Studies of new inorganic species using relativistic quantum chemistry

In the present work the methods of relativistic quantum chemistry have been applied to a number of small systems containing heavy elements, for which relativistic effects are important. First, a thorough introduction of the methods used is presented. This includes some of the general methods of computational chemistry and a special section dealing with how to include the effects of relativity in quantum chemical calculations. Second, after this introduction the results obtained are presented. Investigations on high-valent mercury compounds are presented and new ways to synthesise such compounds are proposed. The methods described were applied to certain systems containing short Pt-Tl contacts. It was possible to explain the interesting bonding situation in these compounds. One of the most common actinide compounds, uranium hexafluoride was investigated and a new picture of the bonding was presented. Furthermore the rareness of uranium-cyanide compounds was discussed. In a foray into the chemistry of gold, well known for its strong relativistic effects, investigations on different gold systems were performed. Analogies between Au$^+$ and platinum on one hand and oxygen on the other were found. New systems with multiple bonds to gold were proposed to experimentalists. One of the proposed systems was spectroscopically observed shortly afterwards. A very interesting molecule, which was theoretically predicted a few years ago is WAu$_{12}$. Some of its properties were calculated and the bonding situation was discussed. In a further study on gold compounds it was possible to explain the substitution pattern in bis[phosphane-gold(I)] thiocyanate complexes. This is of some help to experimentalists as the systems could not be crystallised and the structure was therefore unknown. Finally, computations on one of the heaviest elements in the periodic table were performed. Calculation on compounds containing element 110, darmstadtium, showed that it behaves similarly as its lighter homologue platinum. The extreme importance of relativistic effects for these systems was also shown.

Theory and Analysis of Classic Heavy Metal Harmony

This thesis explores melodic and harmonic features of heavy metal, and while doing so, explores various methods of music analysis; their applicability and limitations regarding the study of heavy metal music. The study is built on three general hypotheses according to which 1) acoustic characteristics play a significant role for chord constructing in heavy metal, 2) heavy metal has strong ties and similarities with other Western musical styles, and 3) theories and analytical methods of Western art music may be applied to heavy metal. It seems evident that in heavy metal some chord structures appear far more frequently than others. It is suggested here that the fundamental reason for this is the use of guitar distortion effect. Subsequently, theories as to how and under what principles heavy metal is constructed need to be put under discussion; analytical models regarding the classification of consonance and dissonance and chord categorization are here revised to meet the common practices of this music. It is evident that heavy metal is not an isolated style of music; it is seen here as a cultural fusion of various musical styles. Moreover, it is suggested that the theoretical background to the construction of Western music and its analysis can offer invaluable insights to heavy metal. However, the analytical methods need to be reformed to some extent to meet the characteristics of the music. This reformation includes an accommodation of linear and functional theories that has been found rather rarely in music theory and musicology.

Haptiisit ja hapteemit : tapaustutkimus kuurosokean henkilön kosketukseen perustuvan kommunikaation kehityksestä

Haptices and haptemes: A case study of developmental process in touch-based communication of acquired deafblind people This research is the first systematic, longitudinal process and development description of communication using touch and body with an acquired deafblind person. The research consists of observational and analysed written and video materials mainly from two informants´ experiences during period of 14 years. The research describes the adaptation of Social-Haptic methods between a couple, and other informants´ experiences, which have been collated from biographies and through giving national and international courses. When the hearing and sight deteriorates due to having an acquired deafblind condition, communication consists of multi-systematic and adaptive methods. A person`s expressive language, spoken or Sign Language, usually remains unchanged, but the methods of receiving information could change many times during a person s lifetime. Haptices are made from haptemes that determines which regulations are analysed. When defining haptemes the definition, classification and varied meanings of touch were discovered. Haptices include sharing a personal body space, meaning of touch-contact, context and using different communication channels. Communication distances are classified as exact distance, estimated distance and touch distance. Physical distance can be termed as very long, long, medium or very close. Social body space includes the body areas involved in sending and receiving haptices and applying different types of contacts. One or two hands can produce messages by using different hand shapes and orientations. This research classifies how the body can be identified into different areas such as body orientation, varied body postures, body position levels, social actions and which side of the body is used. Spatial body space includes environmental and situational elements. Haptemes of movements are recognised as the direction of movements, change of directions on the body, directions between people, pressure, speed, frequency, size, length, duration, pause, change of rhythm, shape, macro and micro movements. Haptices share multidimensional meanings and emotions. Research describes haptices in different situations enhancing sensory information and functioning also as an independent language. Haptices includes social-haptic confirmation system, social quick messages, body drawing, contact to the people and the environment, guiding and sharing art experiences through movements. Five stages of emotional differentiation were identified as very light, light, medium, heavy and very heavy touch. Haptices give the possibility to share different art, hobby and game experiences. A new communication system development based on the analysis of the research data is classified into different phases. These are experimental initiation, social deconstruction, developing the description of Social-Haptic communication and generalisation of the theory as well as finding and conceptualising the haptices and haptemes. The use and description of haptices is a social innovation, which illustrates the adaptive function of the body and perceptual senses that can be taught to a third party. Keywords: deafblindness, hapteme, haptic, haptices, movement, social-haptic communication, social-haptic confirmation system, tactile, touch

Noviisiopettajana peruskoulussa : Aloittelevien opettajien autenttisia kokemuksia ensimmäisestä opettajavuodesta

As a Novice Teacher at Comprehensive School: The authentic experiences of the beginning teachers during their first year of teaching The aim of this study is to explicate the novice year of teaching in the light of teachers´ authentic experiences. The subject of this investigation is the teachers´ subjective world of experience during their first academic year of teaching and the sharing of these experiences in collaborative consulting meetings. The themes discussed in the meetings were introduced into the collaborative group by the novice teachers themselves, and the progress of discussion was con-trolled by them. The research data was gathered in a consultative working group where the way a novice teacher starts to interpret, analyze and identify his/her own complex and dynamic teaching situations was observed. The research data gathered in this way illuminates novice teachers´ world of experience and mental picture as well as the unconscious sides of school life. In a theoretical frame of reference, the work of a teacher is identified, according to systemic scientific thought, as a dynamic triangle in which the basic elements are the personality of the teacher, the role of the teacher and the school as an organization. These basic elements form a whole within which the teacher works. The dynamics of this triangle in a teacher’s work are brought to light through the study of the phenomena of groups and group dynamics since a teacher works either as a member of a group (working community), as a leader of a group (teaching situations) or in a network (parent – teacher cooperation). Therefore, tension and force are always present in teaching work. The main research problem was to explain how a novice teacher experiences his/her first working year as a teacher. The participants (n=5) were teaching at five different comprehensive schools in the city of Helsinki. This was their first long-term post as a teacher. The research data consists of seven collaborative consulting meetings, as well as recordings and transcripts of the meetings. A classificatory framework was developed for data analysis which enabled a sys-tematic qualitative content analysis based on theory and material. In addition to the consulting meetings, the teachers were interviewed at the beginning and at the end of the process of collecting the research material. The interviews were used to interpret the meanings of the content analysis based on raw data. The findings show that there is a gap between teacher education and the reality of school life, which causes difficulties for a novice teacher during his/her first teaching year. The gap is rather a global educational problem than a national one, and therefore it is independent of cultural factors. Novice teachers desire a well-structured theory of teacher education and a clear programme where the themes and content delve deeper and deeper into the subject matter during the study years. According to the novice teachers, teacher education frequently consists of sporadic and unconnected study and class situations. An individual content weakness of teacher education is the lack of insufficient initiation into evaluation processes. The novice teachers suggest that a student must be provided good-quality and competent guidance during the study years and during his or her induction. There should be a well-organized, structured and systematic induction program for novice teachers. The induction program should be overseen by an organization so that the requirements of a qualified induction can be met. The findings show that the novice teachers find the first year of teaching at comprehensive school emotionally loaded. The teachers experienced teaching as difficult work and found the workload heavy. Nevertheless, they enjoyed their job because, as they said, there were more pleasant than unpleasant things in their school day. Their main feeling at school was the joy of success in teaching. The novice teachers felt satisfaction with their pupils. The teachers experienced the more serious feelings of anger and disgust when serious violence took place. The most difficult situations arose from teaching pupils who had mental health problems. The toughest thing in the teacher´s work was teaching groups that are too heterogeneous. The most awkward problems in group dynamics happened when new immigrants, who spoke only their own languages, were integrated into the groups in the middle of the school year. Teachers wanted to help children who needed special help with learning but restated at the same time that the groups being taught shouldn’t be too heterogeneous. The teachers wished for help from school assistants so that they could personally concentrate more on teaching. Not all the parents took care of their children according to the comprehensive school law. The teachers found it hard to build a confidential relationship between home and school. In this study, novice teachers found it hard to join the teaching staff at school. Some of the teachers on staff were very strong and impulsive, reacting loudly and emotionally. These teachers provoked disagreement, conflicts, power struggles and competition among the other teachers. Although the novice teachers of the study were all qualified teachers, three of them were not interested in a permanent teaching job. For these teachers teaching at a primary school was just a project, a short period in their working life. They will remain in the teaching profession as long as they are learning new things and enjoying their teaching job. This study is an independent part of the research project on Interplay – Connecting Academic Teacher Education and Work, undertaken by the Department of Applied Sciences of Education at the University of Helsinki. Key words: novice teacher, emotions, groups and group dynamics, authority, co-operation between home and school, teacher community, leadership at school, induction, consulting

Technicolor

In technicolor theories the scalar sector of the Standard Model is replaced by a strongly interacting sector. Although the Standard Model has been exceptionally successful, the scalar sector causes theoretical problems that make these theories seem an attractive alternative. I begin my thesis by considering QCD, which is the known example of strong interactions. The theory exhibits two phenomena: confinement and chiral symmetry breaking. I find the low-energy dynamics to be similar to that of the sigma models. Then I analyze the problems of the Standard Model Higgs sector, mainly the unnaturalness and triviality. Motivated by the example of QCD, I introduce the minimal technicolor model to resolve these problems. I demonstrate the minimal model to be free of anomalies and then deduce the main elements of its low-energy particle spectrum. I find the particle spectrum contains massless or very light technipions, and also technibaryons and techni-vector mesons with a high mass of over 1 TeV. Standard Model fermions remain strictly massless at this stage. Thus I introduce the technicolor companion theory of flavor, called extended technicolor. I show that the Standard Model fermions and technihadrons receive masses, but that they remain too light. I also discuss flavor-changing neutral currents and precision electroweak measurements. I then show that walking technicolor models partly solve these problems. In these models, contrary to QCD, the coupling evolves slowly over a large energy scale. This behavior adds to the masses so that even the light technihadrons are too heavy to be detected at current particle accelerators. Also all observed masses of the Standard Model particles can be generated, except for the bottom and top quarks. Thus it is shown in this thesis that, excluding the masses of third generation quarks, theories based on walking technicolor can in principle produce the observed particle spectrum.

Computational Methods for Locating and Analyzing Conserved Gene Regulatory DNA Elements

This thesis presents methods for locating and analyzing cis-regulatory DNA elements involved with the regulation of gene expression in multicellular organisms. The regulation of gene expression is carried out by the combined effort of several transcription factor proteins collectively binding the DNA on the cis-regulatory elements. Only sparse knowledge of the 'genetic code' of these elements exists today. An automatic tool for discovery of putative cis-regulatory elements could help their experimental analysis, which would result in a more detailed view of the cis-regulatory element structure and function. We have developed a computational model for the evolutionary conservation of cis-regulatory elements. The elements are modeled as evolutionarily conserved clusters of sequence-specific transcription factor binding sites. We give an efficient dynamic programming algorithm that locates the putative cis-regulatory elements and scores them according to the conservation model. A notable proportion of the high-scoring DNA sequences show transcriptional enhancer activity in transgenic mouse embryos. The conservation model includes four parameters whose optimal values are estimated with simulated annealing. With good parameter values the model discriminates well between the DNA sequences with evolutionarily conserved cis-regulatory elements and the DNA sequences that have evolved neutrally. In further inquiry, the set of highest scoring putative cis-regulatory elements were found to be sensitive to small variations in the parameter values. The statistical significance of the putative cis-regulatory elements is estimated with the Two Component Extreme Value Distribution. The p-values grade the conservation of the cis-regulatory elements above the neutral expectation. The parameter values for the distribution are estimated by simulating the neutral DNA evolution. The conservation of the transcription factor binding sites can be used in the upstream analysis of regulatory interactions. This approach may provide mechanistic insight to the transcription level data from, e.g., microarray experiments. Here we give a method to predict shared transcriptional regulators for a set of co-expressed genes. The EEL (Enhancer Element Locator) software implements the method for locating putative cis-regulatory elements. The software facilitates both interactive use and distributed batch processing. We have used it to analyze the non-coding regions around all human genes with respect to the orthologous regions in various other species including mouse. The data from these genome-wide analyzes is stored in a relational database which is used in the publicly available web services for upstream analysis and visualization of the putative cis-regulatory elements in the human genome.

Elements of Volatility at High Frequency

Volatility is central in options pricing and risk management. It reflects the uncertainty of investors and the inherent instability of the economy. Time series methods are among the most widely applied scientific methods to analyze and predict volatility. Very frequently sampled data contain much valuable information about the different elements of volatility and may ultimately reveal the reasons for time varying volatility. The use of such ultra-high-frequency data is common to all three essays of the dissertation. The dissertation belongs to the field of financial econometrics. The first essay uses wavelet methods to study the time-varying behavior of scaling laws and long-memory in the five-minute volatility series of Nokia on the Helsinki Stock Exchange around the burst of the IT-bubble. The essay is motivated by earlier findings which suggest that different scaling laws may apply to intraday time-scales and to larger time-scales, implying that the so-called annualized volatility depends on the data sampling frequency. The empirical results confirm the appearance of time varying long-memory and different scaling laws that, for a significant part, can be attributed to investor irrationality and to an intraday volatility periodicity called the New York effect. The findings have potentially important consequences for options pricing and risk management that commonly assume constant memory and scaling. The second essay investigates modelling the duration between trades in stock markets. Durations convoy information about investor intentions and provide an alternative view at volatility. Generalizations of standard autoregressive conditional duration (ACD) models are developed to meet needs observed in previous applications of the standard models. According to the empirical results based on data of actively traded stocks on the New York Stock Exchange and the Helsinki Stock Exchange the proposed generalization clearly outperforms the standard models and also performs well in comparison to another recently proposed alternative to the standard models. The distribution used to derive the generalization may also prove valuable in other areas of risk management. The third essay studies empirically the effect of decimalization on volatility and market microstructure noise. Decimalization refers to the change from fractional pricing to decimal pricing and it was carried out on the New York Stock Exchange in January, 2001. The methods used here are more accurate than in the earlier studies and put more weight on market microstructure. The main result is that decimalization decreased observed volatility by reducing noise variance especially for the highly active stocks. The results help risk management and market mechanism designing.

Functional Outcome after Free Flap Reconstructions in Oral and Pharyngeal Cancer

Oral cancer ranks among the 10 most common cancers worldwide. Since it is commonly diagnosed at locally advanced stage, curing the cancer demands extensive tissue resection. The emergent defect is reconstructed generally with a free flap transfer. Repair of the upper aerodigestive track with maintenance of its multiform activities is challenging. The aim of the study was to extract comprehensive treatment outcomes for patients having undergone microvascular free flap transfer because of large oral cavity or pharyngeal cancer. Ninety-four patients were analyzed for postoperative survival and complications. Forty-four patients were followed-up and analyzed for functional outcome, which was determined in terms of quality of life, speech, swallowing, and intraoral sensation. Quality of life was assessed using the University of Washington Head and Neck Questionnaire. Speech was analyzed for aerodynamic parameters and for nasal acoustic energy, as well as perceptually for articulatory proficiency, voice quality, and intelligibility. Videofluorography was performed to determine the swallowing ability. Intraoral sensation was measured by moving 2-point discrimination. The 3-year overall survival was over 40%. The 1-year disease-free survival was 43%. Postoperative complications arose in over half of the patients. Flap success rate was high. Perioperative mortality varied between 2% and 11%. Unemployment and heavy drinking were the strongest predictors of survival. Sociodemographic factors were found to associate with quality of life. The global quality of life score deteriorated and did not return to the preoperative level. Significant reduction was detectable in the domains measuring chewing and speech, and in appearance and shoulder function. The basic elements necessary for normal speech were maintained. Speech intelligibility reduced and was related to the misarticulations of the /r/ and /s/ phonemes. Deviant /r/ and /s/ persisted in most patients. Hoarseness and hypernasality occurred infrequently. One year postoperatively, 98% of the patients had achieved oral nutrition and half of them were on a regular masticated diet. Overt and silent aspiration was encountered throughout the follow-up. At 12-month swallow test, 44% of the patients aspirated, 70% of whom silently. Of these patients, 15% presented with pulmonary changes referring to aspiration. Intraoral sensation weakened but was unrelated to oral functions. The results provide new data for oral reconstructions and highlight the importance of the functional outcome of the treatment for an oral cancer patient. The mouth and the pharynx encompass a unit of utmost functional complexity. Surgery should continue to make progress in this area, and methods that lead to good function should be developed. Operational outcome should always be evaluated in terms of function.