Pitkäketjuisten keteenien valmistusreaktiot ja kinetiikka.

Tämän diplomityön tarkoituksena oli tutkia pitkäketjuisten rasvahappokloridien ja alkyyliketeenidimeerien (AKD) valmistusreaktioiden kinetiikkaa. Työn tavoitteena oli saada mittaustuloksia, joiden perusteella voitaisiin kehittää reaktioille kineettinen kineettinen malli ja suorittaa valmistusprosessien alustava optimointi. Teoreettisessa osassa on selvitetty rasvahappokloridien ja alkyyliketeenidimeerien (AKD) eri valmistustapoja. Lisäksi on perehdytty tarkemmin rasvahappokloridien dehydrohalogenointireaktioiden reaktiomekanismeihin ja valmistusprosessin problematiikkaan. Kokeellisessa osassa tutkittiin rasvahappokloridien valmistusta klooraamalla öljyhappoa 30 mol-% fosforitrikloridiylimäärällä lämpötiloissa 45, 50 ja 55OC. Alkyyliketeenidimeerien valmistusta tutkittiin dehydrohalogenoimalla palmitiini- ja öljyhappokloridia 0-30 mol-% trietyyliamiiniylimäärällä inertissä liuottimessa, lämpötiloissa 45 ja 50OC. Reaktiot toteutettiin puolipanosreaktiona, joissa reaktioastiassa olevaan reagenssin ja liuottimen seokseen lisättiin lähtöaine tasaisena massavirtana. Reaktioiden etenemistä seurattiin FT-IR- ja GC-analyysien avulla. Kalorimetrisilla kokeilla tutkittiin öljyhappokloridin dimeroitumisreaktion reaktiolämmön muodostumista ja UV-VIS-analyyseillä seurattiin öljyhappokloridin vanhenemista. Öljyhappokloridin valmistusreaktiolle saatiin hyvä kineettinen malli. Kineettisen mallin puutteena voidaan pitää sitä, ettei kokeissa saatu tietoa mahdollisten sivutuotteiden muodostumisesta. Sovitusohjelmalla saatiin sovitettua estimaatit reaktionopeusvakioille lämpötiloissa 45, 50 ja 55OC. Happokloridien dimeroitumisreaktioiden kineettisen mallin sopivuudelle saatiin suhteellisen hyvä kuva Kuten öljyhappokloridin tapauksessa, myöskään AKD:n valmistusreaktioissa syntynyt sivutuotteita, joten niiden osuutta oletettuun kineettiseen malliin ei tunneta. Sovitusohjelmalla saatiin sovitettua estimaatit reaktionopeusvakioille lämpötiloissa 45 ja 50OC.

Wet Oxidation of TMP Concentrated Paper Mill Process Water. Kinetics of the reaction

Työn tarkoituksena oli tutkia lämpötilan, paineen, pH:n ja katalyytin vaikutusta paperitehtaan TMP-konsentroidun prosessiveden märkähapetuksessa. Teoriaosio sisältää katsauksen sellu- ja paperiteollisuuteen, jätevesien käsittelyyn, nanosuodatuksen ja märkähapetusprosessin toimintaperiaatteet ja sovellukset hybriditeknologialle nanosuodatus-märkähapetuksessa. Empiirinen osa koostuu märkähapetuskokeista eri lämpötiloissa, paineissa, pH:ssa ja eri katalyyseillä. Työssä tutkittiin näiden vaikutusta kemialliseen hapenkulutukseen (COD), Biologiseen hapenkulutukseen (BOD), Välittömästi saatavana olevan biologisen hapenkulutukseen (IABOD), ligniiniin, täysin orgaanisen hiileen (TOC) ja rasvaliukoisten uuteaineiden (LWEs) pitoisuuteen. Tuloksina kokeellisesta työstä saatiin korkeimmat COD:n alenemat ja BOD/COD (biohajoavuus) suurimmilla lämpötilaolosuhteilla (COD:n alenema 70 % ja BOD/COD 97 % 200 °C:ssa ja hapen 10 bar osapaineella). Tutkimuksessa, jossa selvitettiin hapen osapaineen vaikutusta saatiin tuloksena, että hapen osapaineen kasvu parantaa orgaanisen kuormituksen poistoa: COD poisto oli olosuhteilla130°C, 5bar 5 %, olosuhteilla 130 °C, 15bar 15 %, olosuhteilla 170 °C, 5bar 20 % ja olosuhteilla 170 °C, 15bar 50 %. Lähes täydellinen LWEs –poisto saavutettiin 150 °C ja 10bar olosuhteilla, vaikka tässä lämpötilassa ei saavutettu korkeata orgaanisen kuormituksen poistoa. Emäksinen pH vaikutti suosivan hapettavia reaktioita, koska korkein COD:n poisto saavutettiin näissä olosuhteilla; kuitenkin alkalisen väliaineen tehokkuudelle löydettiin tärkeä lämpötilariippuvuus.

Performance Analysis of Two Quantum Reaction Dynamics Codes: Time-Dependent and Time-Independent Strategies

The computer simulation of reaction dynamics has nowadays reached a remarkable degree of accuracy. Triatomic elementary reactions are rigorously studied with great detail on a straightforward basis using a considerable variety of Quantum Dynamics computational tools available to the scientific community. In our contribution we compare the performance of two quantum scattering codes in the computation of reaction cross sections of a triatomic benchmark reaction such as the gas phase reaction Ne + H2+ %12. NeH++ H. The computational codes are selected as representative of time-dependent (Real Wave Packet [ ]) and time-independent (ABC [ ]) methodologies. The main conclusion to be drawn from our study is that both strategies are, to a great extent, not competing but rather complementary. While time-dependent calculations advantages with respect to the energy range that can be covered in a single simulation, time-independent approaches offer much more detailed information from each single energy calculation. Further details such as the calculation of reactivity at very low collision energies or the computational effort related to account for the Coriolis couplings are analyzed in this paper.

The Swiss reform of the allocation of tasks : The conventions-programs as a new partnership model for vertical cooperation ?

This research examines the impacts of the Swiss reform of the allocation of tasks which was accepted in 2004 and implemented in 2008 to "re-assign" the responsibilities between the federal government and the cantons. The public tasks were redistributed, according to the leading and fundamental principle of subsidiarity. Seven tasks came under exclusive federal responsibility; ten came under the control of the cantons; and twenty-two "common tasks" were allocated to both the Confederation and the cantons. For these common tasks it wasn't possible to separate the management and the implementation. In order to deal with nineteen of them, the reform introduced the conventions-programs (CPs), which are public law contracts signed by the Confederation with each canton. These CPs are generally valid for periods of four years (2008-11, 2012-15 and 2016-19, respectively). The third period is currently being prepared. By using the principal-agent theory I examine how contracts can improve political relations between a principal (Confederation) and an agent (canton). I also provide a first qualitative analysis by examining the impacts of these contracts on the vertical cooperation and on the implication of different actors by focusing my study on five CPs - protection of cultural heritage and conservation of historic monuments, encouragement of the integration of foreigners, economic development, protection against noise and protection of the nature and landscape - applied in five cantons, which represents twenty-five cases studies.

Reaction time asymmetries between expansion and contraction

Different asymmetries between expansion and contraction (radial motions) have been reported in the literature. Often these patterns have been regarded as implying different channels for each type of radial direction (outward versus inwards) operating at a higher level of visual motion processing. In two experiments (detection and discrimination tasks) we report reaction time asymmetries between expansion and contraction. Power functions were fitted to the data. While an exponent of 0.5 accounted for the expansion data better, a value of unity yielded the best fit for the contraction data. Instead of interpreting these differences as corresponding to different higher order motion detectors, we regard these findings as reflecting the fact that expansion and contraction tap two distinct psychophysical input channels underlying the processing of fast and slow velocities respectively.

Lower incisor dentoalveolar compensation and symphysis dimensions among Class I and III malocclusion patients with different facial vertical skeletal patterns

Objective: To compare lower incisor dentoalveolar compensation and mandible symphysis morphology among Class I and Class III malocclusion patients with different facial vertical skeletal patterns. Materials and Methods: Lower incisor extrusion and inclination, as well as buccal (LA) and lingual (LP) cortex depth, and mandibular symphysis height (LH) were measured in 107 lateral cephalometric x-rays of adult patients without prior orthodontic treatment. In addition, malocclusion type (Class I or III) and facial vertical skeletal pattern were considered. Through a principal component analysis (PCA) related variables were reduced. Simple regression equation and multivariate analyses of variance were also used. Results: Incisor mandibular plane angle (P < .001) and extrusion (P  =  .03) values showed significant differences between the sagittal malocclusion groups. Variations in the mandibular plane have a negative correlation with LA (Class I P  =  .03 and Class III P  =  .01) and a positive correlation with LH (Class I P  =  .01 and Class III P  =  .02) in both groups. Within the Class III group, there was a negative correlation between the mandibular plane and LP (P  =  .02). PCA showed that the tendency toward a long face causes the symphysis to elongate and narrow. In Class III, alveolar narrowing is also found in normal faces. Conclusions: Vertical facial pattern is a significant factor in mandibular symphysis alveolar morphology and lower incisor positioning, both for Class I and Class III patients. Short-faced Class III patients have a widened alveolar bone. However, for long-faced and normal-faced Class III, natural compensation elongates the symphysis and influences lower incisor position.

Pathogenic attack and carbon reallocation in soybean leaves (Glycine max. L.): Reinitiation of the glyoxylate cycle as a defence reaction

Pathogenic attack by the fungus Botrytis cinerea (primary pathogen) on soybean leaves (Glycine max. L.; cv. Maple arrow) results in a hypersensitive response (necrotising infected leaves), in the establishment of local acquired resistance, as well as in the systemic induction of genes coding for pathogenesis-related proteins. It now appears that, concomitantly with these already well documented defence reactions, the pathogenic attack also induces the carbon reallocation mechanism based on the reinitiation of the glyoxylate cycle (pseudo-senescence of the infected leaves).

Granulomatous Reaction to Pneumocystis jirovecii Diagnosed in a Bronchoalveolar Lavage: A Case Report.

BACKGROUND: Granulomatous reaction to Pneumocystis jirovecii is a rare but well-known pathological finding encountered in the setting of immunosuppression, HIV infection being the most common cause. It can also potentially complicate the treatment of hematological malignancies, typically when drugs lowering the count and function of lymphocytes are used. Lung biopsy is considered the gold standard for the diagnosis of granulomatous P. jirovecii pneumonia, whereas the diffuse alveolar form is usually detected cytologically in bronchoalveolar lavage (BAL). CASE: A female patient pursuing R-CHOP chemotherapy for the treatment of multiple hematological malignancies developed a rapidly progressing dyspnea. Chest CT scans revealed a worsening of a known infiltrative lung disease thought to be secondary to her chemotherapy. Alterations compatible with a drug-induced interstitial lung disease and well-formed focally necrotizing granulomas were observed on an open lung biopsy, but no microorganism was identified with special stains. Eventually, a granulomatous reaction to P. jirovecii was found in a BAL and allowed appropriate treatment with rapid improvement of the dyspnea. CONCLUSION: Because granulomas are tissue-bound structures, they are rarely described in BAL. This article describes the first reported cytological diagnosis of a granulomatous reaction to P. jirovecii and the potential diagnostic interest of such a peculiar finding.

The vertical dimension of social relations and accurate interpersonal perception: A meta-analysis (Publishd online: 24 Oct. 2014)

There is little consensus regarding how verticality (social power, dominance, and status) is related to accurate interpersonal perception. The relation could be either positive or negative, and there could be many causal processes at play. The present article discusses the theoretical possibilities and presents a meta-analysis of this question. In studies using a standard test of interpersonal accuracy, higher socioeconomic status (SES) predicted higher accuracy defined as accurate inference about the meanings of cues; also, higher experimentally manipulated vertical position predicted higher accuracy defined as accurate recall of others' words. In addition, although personality dominance did not predict accurate inference overall, the type of personality dominance did, such that empathic/responsible dominance had a positive relation and egoistic/aggressive dominance had a negative relation to accuracy. In studies involving live interaction, higher experimentally manipulated vertical position produced lower accuracy defined as accurate inference about cues; however, methodological problems place this result in doubt.

Avaliação radiográfica da idade óssea em crianças infectadas pelo HIV por via vertical

OBJETIVO: O presente trabalho teve por objetivo avaliar o desenvolvimento de crianças infectadas pelo vírus da imunodeficiência adquirida (HIV) por contaminação vertical, comparando-se dois métodos determinantes da idade óssea. MATERIAIS E MÉTODOS: Analisou-se uma amostra de 100 crianças, com idades variando de 4 anos e 2 meses a 11 anos e 9 meses, que realizaram radiografias de mão e punho tecnicamente padronizadas e que, posteriormente, foram analisadas segundo os critérios dos métodos de Greulich e Pyle (1959) e de Eklöf e Ringertz (1967). RESULTADOS: Os resultados obtidos mostraram diferenças estatísticas entre os métodos de análise radiográfica do desenvolvimento esquelético utilizados, com destaque para a maior sensibilidade em relação ao método de Eklöf e Ringertz (p < 0,05). O grupo feminino apresentou diferenças estatisticamente significantes entre os casos controle e HIV+ (sete casos) quando avaliados por este método (p < 0,05). CONCLUSÃO: Constatou-se, com a presente pesquisa, que houve a influência do HIV sobre o desenvolvimento esquelético neste grupo de pacientes.

Vertical relations and local competition : an empirical approach

The analysis of vertical industry relations forms an essential element in the field of industrial organization. This paper tests hypotheses derived from transaction cost theory and the principal-agent problem in Chile’s petrol market. It shows that local competition plays an important role in the choice of a disintegrated vertical structure, and that low levels of service investment have the same effect. Conversely, the number of own-brand outlets and a high level of investment in services reduce the probability of disintegration. The paper demonstrates that vertical disintegration has a null effect on wholesale petrol prices and a positive effect on retail petrol prices of between 1.6 and 7 per cent, depending on fuel type.

Oligonucleotide cyclization: The thiol-maleimide reaction revisited

A novel method to synthesize cyclic oligonucleotides (5- to 26-mer) using the thiol-maleimide reaction is described. The target molecules were obtained after subsequent removal of thiol and maleimide protecting groups from 5′-maleimido-3′-thiol-derivatized linear precursors. Retro-Diels-Alder conditions deprotecting the maleimide simultaneously promoted cyclization cleanly and in high yield.