Delineamentos experimentais eficientes para estudos de cinética química

In this paper we show how to obtain efficient designs of experiments for fitting Michaelis-Menten and Hill equations useful in chemical studies. The search of exact D-optimal designs by using local and pseudo-Bayesian approaches is considered. Optimal designs were compared to those commonly used in practice using an efficiency measure and theoretical standard errors of the kinetic parameter estimates. In conclusion, the D-optimal designs based on the Hill equation proved efficient for estimating the parameters of both models. Furthermore, these are promising with respect to practical issues, allowing efficient estimation as well as goodness-of-fit tests and comparisons between some kinetic models.

Alusöljyvahingon seurauksena rantautuvan öljyn lajitteluohjeiston muodostaminen

Työn tärkeimpänä päämääränä oli muodostaa öljyvahinkojätejakeille yksityiskohtaiset ja käytännön olosuhteissa mahdollisimman hyvin toimivat lajitteluohjeet. Lähtökohtana oli se, että edeltävien lajitteluohjeiden soveltuvuutta haluttiin tarkastella useista eri näkökulmista, kuten muodostuvien kustannusten kannalta. Työn muut tavoitteet olivat: jäteastioiden määrän ja laadun selvitys sekä lainsäädännön asettamien rajoitteiden selvittäminen. Riskijäte rajattiin työn ulkopuolelle. Tutkimus toteutettiin pääasiassa kirjallisiin lähteisiin, sähköpostikyselyihin ja puhelinhaastatteluihin perustuvien tietojen avulla. Tärkeimmäksi selvitettäväksi seikaksi osoittautui lajittelusta aiheutuvien kustannusten määrittäminen. Etenkin käsittelykustannuksista saatiin viitteitä optimaalisesta lajitteluvaihtoehdosta. Taloudellisessa tarkastelussa käytiin läpi öljyvahinkojätteiden kulkeutuminen rannalta käsittelyyn saakka, jolloin eri vaihtoehtojen eroavaisuudet saatiin selville. Taloudellisen tarkastelun perusteella paras vaihtoehto oli lajitellun jätteen käsittely siirrettävällä termodesorptiolaitoksella yhdistettynä Kotkan hyötyvoimalaitokseen. Tämän perusteella voidaan päätellä, että öljyinen maa-aines ja öljyinen sekajäte kannattaa käsitellä erillisinä jakeina. Tällöin öljyinen maa-aines ja öljyinen sekajäte kannattaa myös lajitella omiin jakeisiinsa. Keräysastioista on vaikeaa antaa suosituksia ilman riittävän kattavia kenttäkokeita. Taloudellisessa tarkastelussa muoviastiat osoittautuivat edullisimmaksi vaihtoehdoksi. Monissa selvityksissä on öljyvahinkojätteiden käsittelyvaihtoehdoksi valittu Riihimäen Ekokem Oy Ab. Se tuli kuitenkin huomattavasti kalliimmaksi kuin siirrettävän termodesorptiolaitoksen sisältävät laskuesimerkit, joten myös muita vaihtoehtoja kannattaisi harkita. Muita kuin muovisia keräysastioita tulisi vielä testata käytännön öljyntorjuntaharjoituksissa, jotta niiden lopullinen käyttökelpoisuus varmistuu. Harjoitukset tulisi suorittaa mahdollisimman vaihtelevissa sää- ja maasto-olosuhteissa, jotta saadaan tarpeeksi kattavaa tutkimustietoa astioiden soveltuvuudesta.

Effect of Fusarium graminearum and infection index on germination and vigor of maize seeds

Pathogens in maize (Zea mays) seeds cause serious problems, such as the loss of their capacity to germinative. The objectives of this study were to identify the optimal period for infection of maize seeds on agar colonized by Fusarium graminearum, when incubated for 4, 8, 16 and 32 h, and to evaluate the effect of the fungus on the germination and vigor of seeds with different infection levels. After the respective incubation periods, the seeds were removed from the culture medium and submitted to the blotter test for 3 min with and without superficial disinfection with 1% solution of sodium hypochlorite. Once the optimal period for seed incubation was identified, seeds from the same sample were again placed on the colonized agar for infection. Germination and vigor tests (accelerated aging and cold test) were performed with a mixture of healthy seeds (placed on PDA medium) and inoculated seeds, resulting in seeds with 0, 20, 40, 60, 80 and 100% rates of infection. The results showed that a period of 32 h was long enough to obtain seeds infected by the pathogen. There were no significant effects of fungal infection on seed germination at any of the infection levels, probably due to the high vigor of the maize seed lot tested. Regarding vigor tests, infection levels differed significantly from the control (0% infection), but there were no significant differences among the infection levels.

Estimation of existing cable systems in generator-busbar unit and choice the optimal solution for its modernization

The aim of this master’s thesis is to develop an algorithm to calculate the cable network for heat and power station CHGRES. This algorithm includes important aspect which has an influence on the cable network reliability. Moreover, according to developed algorithm, the optimal solution for modernization cable system from economical and technical point of view was obtained. The conditions of existing cable lines show that replacement is necessary. Otherwise, the fault situation would happen. In this case company would loss not only money but also its prestige. As a solution, XLPE single core cables are more profitable than other types of cable considered in this work. Moreover, it is presented the dependence of value of short circuit current on number of 10/110 kV transformers connected in parallel between main grid and considered 10 kV busbar and how it affects on final decision. Furthermore, the losses of company in power (capacity) market due to fault situation are presented. These losses are commensurable with investment to replace existing cable system.

Uutto-olosuhteiden vaikutus kasviperäisen indigon saantoon

Indigo on väriaine, jota valmistetaan petrokemianteollisuuden välituotteena syntyvästä aniliinista. Indigolla on kuitenkin pitkä historia. Sitä on valmistettu perinteisesti eri viljelykasveista, joista Euroopassa merkittävin on ollut morsinko. Luonnonmukaisten tuotteiden suosion kasvaessa on ryhdytty selvittämään morsingon viljelyn potentiaalia. Viljelyn kannattavuuden kannalta olennaista on kasvin lehdissä esiintyvien indigon esiasteiden mahdollisimman täydellinen eristäminen. Indigoa tuotetaan uuttamalla indigon esiasteet veteen. Esiasteet hajoavat synnyttäen indoksyyliä, josta hapen vaikutuksella muodostuu indigoa. Syntynyt indigo saostuu ja laskeutuu pohjalle. Samalla kuitenkin tapahtuu epätoivottuja sivureaktioita, jotka vähentävät indigon saantoa. Tutkimuksen tavoitteena oli laboratorio- ja kenttäkokeiden avulla löytää indigon saantoa parantavat uutto-olosuhteet. Kokeiden perusteella havaittiin, että indigon saantoon vaikuttavat positiivisesti pH:n laskeminen, lämpötilan nostaminen, morsingon lehtien pilkkominen ja uuttoliuoksen sekoittaminen. Uuttoliuoksen suolapitoisuuden havaittiin puolestaan vaikuttavan indigon saantoon negatiivisesti. Laboratoriokokeiden perusteella havaittu pH:n laskemisen vaikutus indigon saantoon todistettiin myös kenttäolosuhteissa. Kokeiden havaintojen perusteella esitettiin olosuhteiden indigosaantoa parantavien vaikutusten johtuvan kahdesta tekijästä: indoksyylin stabiloitumisesta happamassa ympäristössä, jolloin sivureaktioiden osuus vähenee, sekä aineensiirron paranemisella sekoituksen, faasien rajapinnan kasvamisen ja etenkin lehtien vahakerroksen rikkoutumisen kuuman veden ja hapon vaikutuksesta.

Studies on 68Ga-Based Agents for PET Imaging of Cancer and Inflammation

Studies on ⁶⁸Ga-Based Agents for PET Imaging of Cancer and Inflammation Positron emission tomography (PET) is based on the use of radiolabeled agents and facilitates in vivo imaging of biological processes, such as cancer. Because the detection of cancer is demanding and is often obscured by inflammation, there is a demand for better PET imaging agents. The aim was to preliminarily evaluate new PET agents for imaging cancer and inflammation using experimental models. ⁶⁸Ga-chloride and peptides, ⁶⁸Ga-labeled through 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA), targeting matrix metalloproteinase-9 (MMP-9) were tested for tumor imaging. In addition, a ⁶⁸Ga-DOTA-conjugated peptide targeting vascular adhesion protein-1 (VAP-1), was tested for inflammation imaging. The ⁶⁸Ga-based imaging agents described here showed potential features by passing the essential in vitro tests, proceeding further to preclinical in vivo evaluation and being able to visualize the target. The target uptake and target-to-background ratios of ⁶⁸Ga-based agents were, however, not optimal. ⁶⁸Ga-chloride showed slow clearance caused by its binding to blood transferrin. In the case of ⁶⁸Ga-DOTA-peptides low in vivo stability and/or low lipophilicity led to too rapid blood clearance and urinary excretion. The properties of ⁶⁸Ga-labeled peptides are modifiable, as shown with matrix metalloproteinase-9 targeting ligands. In the conclusion of this PhD thesis, ⁶⁸Ga-based agents for PET imaging of cancer and inflammation could be applied in the development of drugs, earlier diagnostics and following-up of the efficacy of therapies.

Choosing the optimal energy system for buildings and districts

The purpose of this master’s thesis was to develop a method to be used in the selection of an optimal energy system for buildings and districts. The term optimal energy system was defined as the energy system which best fulfils the requirements of the stakeholder on whose preferences the energy systems are evaluated. The most influential stakeholder in the process of selecting an energy system was considered to be the district developer. The selection method consisted of several steps: Definition of the district, calculating the energy consumption of the district and buildings within the district, defining suitable energy system alternatives for the district, definition of the comparing criteria, calculating the parameters of the comparing criteria for each energy system alternative and finally using a multi-criteria decision method to rank the alternatives. For the purposes of the selection method, the factors affecting the energy consumption of buildings and districts and technologies enabling the use of renewable energy were reviewed. The key element of the selection method was a multi-criteria decision making method, PROMETHEE II. In order to compare the energy system alternatives with the developed method, the comparing criteria were defined in the study. The criteria included costs, environmental impacts and technological and technical characteristics of the energy systems. Each criterion was given an importance, based on a questionnaire which was sent for the steering groups of two district development projects. The selection method was applied in two case study analyses. The results indicate that the selection method provides a viable and easy way to provide the decision makers alternatives and recommendations regarding the selection of an energy system. Since the comparison is carried out by changing the alternatives into numeric form, the presented selection method was found to exclude any unjustified preferences over certain energy systems alternatives which would affect the selection.

Lämpöyrittäjäkonsepti biotuotteelle

Fossiilisista polttoaineista aiheutuvia hiilidioksidipäästöjä yritetään vähentää muun muassa lisäämällä uusiutuvien polttoaineiden käyttöä. Kiinteän biomassan ominaisuudet eroavat fossiilisesta kivihiilestä kuitenkin niin paljon, ettei biomassalla voida suoraan korvata kivihiiltä. Biomassan lämpökäsittely muuttaa sen ominaisuuksia kivihiilen kaltaiseksi, jolloin sillä on mahdollista korvata kivihiiltä. Tässä diplomityössä on tutkittu biomassan lämpökäsittelyä eli torrefiointia. Työn lähtökohtana on luoda pohjaa liikeidealle, jossa torrefioitua biomassaa tuotetaan pienissä lämpölaitoksissa lämmöntuotannon ohella. Työ sisältää laboratoriokokeita, joissa tarkastellaan käytännön kokeilla biomassan torrefioinnissa tapahtuvia ominaisuuksien muutoksia. Biomassan torrefiointiin suunnitellaan lisäksi pientä koelaitetta, jonka kokoa on mahdollista suurentaa jatkossa lämpölaitoskokoluokkaan asti. Torrefioidun biomassan tuotantokustannuksia on tarkasteltu laiteinvestointien, raaka-aine- sekä käyttökustannuksien kautta. Laboratoriokokeiden perusteella on saatu tuloksia optimaalisista toiminta-arvoista lämpökäsittelymenetelmille. Lämpöyrittäjälle on luotu perustoiminta-ajatus torrefioidun biomassan tuotannolle, jossa on tarkasteltu myös tuotannon kannattavuutta. Tämä työ antaa pohjaa aiheen jatkotutkimukselle ja -kehitykselle.

Optimal trading of wind power in the short term market

The energy reform, which is happening all over the world, is caused by the common concern of the future of the humankind in our shared planet. In order to keep the effects of the global warming inside of a certain limit, the use of fossil fuels must be reduced. The marginal costs of the renewable sources, RES are quite high, since they are new technology. In order to induce the implementation of RES to the power grid and lower the marginal costs, subsidies were developed in order to make the use of RES more profitable. From the RES perspective the current market is developed to favor conventional generation, which mainly uses fossil fuels. Intermittent generation, like wind power, is penalized in the electricity market since it is intermittent and thus diffi-cult to control. Therefore, the need of regulation and thus the regulation costs to the producer differ, depending on what kind of generation market participant owns. In this thesis it is studied if there is a way for market participant, who has wind power to use the special characteristics of electricity market Nord Pool and thus reach the gap between conventional generation and the intermittent generation only by placing bids to the market. Thus, an optimal bid is introduced, which purpose is to minimize the regulation costs and thus lower the marginal costs of wind power. In order to make real life simulations in Nord Pool, a wind power forecast model was created. The simulations were done in years 2009 and 2010 by using a real wind power data provided by Hyötytuuli, market data from Nord Pool and wind forecast data provided by Finnish Meteorological Institute. The optimal bid needs probability intervals and therefore the methodology to create probability distributions is introduced in this thesis. In the end of the thesis it is shown that the optimal bidding improves the position of wind power producer in the electricity market.

Computational modeling for irrigated agriculture planning. Part I: general description and linear programming

Linear programming models are effective tools to support initial or periodic planning of agricultural enterprises, requiring, however, technical coefficients that can be determined using computer simulation models. This paper, presented in two parts, deals with the development, application and tests of a methodology and of a computational modeling tool to support planning of irrigated agriculture activities. Part I aimed at the development and application, including sensitivity analysis, of a multiyear linear programming model to optimize the financial return and water use, at farm level for Jaíba irrigation scheme, Minas Gerais State, Brazil, using data on crop irrigation requirement and yield, obtained from previous simulation with MCID model. The linear programming model outputted a crop pattern to which a maximum total net present value of R$ 372,723.00 for the four years period, was obtained. Constraints on monthly water availability, labor, land and production were critical in the optimal solution. In relation to the water use optimization, it was verified that an expressive reductions on the irrigation requirements may be achieved by small reductions on the maximum total net present value.

Static tests of constructive tires using hydraulic press on the soil

ABSTRACT The power consumption and load capacity of agricultural machines have grown and the effects of pressure on the soil by tires have been still little investigated. In concern with sustainable development, the relationship machine-tire-soil must be in balance to give more consistency on the best use of tires for a given load. This study aimed to evaluate four tires of two constructive types, the bias belted tires and radial tires, both with respective rim diameters of 22.5 and 26.5 inches with variables measuring the footprint, elastic deformation, sinkage and resistance to penetration. A hydraulic press with an attachment shaft for tire mounting and a box of soil in which the tire has been imposed on a load of 53.00 kN using nominal pressures recommended by the tire manufacturer. The radial construction tire with rim diameter of 26.5 inches obtained less sinkage and resistance to penetration; however, greater elastic deformation and footprint compared to other tires. The bias-belted tire with 22.5-inch rim presented the highest resistance to penetration and the lowest elastic deformation.

Testing Futures Market Efficiency and Optimal Hedge Ratio Estimation: Evidence from Futures and Options on RTS

This study investigates futures market efficiency and optimal hedge ratio estimation. First, cointegration between spot and futures prices is studied using Johansen method, with two different model specifications. If prices are found cointegrated, restrictions on cointegrating vector and adjustment coefficients are imposed, to account for unbiasedness, weak exogeneity and prediction hypothesis. Second, optimal hedge ratios are estimated using static OLS, and time-varying DVEC and CCC models. In-sample and out-of-sample results for one, two and five period ahead are reported. The futures used in thesis are RTS index, EUR/RUB exchange rate and Brent oil, traded in Futures and options on RTS.(FORTS) For in-sample period, data points were acquired from start of trading of each futures contract, RTS index from August 2005, EUR/RUB exchange rate March 2009 and Brent oil October 2008, lasting till end of May 2011. Out-of-sample period covers start of June 2011, till end of December 2011. Our results indicate that all three asset pairs, spot and futures, are cointegrated. We found RTS index futures to be unbiased predictor of spot price, mixed evidence for exchange rate, and for Brent oil futures unbiasedness was not supported. Weak exogeneity results for all pairs indicated spot price to lead in price discovery process. Prediction hypothesis, unbiasedness and weak exogeneity of futures, was rejected for all asset pairs. Variance reduction results varied between assets, in-sample in range of 40-85 percent and out-of sample in range of 40-96 percent. Differences between models were found small, except for Brent oil in which OLS clearly dominated. Out-of-sample results indicated exceptionally high variance reduction for RTS index, approximately 95 percent.

Molecular diagnostics of rare inherited SYNDROMES with a view on diagnostic test development

CHARGE syndrome, Sotos syndrome and 3p deletion syndrome are examples of rare inherited syndromes that have been recognized for decades but for which the molecular diagnostics only have been made possible by recent advances in genomic research. Despite these advances, development of diagnostic tests for rare syndromes has been hindered by diagnostic laboratories having limited funds for test development, and their prioritization of tests for which a (relatively) high demand can be expected. In this study, the molecular diagnostic tests for CHARGE syndrome and Sotos syndrome were developed, resulting in their successful translation into routine diagnostic testing in the laboratory of Medical Genetics (UTUlab). In the CHARGE syndrome group, mutation was identified in 40.5% of the patients and in the Sotos syndrome group, in 34%, reflecting the use of the tests in routine diagnostics in differential diagnostics. In CHARGE syndrome, the low prevalence of structural aberrations was also confirmed. In 3p deletion syndrome, it was shown that small terminal deletions are not causative for the syndrome, and that testing with arraybased analysis provides a reliable estimate of the deletion size but benign copy number variants complicate result interpretation. During the development of the tests, it was discovered that finding an optimal molecular diagnostic strategy for a given syndrome is always a compromise between the sensitivity, specificity and feasibility of applying a new method. In addition, the clinical utility of the test should be considered prior to test development: sometimes a test performing well in a laboratory has limited utility for the patient, whereas a test performing poorly in the laboratory may have a great impact on the patient and their family. At present, the development of next generation sequencing methods is changing the concept of molecular diagnostics of rare diseases from single tests towards whole-genome analysis.