Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Determinants of credit default swap spread, the effect of the financial crisis in the us markets

The purpose of this study is to define what determinants affect the Credit spread. There are two theoretical frameworks to study this: structural models and reduced form models. Structural models indicate that the main determinants are company leverage, volatility and risk-free interest rate, and other market and firm-specific variables. The purpose is to determine which of these theoretical determinants can explain the CDS spread and also how these theoretical determinants are affected by the financial crisis in 2007. The data is collected from 30 companies in the US Markets, mainly S&P Large Cap. The sample time-frame is 31.1.2004 – 31.12.2009. Empirical studies indicate that structural models can explain the CDS spreads well. Also, there were significant differences between bear and bull markets. The main determinants explaining CDS spreads were leverage and volatility. The other determinants were significant, depending on the sample period. However, these other variables did not explain the spread consistently.

Financier’s credit risk: A Performance-Based Classification Model

The purpose of this study is to view credit risk from the financier’s point of view in a theoretical framework. Results and aspects of the previous studies regarding measuring credit risk with accounting based scoring models are also examined. The theoretical framework and previous studies are then used to support the empirical analysis which aims to develop a credit risk measure for a bank’s internal use or a risk management tool for a company to indicate its credit risk to the financier. The study covers a sample of Finnish companies from 12 different industries and four different company categories and employs their accounting information from 2004 to 2008. The empirical analysis consists of six stage methodology process which uses measures of profitability, liquidity, capital structure and cash flow to determine financier’s credit risk, define five significant risk classes and produce risk classification model. The study is confidential until 15.10.2012.

Characteristics of credit risk assessment methods of major Nordic banks in allocating capital when extending credits to large corporations

Credit risk assessment is an integral part of banking. Credit risk means that the return will not materialise in case the customer fails to fulfil its obligations. Thus a key component of banking is setting acceptance criteria for granting loans. Theoretical part of the study focuses on key components of credit assessment methods of Banks in the literature when extending credits to large corporations. Main component is Basel II Accord, which sets regulatory requirement for credit risk assessment methods of banks. Empirical part comprises, as primary source, analysis of major Nordic banks’ annual reports and risk management reports. As secondary source complimentary interviews were carried out with senior credit risk assessment personnel. The findings indicate that all major Nordic banks are using combination of quantitative and qualitative information in credit risk assessment model when extending credits to large corporations. The relative input of qualitative information depends on the selected approach to the credit rating, i.e. point-in-time or through-the-cycle.

Intercultural bridges in teenagers' theatrical events : performing self and constructing cultural identity through a creative drama process

The overriding aim of this drama educational case study is to deepen the understanding of meaning making in a creative intercultural youth theatre process and to examine it in the context of the 10th European Children's TheatreEncounter. The research task is to give a theoretical description of some key features of a creative drama process as the basis for theory about meaning makingin physical theatre. The first task is to illuminate the culture-historical connections of the multilayered practice of the EDERED-association. The second taskis to analyse and interpret theatrical meaning making. The ethnographical research site is regarded as a theatrical event. The analysis of the theatrical eventis divided into four segments: cultural contexts, contextual theatricality, theatrical playing and playing culture. These segments are connected with four research questions: What are the cultural contexts of a creative drama process? How can the organisation of the Encounter, genres, aesthetic codes and perception ofcodes be seen to influence the lived experiences of the participants? What are some of the key phases and characteristics in a creative practice? What kind of cultural learning can be interpreted from the performance texts? The interpretative question concerns identity and community (re)construction. How are the categories, `community´ and `child´ constructed in the Encounter culture? In this drama educational case study the research material (transcribed interviews, coded questionnaire answers, participant drawings, videotaped process text and performance texts) are examined in a multi-method analysis in the meta-theoretical framework of Dewey's naturalistic pragmatism. A three-dimensional research interest through a combination of lived experiences, social contexts and cultural-aesthetical practices compared with drama-educational practices required the methodological project of cultural studies. Furthermore, the critical interpretation of cultural texts is divided into three levels of analyses which are called description, structural analysis and theoretical interpretation. Dialogic validity (truthfulness, self-reflexivity and polyvocality) is combined with contextual validity (sensitivity to social context and awareness of historicity) and with deconstructive validity (awareness of the social discourses). My research suggests that itis possible, by means of physical theatre, to construct symbolic worlds where questions about intercultural identity and multilingual community are examined and where provisional answers are constructed in social interaction.

Airway surgery for obstructive sleep apnea and partial upper airway obstruction during sleep

This study analyzed the feasibility and efficacy of surgical therapies in patients with sleep-disordered breathing ranging from partial upper airway obstruction during sleep to severe obstructive sleep apnea syndrome. The surgical procedures evaluated were tracheostomy, laser-assisted uvulopalatoplasty (LUPP) and uvulopalatopharyngoplasty (UPPP) with laser or ultrasound scalpel. Obstructive sleep apnea and partial upper airway obstruction during sleep were measured with the static charge-sensitive bed (SCSB) and pulse oximeter. The patients with severe obstructive sleep apnea syndrome were treated with tracheostomy. Palatal surgery was performed only if the upper airway narrowing occurred exclusively at the soft palate level in patients with partial upper airway obstruction during sleep. The ultrasound scalpel technique was compared to laser-assisted UPPP. The efficacy of LUPP to reduce partial upper airway obstruction during sleep was assessed and histology of uvulopalatal specimen was compared to body fat distributional parameters and sleep study findings. Tracheostomy was effective therapy in severe obstructive sleep apnea. Partial upper airway obstruction and arterial oxyhemoglobin desaturation index during sleep decreased significantly after LUPP. The minimal retropalatal airway dimension increased and soft palate collapsibility decreased at the level where the velopharyngeal obstruction had occurred before the surgery. Ultrasound scalpel did not offer any significant benefits over the laser-assisted technique, except fewer postoperative haemorrhage events. The loose connective tissue as a manifestation of edema was the only histological finding showing correlation with partial upper airway obstruction parameters of SCSB. Tracheostomy remains a life-saving therapy and also long-term option when adherence to CPAP fails in patients with obstructive sleep apnea syndrome. LUPP effectively reduces partial upper airway obstruction during sleep provided that obstruction at the other levels than the soft palate and uvula were preoperatively excluded. Technically the ultrasound scalpel or laser surgeries are equal. In patients with partial upper airway obstruction the loose connective tissue is more important than fat accumulation in the soft palate. This supports the hypothesis that edema is a primary trigger for aggravation of upper airway narrowing during sleep at the soft palate level and evolution towards partial or complete upper airway obstruction during sleep.

From Fluid Dynamics to Human Psychology.What Drives Financial Markets Towards Extreme Events

For decades researchers have been trying to build models that would help understand price performance in financial markets and, therefore, to be able to forecast future prices. However, any econometric approaches have notoriously failed in predicting extreme events in markets. At the end of 20th century, market specialists started to admit that the reasons for economy meltdowns may originate as much in rational actions of traders as in human psychology. The latter forces have been described as trading biases, also known as animal spirits. This study aims at expressing in mathematical form some of the basic trading biases as well as the idea of market momentum and, therefore, reconstructing the dynamics of prices in financial markets. It is proposed through a novel family of models originating in population and fluid dynamics, applied to an electricity spot price time series. The main goal of this work is to investigate via numerical solutions how well theequations succeed in reproducing the real market time series properties, especially those that seemingly contradict standard assumptions of neoclassical economic theory, in particular the Efficient Market Hypothesis. The results show that the proposed model is able to generate price realizations that closely reproduce the behaviour and statistics of the original electricity spot price. That is achieved in all price levels, from small and medium-range variations to price spikes. The latter were generated from price dynamics and market momentum, without superimposing jump processes in the model. In the light of the presented results, it seems that the latest assumptions about human psychology and market momentum ruling market dynamics may be true. Therefore, other commodity markets should be analyzed with this model as well.

Correlation between the Alvarado Scale and the macroscopic aspect of the appendix in patients with appendicitis

Objective: To evaluate the possible association between the scale of Alvarado (EA) and macroscopic appearance (MA) of the appendix in patients with acute appendicitis.Methods: after receiving the diagnosis of acute appendicitis, EA data were collected. During appendectomy, MA data were collected. Data from patients without appendicitis were excluded. The Spearman correlation test was used to compare EA with Appendix MA (p < 0.05). Other variables were represented by simple frequency. The confidence interval (CI) of 95% was calculated for the correlation test.Results: Data were collected from 67 consecutive patients. The mean age was 37.1 ± 12.5 years and 77.6% of patients were male. The Spearman correlation test used for EA and MA was + 0.77 (95% CI 0.65-0.85, p < 0.0001).Conclusion: although correlation was not perfect, our data indicate that a high score on the scale of Alvarado in patients with appendicitis is correlated with advanced stages of the inflammatory process of acute appendicitis.

Correlation between the oropharyngo-laryngoscopic findings and the severity of obstructive sleep apnea

Objective: To correlate anatomical and functional changes of the oral cavity, pharynx and larynx to the severity of obstructive sleep apnea syndrome (OSAS). Methods : We conducted a cross-sectional study of 66 patients of both genders, aged between 21 and 59 years old with complaints of snoring and / or apnea. All underwent full clinical evaluation, including physical examination, nasolarybgoscopy and polisonography. We classified individuals into groups by the value of the apnea-hypopnea index (AHI), calculated measures of association and analyzed differences by the Kruskal-Wallis and chi-square tests. Results : all patients with obesity type 2 had OSAS. We found a relationship between the uvula projection during nasoendoscopy and OSAS (OR: 4.9; p-value: 0.008; CI: 1.25-22.9). In addition, there was a major strength of association between the circular shape of the pharynx and the presence of moderate or severe OSAS (OR: 9.4, p-value: 0.002), although the CI was wide (1.80-53.13). The septal deviation and lower turbinate hypertrophy were the most frequent nasal alterations, however unrelated to gravity. Nasal obstruction was four times more common in patients without daytime sleepiness. The other craniofacial anatomical changes were not predictors for the occurrence of OSAS. Conclusion : oral, pharyngeal and laryngeal disorders participate in the pathophysiology of OSAS. The completion of the endoscopic examination is of great value to the evaluation of these patients.

Measuring the performance of corporate events : an empirical study of measuring practices in Finnish companies

Corporate events as an effective part of marketing communications strategy seem to be underestimated in Finnish companies. In the rest of the Europe and the USA, investments in events are increasing, and their share of the marketing budget is significant. The growth of the industry may be explained by the numerous advantages and opportunities that events provide for attendees, such as face-to-face marketing, enhancing corporate image, building relationships, increasing sales, and gathering information. In order to maximize these benefits and return on investment, specific measurement strategies are required, yet there seems to exist a lack of understanding of how event performance should be perceived or evaluated. To address this research gap, this research attempts to describe the perceptions of and strategies for evaluating corporate event performance in the Finnish events industry. First, corporate events are discussed in terms of definitions and characteristics, typologies, and their role in marketing communications. Second, different theories on evaluating corporate event performance are presented and analyzed. Third, a conceptual model is presented based on the literature review, which serves as a basis for the empirical research conducted as an online questionnaire. The empirical findings are to a great extent in line with the existing literature, suggesting that there remains a lack of understanding corporate event performance evaluation, and challenges arise in determining appropriate measurement procedures for it. Setting clear objectives for events is a significant aspect of the evaluation process, since the outcomes of events are usually evaluated against the preset objectives. The respondent companies utilize many of the individual techniques that were recognized in theory, such as calculating the number of sales leads and delegates. However, some of the measurement tools may require further investments and resources, thus restricting their application especially in smaller companies. In addition, there seems to be a lack of knowledge of the most appropriate methods in different contexts, which take into account the characteristics of the organizing party as well as the size and nature of the event. The lack of inhouse expertise enhances the need for third-party service-providers in solving problems of corporate event measurement.

Correlation between placental thickness in the second and third trimester and fetal weight

PURPOSE: To investigate relationship between placental thickness during the second and third trimesters and placental and birth weights. METHODS: From January 2011 to June 2012, a total of 250 singleton pregnant women presented at our antenatal clinic were enrolled in this prospective study. All recruited women were assessed at the 1st trimester screening for baseline demographic and obstetric data. The placental thickness was measured trans-abdominally by placing the ultrasound transducer perpendicularly to the plane of the placenta, in the area of the cord insertion at second and third trimester. Pearson's correlation analysis was used to establish the degree of relationship between placental thickness and birth and placental weights. RESULTS: Of 250 recruited participants, 205 women were able to complete the study. The mean age of cases was 26.4±5.1. Values of mean birth and placental weights were 305.56±657.0 and 551.7±104.8 grams respectively. Ultrasonographic measures of placental thickness in second and third trimester and changes between them were 21.68±4.52, 36.26±6.46 and 14.67±5.67 mm respectively. There was a significant positive correlation between placental thickness and birth weight in the second and third trimesters (r=0.15, p=0.03; r=0.14, p=0.04 correspondingly). CONCLUSION: According to our study, birth weight has a positive relation with both second and third trimester placental thickness; however, placental thickness change could not predict low birth weight.

Immunohistochemical evaluation of e-cadherin, Ki-67 and PCNA in canine mammary neoplasias: correlation of prognostic factors and clinical outcome

E-cadherin is a cell-cell adhesion molecule and low e-cadherin expression is related to invasiveness and may indicate a bad prognosis in mammary neoplasms. The expression of cell proliferation markers PCNA and especially Ki-67, has also proved to have a strong prognostic value in this tumor class. The expression of these markers was related to the clinical-pathological characteristics of 73 surgically removed mammary tumors in female dogs by immunohistochemistry. There was no statistical correlation between these markers and death by neoplasm, survival time and disease-free interval. However, the loss of e-cadherin expression and marked Ki-67 expression (p=0.016) were considered statistically significant for the diagnosis (p=0.032). When evaluated as independent factors, there was evidence of the relationship between the loss of e-cadherin expression and high PCNA expression with changes in the body status (divided into obese, normal and cachectic) of female dogs (p=0.030); there was also evidence of the relationship between pseudopregnancy and e-cadherin alone (p=0.021) and for ulceration and PCNA alone (p=0.035). The significant correlation between the markers expression and these well known prognostic factors used individually or in combination suggests their prognostic value in canine mammary tumors.

Experimental poisoning of goats by Ipomoea carnea subsp. fistulosa in Argentina: a clinic and pathological correlation with special consideration on the central nervous system

Ipomoea carnea subsp. fistulosa, aguapei or mandiyura, is responsible for lysosomal storage in goats. The shrub contains several alkaloids, mainly swansonine which inhibits lysosomal α-mannosidase and Golgi mannosidase II. Poisoning occurs by inhibition of these hydrolases. There is neuronal vacuolation, endocrine dysfunction, cardiovascular and gastrointestinal injury, and immune disorders. Clinical signs and pathology of the experimental poisoning of goats by Ipomoea carnea in Argentina are here described. Five goats received fresh leaves and stems of Ipomoea. At the beginning, the goats did not consume the plant, but later, it was preferred over any other forage. High dose induced rapid intoxication, whereas with low doses, the course of the toxicosis was more protracted. The goats were euthanized when they were recumbent. Cerebrum, cerebellum, medulla oblongata, pons and colliculi, were routinely processed for histology. In nine days, the following clinical signs developed: abnormal fascies, dilated nostrils and abnormal postures of the head, cephalic tremors and nystagmus, difficulty in standing. Subsequently, the goats had a tendency to fall, always to the left, with spastic convulsions. There was lack in coordination of voluntary movements due to Purkinje and deep nuclei neurons damage. The cochlear reflex originated hyperreflexia, abnormal posture, head movements and tremors. The withdrawal reflex produced flexor muscles hypersensitivity at the four legs, later depression and stupor. Abnormal responses to sounds were related to collicular lesions. Thalamic damage altered the withdrawal reflex, showing incomplete reaction. The observed cervical hair bristling was attributed to a thalamic regulated nociceptive response. Depression may be associated with agonists of lysergic acid contained in Ipomoea. These clinical signs were correlated with lesions in different parts of the CNS.

System-level characterization of Th2 cell development and immune cell responses to ZnO and TiO2 nanoparticles

Asthma and allergy are common diseases and their prevalence is increasing. One of the hypotheses that explains this trend is exposure to inhalable chemicals such as traffi c-related air pollution. Epidemiological research supports this theory, as a correlation between environmental chemicals and allergic respiratory diseases has been found. In addition to ambient airborne particles, one may be exposed to engineered nanosized materials that are actively produced due to their favorable physico-chemical properties compared to their bulk size counterparts. On the cellular level, improper activity of T helper (Th) cells has been connected to allergic reactions. Th cells can differentiate into functionally different effector subsets, which are identifi ed according to their characteristic cytokine profi les resulting in specifi c ability to communicate with other cells. Th2 cells activate humoral immunity and stimulate eradication of extracellular pathogens. However, persistent predominance of Th2 cells is involved in a development of number of allergic diseases. The cytokine environment at the time of antigen recognition is the major factor determining the polarization of a naïve Th cell. Th2 cell differentiation is initiated by IL4, which signals via transcription factor STAT6. Although the importance of this pathway has been evaluated in the mouse studies, the signaling components involved have been largely unknown. The aim of this thesis was to identify molecules, which are under the control of IL4 and STAT6 in Th cells. This was done by using system-level analysis of STAT6 target genes at genome, mRNA and protein level resulting in identifi cation of various genes previously not connected to Th2 cell phenotype acquisition. In the study, STAT6-mediated primary and secondary target genes were dissection from each other and a detailed transcriptional kinetics of Th2 cell polarization of naïve human CD4+ T cells was collected. Integration of these data revealed the hierarchy of molecular events that mediates the differentiation towards Th2 cell phenotype. In addition, the results highlighted the importance of exploiting proteomics tools to complement the studies on STAT6 target genes identifi ed through transcriptional profi ling. In the last subproject, the effects of the exposure with ZnO and TiO2 nanoparticles was analyzed in Jurkat T cell line and in primary human monocyte-derived macrophages and dendritic cells to evaluate their toxicity and potential to cause infl ammation. Identifi cation of ZnO-derived gene expression showed that the same nanoparticles may elicit markedly distinctive responses in different cell types, thus underscoring the need for unbiased profi ling of target genes and pathways affected. The results gave additional proof that the cellular response to nanosized ZnO is due to leached Zn2+ ions. The approach used in ZnO and TiO2 nanoparticle study demonstrated the value of assessing nanoparticle responses through a toxicogenomics approach. The increased knowledge of Th2 cell signaling will hopefully reveal new therapeutic nodes and eventually improve our possibilities to prevent and tackle allergic infl ammatory diseases.

Sovereign Credit Rating Announcements and Equity Market Response: Evidence from the European Markets

This thesis examines the equity market reactions on credit rating announcements. The study covers 12 European countries during the period of 2000-2012. By using an event study methodology and daily collected stock market returns, the impact of the sovereign credit rating announcements to national stock indices is examined. The thesis finds evidence for the rating downgrades having a statistically significant negative effect on the stock markets. This finding is in line with earlier literature (see Brooks, 2004). The paper also discusses whether the changes in the sovereign credit ratings are contagious, anticipated by the market, and persistent. There is some evidence found for the contagion effects in case of downgrades, but not for upgrades. Markets seem to anticipate rating upgrades, but not downgrades. In addition, market´s reaction towards rating announcements seems not to be persistent.