikoituksen, nopean asetusajan ja yksinkertaisen kappaleenvaihdon. Työssä tutkitaan nollapistekiinnittimien ominaisuuksia ja käyttökohteita, esitellään erityyppisiä nollapistekiinnittimiä ja vertaillaan niitä perinteisiin kiinnitysmenetelmiin. Työn kokeellisen osuuden tavoite oli tutkia nollapistekiinnittimen ominaisuuksia ja toimintaa ja pohtia mahdollisuuksia muovaustyökalun valmistuksessa ja kiinnittämisessä muovauspuristimeen. Kokeet tehtiin LTY:n konepajatekniikan laboratoriossa kesä- ja heinäkuussa 2010.

Diskreettiaikainen liukuvan moodin säätö kiinteäoksidipolttokennon DC-tasonnostossa

Huoli ympäristön tilasta ja fossiilisten polttoaineiden hinnan nousu ovat vauhdittaneet tutkimusta uusien energialähteiden löytämiseksi. Polttokennot ovat yksi lupaavimmista tekniikoista etenkin hajautetun energiantuotannon, varavoimalaitosten sekä liikennevälineiden alueella. Polttokenno on tehonlähteenä kuitenkin hyvin epäideaalinen, ja se asettaa tehoelektroniikalle lukuisia erityisvaatimuksia. Polttokennon kytkeminen sähköverkkoon on tavallisesti toteutettu käyttämällä galvaanisesti erottavaa DC/DC hakkuria sekä vaihtosuuntaajaa sarjassa. Polttokennon kulumisen estämiseksi tehoelektroniikalta vaaditaan tarkkaa polttokennon lähtövirran hallintaa. Perinteisesti virran hallinta on toteutettu säätämällä hakkurin tulovirtaa PI (Proportional and Integral) tai PID (Proportional, Integral and Derivative) -säätimellä. Hakkurin epälineaarisuudesta johtuen tällainen ratkaisu ei välttämättä toimi kaukana linearisointipisteestä. Lisäksi perinteiset säätimet ovat herkkiä mallinnusvirheille. Tässä diplomityössä on esitetty polttokennon jännitettä nostavan hakkurin tilayhtälökeskiarvoistusmenetelmään perustuva malli, sekä malliin perustuva diskreettiaikainen integroiva liukuvan moodin säätö. Esitetty säätö on luonteeltaan epälineaarinen ja se soveltuu epälineaaristen ja heikosti tunnettujen järjestelmien säätämiseen.

Critical-point model to estimate yield loss caused by Asian soybean rust

ABSTRACTA model to estimate yield loss caused by Asian soybean rust (ASR) (Phakopsora pachyrhizi) was developed by collecting data from field experiments during the growing seasons 2009/10 and 2010/11, in Passo Fundo, RS. The disease intensity gradient, evaluated in the phenological stages R5.3, R5.4 and R5.5 based on leaflet incidence (LI) and number of uredinium and lesions/cm2, was generated by applying azoxystrobin 60 g a.i/ha + cyproconazole 24 g a.i/ha + 0.5% of the adjuvant Nimbus. The first application occurred when LI = 25% and the remaining ones at 10, 15, 20 and 25-day intervals. Harvest occurred at physiological maturity and was followed by grain drying and cleaning. Regression analysis between the grain yield and the disease intensity assessment criteria generated 56 linear equations of the yield loss function. The greatest loss was observed in the earliest growth stage, and yield loss coefficients ranged from 3.41 to 9.02 kg/ha for each 1% LI for leaflet incidence, from 13.34 to 127.4 kg/ha/1 lesion/cm2 for lesion density and from 5.53 to 110.0 kg/ha/1 uredinium/cm2 for uredinium density.

Accuracy and efficiency evaluation of point-centered quarter method variations for vegetation sampling in an araucaria forest

In order to verify Point-Centered Quarter Method (PCQM) accuracy and efficiency, using different numbers of individuals by per sampled area, in 28 quarter points in an Araucaria forest, southern Paraná, Brazil. Three variations of the PCQM were used for comparison associated to the number of sampled individual trees: standard PCQM (SD-PCQM), with four sampled individuals by point (one in each quarter), second measured (VAR1-PCQM), with eight sampled individuals by point (two in each quarter), and third measuring (VAR2-PCQM), with 16 sampled individuals by points (four in each quarter). Thirty-one species of trees were recorded by the SD-PCQM method, 48 by VAR1-PCQM and 60 by VAR2-PCQM. The level of exhaustiveness of the vegetation census and diversity index showed an increasing number of individuals considered by quadrant, indicating that VAR2-PCQM was the most accurate and efficient method when compared with VAR1-PCQM and SD-PCQM.

Characterisation of Human Neutral and Lysosomal alpha-Mannosidases

Neutral alpha-mannosidase and lysosomal MAN2B1 alpha-mannosidase belong to glycoside hydrolase family 38, which contains essential enzymes required for the modification and catabolism of asparagine-linked glycans on proteins. MAN2B1 catalyses lysosomal glycan degradation, while neutral α-mannosidase is most likely involved in the catabolism of cytosolic free oligosaccharides. These mannose containing saccharides are generated during glycosylation or released from misfolded glycoproteins, which are detected by quality control in the endoplasmic reticulum. To characterise the biological function of human neutral α-mannosidase, I cloned the alpha-mannosidase cDNA and recombinantly expressed the enzyme. The purified enzyme trimmed the putative natural substrate Man9GlcNAc to Man5GlcNAc, whereas the reducing end GlcNAc2 limited trimming to Man8GlcNAc2. Neutral α-mannosidase showed highest enzyme activity at neutral pH and was activated by the cations Fe₂+, Co2+ and Mn₂+, Cu2+ in turn had a strong inhibitory effect on alpha-mannosidase activity. Analysis of its intracellular localisation revealed that neutral alpha-mannosidase is cytosolic and colocalises with proteasomes. Further work showed that the overexpression of neutral alpha-mannosidase affected the cytosolic free oligosaccharide content and led to enhanced endoplasmic reticulum associated degradation and underglycosylation of secreted proteins. The second part of the study focused on MAN2B1 and the inherited lysosomal storage disorder α-mannosidosis. In this disorder, deficient MAN2B1 activity is associated with mutations in the MAN2B1 gene. The thesis reports the molecular consequences of 35 alpha-mannosidosis associated mutations, including 29 novel missense mutations. According to experimental analyses, the mutations fall into four groups: Mutations, which prevent transport to lysosomes are accompanied with a lack of proteolytic processing of the enzyme (groups 1 and 3). Although the rest of the mutations (groups 2 and 4) allow transport to lysosomes, the mutated proteins are less efficiently processed to their mature form than is wild type MAN2B1. Analysis of the effect of the mutations on the model structure of human lysosomal alpha-mannosidase provides insights on their structural consequences. Mutations, which affect amino acids important for folding (prolines, glycines, cysteines) or domain interface interactions (arginines), arrest the enzyme in the endoplasmic reticulum. Surface mutations and changes, which do not drastically alter residue volume, are tolerated better. Descriptions of the mutations and clinical data are compiled in an α-mannosidosis database, which will be available for the scientific community. This thesis provides a detailed insight into two ubiquitous human alpha-mannosidases. It demonstrates that neutral alpha-mannosidase is involved in the degradation of cytosolic oligosaccharides and suggests that the regulation of this α-mannosidase is important for maintaining the cellular homeostasis of N-glycosylation and glycan degradation. The study on alpha-mannosidosis associated mutations identifies multiple mechanisms for how these mutations are detrimental for MAN2B1 activity. The α-mannosidosis database will benefit both clinicians and scientific research on lysosomal alpha‑mannosidosis.