On convergence of transforms based on parabolic scaling

This thesis studies properties of transforms based on parabolic scaling, like Curvelet-, Contourlet-, Shearlet- and Hart-Smith-transform. Essentially, two di erent questions are considered: How these transforms can characterize H older regularity and how non-linear approximation of a piecewise smooth function converges. In study of Hölder regularities, several theorems that relate regularity of a function f : R2 → R to decay properties of its transform are presented. Of particular interest is the case where a function has lower regularity along some line segment than elsewhere. Theorems that give estimates for direction and location of this line, and regularity of the function are presented. Numerical demonstrations suggest also that similar theorems would hold for more general shape of segment of low regularity. Theorems related to uniform and pointwise Hölder regularity are presented as well. Although none of the theorems presented give full characterization of regularity, the su cient and necessary conditions are very similar. Another theme of the thesis is the study of convergence of non-linear M ─term approximation of functions that have discontinuous on some curves and otherwise are smooth. With particular smoothness assumptions, it is well known that squared L2 approximation error is O(M-2(logM)3) for curvelet, shearlet or contourlet bases. Here it is shown that assuming higher smoothness properties, the log-factor can be removed, even if the function still is discontinuous.

A SECOND OPINION ON RELATIVE TRUTH

In 'An undermining diagnosis of relativism about truth', Horwich claims that the notion of relative truth is either explanatorily sterile or explanatorily superfluous. In the present paper, I argue that Horwich's explanatory demands set the bar unwarrantedly high: given the philosophical import of the theorems of a truth-theoretic semantic theory, Horwich's proposed explananda, what he calls acceptance facts, are too indirect for us to expect a complete explanation of them in terms of the deliverances of a theory of meaning based on the notion of relative truth. And, to the extent that there might be such an explanation in certain cases, there is no reason to expect relative truth to play an essential, ineliminable role, nor to endorse the claim that it should play such a role in order to be a theoretically useful notion.

Miehistönkuljetusajoneuvon rungon suunnittelu

Tämän diplomityön tavoitteena oli suunnitella miehistönkuljetusajoneuvon runko. Rungosta suunniteltiin mahdollisimman hyvin energiaa absorboiva. Rakenne toteutettiin kennora-kenteena. Suunnittelussa sovellettiin koneensuunnittelun periaatteiden lisäksi energiaa ab-sorboivien rakenteiden suunnittelun periaatteita. Myös valmistustekniset näkökohdat otet-tiin huomioon. Rakenteessa hyödynnettiin Ruukki Oy:n Ramor 500 suojausterästä sekä OPTIM 500 MC terästä. Lisäksi erilaisten täyteaineiden käyttöä tutkittiin. Suunnittelun työkaluna käytettiin epälineaarista elementtimenetelmää, koska energiaa ab-sorboivien rakenteiden suunnittelussa on otettava huomioon materiaalien epälineaarinen käyttäytyminen. Rakenteen suunnittelu jakaantui viiteen vaiheeseen. Aluksi rakenteeseen kohdistuvat kuormitukset laskettiin elementtimenetelmän avulla. Esisuunnittelussa lasket-tiin plastisuusteorian avulla alustavasti tarvittavat materiaalipaksuudet. Tämän jälkeen ra-kenteen ydingeometria optimoitiin mahdollisimman hyvin energiaa absorboivaksi. Opti-moinnissa hyödynnettiin elementtimenetelmää. Seuraavassa vaiheessa varmistettiin raken-teen globaalit ominaisuudet. Lopuksi rakenteen kestävyyttä tarkasteltiin elementtimene-telmällä. Runko ei mallien mukaan kestänyt siltä vaadittuja kuormitustapauksia. Mallin kaikki ole-tukset pidettiin varmalla puolella. Reunaehdot oletettiin todellisuutta jäykemmiksi. Myös-kään materiaalin venymänopeudesta johtuvaa lujittumista ei otettu huomioon. Koska mii-naräjähdys on monimutkainen tapahtuma, rungon todellinen kestävyys joudutaan ar-viomaan räjähdystesteillä. Elementtimallien perusteella voidaan kuitenkin sanoa, että ener-giaa absorboiva ajoneuvon runko on mahdollista toteuttaa kennorakenteena. Lisäksi voi-daan todeta, että elementtimenetelmää sopii työvälineeksi tämän tyyppisten rakenteiden suunnitteluun.

Development of racemization catalysts for dynamic kinetic resolution

Preparation of optically active compounds is of high importance in modern medicinal chemistry. Despite recent advances in the field of asymmetric synthesis, resolution of racemates still remains the most utilized way for preparation of single enantiomers in industrial scale due to its cost-efficiency and simplicity. Enzymatic kinetic resolution (KR) of racemates is a classical method for separation of enantiomers. One of its drawbacks is the limitation of target enantiomer yield to 50%. Dynamic Kinetic Resolution (DKR) allows to reach yields up to 100% by in situ racemization of the less reactive enantiomer. In the first part of this thesis, a number of half-sandwich ruthenium complexes were prepared and evaluated as catalysts for racemization of optically active secondary alcohols. A leading catalyst, Bn5CpRu(CO)2Cl, was identified. The catalyst discovered was extensively characterized by its application for DKR of a broad range of secondary alcohols in a wide range of reaction loadings (1 mmol – 1 mol). Cost-efficient chromatography-free procedure for preparation of this catalyst was developed. Further, detailed kinetic and mechanistic studies of the racemization reactions were performed. Comparison of racemization rates in the presence of Bn5CpRu(CO)2Cl and Ph5CpRu(CO)2Cl catalysts reveals that the performance of the catalytic system can be adjusted by matching of the electronic properties of the catalysts and the substrates. Moreover, dependence of the rate-limiting step from the electronic properties of the reagents was observed. Important conclusions about reaction mechanism were made. Finally, an alternative approach to DKR of amines based on space separated vessels was addressed. This procedure allows the combination of thermolabile enzyme with racemization catalysts active only at high temperatures.

Power cycling lifetime estimation of IGBT power modules based on chip temperature modeling

In this doctoral thesis, methods to estimate the expected power cycling life of power semiconductor modules based on chip temperature modeling are developed. Frequency converters operate under dynamic loads in most electric drives. The varying loads cause thermal expansion and contraction, which stresses the internal boundaries between the material layers in the power module. Eventually, the stress wears out the semiconductor modules. The wear-out cannot be detected by traditional temperature or current measurements inside the frequency converter. Therefore, it is important to develop a method to predict the end of the converter lifetime. The thesis concentrates on power-cycling-related failures of insulated gate bipolar transistors. Two types of power modules are discussed: a direct bonded copper (DBC) sandwich structure with and without a baseplate. Most common failure mechanisms are reviewed, and methods to improve the power cycling lifetime of the power modules are presented. Power cycling curves are determined for a module with a lead-free solder by accelerated power cycling tests. A lifetime model is selected and the parameters are updated based on the power cycling test results. According to the measurements, the factor of improvement in the power cycling lifetime of modern IGBT power modules is greater than 10 during the last decade. Also, it is noticed that a 10 C increase in the chip temperature cycle amplitude decreases the lifetime by 40%. A thermal model for the chip temperature estimation is developed. The model is based on power loss estimation of the chip from the output current of the frequency converter. The model is verified with a purpose-built test equipment, which allows simultaneous measurement and simulation of the chip temperature with an arbitrary load waveform. The measurement system is shown to be convenient for studying the thermal behavior of the chip. It is found that the thermal model has a 5 C accuracy in the temperature estimation. The temperature cycles that the power semiconductor chip has experienced are counted by the rainflow algorithm. The counted cycles are compared with the experimentally verified power cycling curves to estimate the life consumption based on the mission profile of the drive. The methods are validated by the lifetime estimation of a power module in a direct-driven wind turbine. The estimated lifetime of the IGBT power module in a direct-driven wind turbine is 15 000 years, if the turbine is located in south-eastern Finland.

Coupling of palmitate to ovalbumin inhibits the induction of oral tolerance

Oral tolerance is a phenomenon that may occur in animals exposed to protein antigens for the first time by the oral route. They become unable to produce immune responses at the levels normally observed when they are immunized parenterally with antigen in the presence of adjuvants. Lipids have been used as adjuvants for both parenteral and oral immunization. In the present study we coupled ovalbumin with palmitate residues by incubating the protein with the N-hydroxysuccinimide palmitate ester and tested the preparation for its ability to induce oral tolerance. This was performed by giving 20 mg of antigen to mice by the oral route 7 days prior to parenteral immunization in the presence of Al(OH)3. Mice were bled one week after receiving a booster that was given 2 weeks after primary immunization. Specific antibodies were detected by ELISA. Despite the fact that the conjugates are as immunogenic as the unmodified protein when parenterally injected in mice, they failed to induce oral tolerance. This discrepancy could be explained by differences in the intestinal absorption of the two forms of the antigen. In fact, when compared to the non-conjugated ovalbumin, a fast and high absorption of the lipid-conjugated form of ovalbumin was observed by "sandwich" ELISA.

Serum cytokine profile in the subclinical form of visceral leishmaniasis

The factors determining the development or not of visceral leishmaniasis (VL) have not been completely identified, but a Leishmania-specific cellular immune response seems to play a fundamental role in the final control of infection. Few studies are available regarding the production of cytokines in the subclinical form of VL, with only the production of IFN-g and TNF-a known. The aim of the present study was to identify immunological markers for the oligosymptomatic or subclinical form of VL. A prospective cohort study was conducted on 784 children aged 0 to 5 years from an endemic area in the State of Maranhão, Brazil, between January 1998 and December 2001. During 30 consecutive months of follow-up, 33 children developed the oligosymptomatic form of the disease and 12 the acute form. During the clinical manifestations, serum cytokine levels were determined in 27 oligosymptomatic children and in nine patients with the acute form using a quantitative sandwich enzyme immunoassay. In the subclinical form of VL, variable levels of IL-2 were detected in 52.3% of the children, IL-12 in 85.2%, IFN-g in 48.1%, IL-10 in 88.9%, and TNF-a in 100.0%, with the last two cytokines showing significantly lower levels than in the acute form. IL-4 was not detected in oligosymptomatic individuals. Multiple discriminant analysis used to determine the profile or combination of cytokines predominating in the subclinical form revealed both a Leishmania resistance (Th1) and susceptibility (Th2) profile. The detection of both Th1 and Th2 cytokine profiles explains the self-limited evolution accompanied by the discrete alterations observed for the subclinical form of VL.

High levels of serum mannose-binding lectin are associated with the severity of clinical signs of leptospirosis

The clinical heterogeneity observed in leptospirosis may be associated with host factors or bacteria virulence. Human serum mannose-binding lectin (MBL) recognizes many pathogens, and low levels of this lectin are associated with susceptibility to infection. MBL is also implicated in the modulation of the inflammatory process. We determined the levels of serum MBL during leptospirosis infection. A double-antibody sandwich ELISA was used to detect the immunoreactive serum MBL. The ELISA plates were coated with monoclonal antibody to MBL and bound MBL or recombinant human MBL were detected by rabbit anti-human MBL serum. HRPO-conjugated goat anti-rabbit antibody was used for detection of the reaction. Two groups of patients seen at referral hospitals in Recife, PE, Brazil, were divided according to the year of infection, 2001 (N = 61) or 2002 (N = 57) and compared in terms of disease severity and levels of serum MBL. A group of healthy volunteers (N = 97) matched by age, gender, and ethnic background was used as control. Patients infected in 2001 had more severe outcomes than those infected in 2002, including jaundice, hemorrhage, respiratory alteration, and renal complication (P = 0.0009; chi-square test). The frequency of patients producing serum MBL >1000 ng/mL was higher in the 2001 group than in the 2002 and control groups (P < 0.01), suggesting an association of MBL level with disease severity. The involvement of MBL and genetic variation of the MBL2 gene should be further evaluated to establish the role of this lectin in the pathogenesis of leptospirosis.

Inflammatory cytokines and plasma redox status responses in hypertensive subjects after heat exposure

Hypertension is characterized by a pro-inflammatory status, including redox imbalance and increased levels of pro-inflammatory cytokines, which may be exacerbated after heat exposure. However, the effects of heat exposure, specifically in individuals with inflammatory chronic diseases such as hypertension, are complex and not well understood. This study compared the effects of heat exposure on plasma cytokine levels and redox status parameters in 8 hypertensive (H) and 8 normotensive (N) subjects (age: 46.5±1.3 and 45.6±1.4 years old, body mass index: 25.8±0.8 and 25.6±0.6 kg/m2, mean arterial pressure: 98.0±2.8 and 86.0±2.3 mmHg, respectively). They remained at rest in a sitting position for 10 min in a thermoneutral environment (22°C) followed by 30 min in a heated environmental chamber (38°C and 60% relative humidity). Blood samples were collected before and after heat exposure. Plasma cytokine levels were measured using sandwich ELISA kits. Plasma redox status was determined by thiobarbituric acid reactive substances (TBARS) levels and ferric reducing ability of plasma (FRAP). Hypertensive subjects showed higher plasma levels of IL-10 at baseline (P<0.05), although levels of this cytokine were similar between groups after heat exposure. Moreover, after heat exposure, hypertensive individuals showed higher plasma levels of soluble TNF receptor (sTNFR1) and lower TBARS (P<0.01) and FRAP (P<0.05) levels. Controlled hypertensive subjects, who use angiotensin-converting-enzyme inhibitor (ACE inhibitors), present an anti-inflammatory status and balanced redox status. Nevertheless, exposure to a heat stress condition seems to cause an imbalance in the redox status and an unregulated inflammatory response.

Bio and chemocatalysis for stereo and regioselective one-pot reaction applications

The development of cost efficient, selective and sustainable chemical processes for production of chiral building blocks is of great importance in synthetic and industrial organic chemistry. One way to reach these objectives is to carry out several reactions steps in one vessel at one time. Furthermore, when this kind of one-pot multi step reactions are catalyzed by heterogeneous chemo- and bio-catalysts, which can be separated from the reaction products by filtration, practical access to chiral small molecules for further utilization can be obtained. The initial reactions studied in this thesis are the two step dynamic kinetic resolution of rac-2-hydroxy-1-indanone and the regioselective hydrogenation of 1,2-indanedione. These reactions are then combined in a new heterogeneously catalyzed one-pot reaction sequence enabling simple recovery of the catalysts by filtration, facilitating simple reaction product isolation. Conclusively, the readily available 1,2-indanedione is by the presented one-pot sequence, utilizing heterogeneous enzyme and transition metal based catalysts, transferred with high regio- and stereoselectivity to a useful chiral vicinal hydroxyl ketone structure. Additional and complementary investigation of homogeneous half-sandwich ruthenium complexes for catalyzing the epimerization of chiral secondary alcohols of five natural products containing additional non-functionalized stereocenters was conducted. In principle, this kind of epimerization reactions of single stereocenters could be utilized for converting inexpensive starting materials, containing other stereogenic centers, into diastereomeric mixtures from which more valuable compounds can be isolated by traditional isolation techniques.

Mikrofluidiikkaan perustuvien potilasläheisten määritysjärjestelmien hyödyt ja ongelmakohdat sekä Tyreotropiinimäärityksen optimointi ja mikrofluidiikan hallinta vieritestaukseen soveltuvalla määritysalustalla

Keskitettyihin laboratoriotutkimuksiin verrattuna potilaan tai näytteenottopaikan läheisyydessä tehtävä vieritestaus on useimmiten kustannustehokkaampaa, helpompaa ja huomattavasti nopeampaa, eikä testin suorittamiseen välttämättä vaadita erityiskoulutettua henkilökuntaa. Potilasläheinen diagnostiikka on muokannut terveydenhoitoalaa siirtämällä päivittäisiä ja rutiininomaisia määrityksiä lähelle potilasta, tulosten ollessa selvillä lähes välittömästi. Nopea diagnostiikkaa saattaa myös vaikuttaa jatkohoitopäätöksen tekemiseen sairaalaolosuhteissa. Riittävän herkkyyden omaavien määritysjärjestelmien suunnittelu ja valmistus on kuitenkin hankalaa, lisäksi valmistusmateriaalien ja käytettyjen reagenssien tasalaatuisuus ei aina ole itsestään selvää. Laatuvirheet ovat yleisesti vaikeasti havaittavia sekä vaikuttavat olennaisesti määrityksen suorittamiseen ja tulokseen. Mikroskaalalla materiaalien fysikaalinen käytös muuttuu, ominaisuus otettava huomioon järjestelmiä suunnitellessa. Tutkielman kokeellisessa osassa optimoitiin 107 nm:n ja 92 nm:n Eu3+-ioneja sisältäviä polystyreeni-nanopartikkeleita sekä kahta eri anti-TSH vasta-ainetta hyödyntävä heterogeeninen sandwich-tyyppinen immunomääritys uudelle määritysalustalle. Työssä tarkasteltiin immunomäärityksen optimaaliselle toiminnalle olennaisia asioita kuten lämpötilaa määrityksen eri pisteissä, reaktiotilavuuksia ja -aikoja, puskureiden koostumuksia ja pitoisuuksia, leima-ainemääriä, säilytysolosuhteita sekä mikrofluidiikan vaikutuksia ja toimintaa tietokoneohjatulla mekaanisella ruiskujärjestelmällä. Diagnostiikkakasetin reaktiokammion pesutekniikat sekä pesuaineen vahvuus sekä koostumus olivat myös tarkasteltavina. Nanopartikkeleiden tuottama pitkäikäinen fluoresenssi mitattiin reaktiokammion pinnalta Victor-levylukijalla. Haastetta työhön toi mikrofluidiikan hallinta ja sen ominaisuudet, pääasiassa nesteliike, kuplanmuodostus sekä reaktiokammion onnistunut pesu. Määritys toimii teknisesti hyvin ja oikealla tavalla. Määritysaika oli 15 minuuttia. Aivan pienimpiä pitoisuuksia ei kuitenkaan kyetty erottamaan taustasta. TSH-määrityksen optimointi tuotti runsaasti teknistä perustietoa heterogeenisen immunomäärityksen toimivuudesta kasetti-ympäristössä, mikä helpottaa muiden samalla periaatteella toimivien määritysten käyttöönottoa. Määritysjärjestelmää voidaan tulevaisuudessa käyttää esimerkiksi kilpirauhasen vajaa- tai liikatoiminnan havaitsemisen lisäksi muun muassa sydäninfarktin varhaiseen ja nopeaan toteamiseen.

Towards automated derivation in the theory of allegories

We provide an algorithm that automatically derives many provable theorems in the equational theory of allegories. This was accomplished by noticing properties of an existing decision algorithm that could be extended to provide a derivation in addition to a decision certificate. We also suggest improvements and corrections to previous research in order to motivate further work on a complete derivation mechanism. The results presented here are significant for those interested in relational theories, since we essentially have a subtheory where automatic proof-generation is possible. This is also relevant to program verification since relations are well-suited to describe the behaviour of computer programs. It is likely that extensions of the theory of allegories are also decidable and possibly suitable for further expansions of the algorithm presented here.

Gilbert McMicken document, n.d.

Gilbert McMicken emigrated to Upper Canada in 1832 and settled in Chippawa. In 1835 he was married to Ann Theresa Duff. In 1837 the family moved to Queenston where he was directly involved in the Kingston-Queenston trade endeavours begun by Robert Hamilton. He had a variety of interests, including a partnership with James Hamilton, son of Robert Hamilton. He was also a collector of customs in Queenston and operated the Niagara Suspension Bridge Bank for a time. He entered politics and represented Niagara as well as becoming mayor of Clifton, now part of Niagara Falls, Ont., in 1856. McMicken went on to have an illustrious career, serving as land agent and leader of Canada’s first undercover agency. McMicken moved to Manitoba and was active in business and politics. He died in Winnipeg in 1891. Source: Dictionary of Canadian Biography – Gilbert McMicken website (March 22, 2010)

Extending relAPS to first order logic

RelAPS is an interactive system assisting in proving relation-algebraic theorems. The aim of the system is to provide an environment where a user can perform a relation-algebraic proof similar to doing it using pencil and paper. The previous version of RelAPS accepts only Horn-formulas. To extend the system to first order logic, we have defined and implemented a new language based on theory of allegories as well as a new calculus. The language has two different kinds of terms; object terms and relational terms, where object terms are built from object constant symbols and object variables, and relational terms from typed relational constant symbols, typed relational variables, typed operation symbols and the regular operations available in any allegory. The calculus is a mixture of natural deduction and the sequent calculus. It is formulated in a sequent style but with exactly one formula on the right-hand side. We have shown soundness and completeness of this new logic which verifies that the underlying proof system of RelAPS is working correctly.