Iron(III) as Lewis acid catalyst in organosilicon and carbonyl chemistry

Iron is one of the most common elements in the earth’s crust and thus its availability and economic viability far exceed that of metals commonly used in catalysis. Also the toxicity of iron is miniscule, compared to the likes of platinum and nickel, making it very desirable as a catalyst. Despite this, prior to the 21st century, the applicability of iron in catalysis was not thoroughly investigated, as it was considered to be inefficient and unselective in desired transformations. In this doctoral thesis, the application of iron catalysis in combination with organosilicon reagents for transformations of carbonyl compounds has been investigated together with insights into iron catalyzed chlorination of silanes and silanols. In the first part of the thesis, the synthetic application of iron(III)-catalyzed chlorination of silanes (Si-H) and the monochlorination of silanes (SiH2) using acetyl chloride as the chlorine source is described. The reactions proceed under ambient conditions, although some compounds need to be protected from excess moisture. In addition, the mechanism and kinetics of the chlorination reaction are briefly adressed. In the second part of this thesis a versatile methodology for transformation of carbonyl compounds into three different compound classes by changing the conditions and amounts of reagents is discussed. One pot reductive benzylation, reductive halogenation and reductive etherification of ketones and aldehydes using silanes as the reducing agent, halide source or cocatalyst, were investigated. Also the reaction kinetics and mechanism of the reductive halogenation of acetophenone are briefly discussed.

Kalman filter for computational market dynamics

Kalman filter is a recursive mathematical power tool that plays an increasingly vital role in innumerable fields of study. The filter has been put to service in a multitude of studies involving both time series modelling and financial time series modelling. Modelling time series data in Computational Market Dynamics (CMD) can be accomplished using the Jablonska-Capasso-Morale (JCM) model. Maximum likelihood approach has always been utilised to estimate the parameters of the JCM model. The purpose of this study is to discover if the Kalman filter can be effectively utilized in CMD. Ensemble Kalman filter (EnKF), with 50 ensemble members, applied to US sugar prices spanning the period of January, 1960 to February, 2012 was employed for this work. The real data and Kalman filter trajectories showed no significant discrepancies, hence indicating satisfactory performance of the technique. Since only US sugar prices were utilized, it would be interesting to discover the nature of results if other data sets are employed.

Computational studies of deformation in stainless steel rings due to torch heating

A support ring of AISI 304L stainless steel that holds vertical, parallel wires arranged in a circle forming a cylinder is studied. The wires are attached to the ring with heat-induced shrinkage. When the ring is heated with a torch the heat affected zone tries to expand while the adjacent cool structure obstructs the expansion causing upsetting. During cooling, the ring shrinks smaller than its original size clamping the wires. The most important requirement for the ring is that it should be as round as possible and the deformations should occur as overall shrinkage in the ring diameter. A three-dimensional nonlinear transient sequential thermo-structural Abaqus model is used together with a Fortran code that enters the heat flux to each affected element. The local and overall deformations in one ring inflicted by the heating are studied with a small amount of inspection on residual stresses. A variety of different cases are chosen to be studied with the model constructed to provide directional knowledge; torch flux with the means of speed, location of the wires, heating location and structural factors. The decrease of heating speed increases heat flux that rises the temperature increasing shrinkage. In a single progressive heating uneven distribution of shrinkage appears to the start/end region that can be partially fixed with using speeded heating’s to strengthen the heating of that region. Location of the wires affect greatly to the caused shrinkage unlike heating location. The ring structure affects also greatly to the shrinkage; smaller diameter, bigger ring height, thinner thickness and greater number of wires increase shrinkage.

Structural and Computational Existence Results for Multidimensional Subshifts

Symbolic dynamics is a branch of mathematics that studies the structure of infinite sequences of symbols, or in the multidimensional case, infinite grids of symbols. Classes of such sequences and grids defined by collections of forbidden patterns are called subshifts, and subshifts of finite type are defined by finitely many forbidden patterns. The simplest examples of multidimensional subshifts are sets of Wang tilings, infinite arrangements of square tiles with colored edges, where adjacent edges must have the same color. Multidimensional symbolic dynamics has strong connections to computability theory, since most of the basic properties of subshifts cannot be recognized by computer programs, but are instead characterized by some higher-level notion of computability. This dissertation focuses on the structure of multidimensional subshifts, and the ways in which it relates to their computational properties. In the first part, we study the subpattern posets and Cantor-Bendixson ranks of countable subshifts of finite type, which can be seen as measures of their structural complexity. We show, by explicitly constructing subshifts with the desired properties, that both notions are essentially restricted only by computability conditions. In the second part of the dissertation, we study different methods of defining (classes of ) multidimensional subshifts, and how they relate to each other and existing methods. We present definitions that use monadic second-order logic, a more restricted kind of logical quantification called quantifier extension, and multi-headed finite state machines. Two of the definitions give rise to hierarchies of subshift classes, which are a priori infinite, but which we show to collapse into finitely many levels. The quantifier extension provides insight to the somewhat mysterious class of multidimensional sofic subshifts, since we prove a characterization for the class of subshifts that can extend a sofic subshift into a nonsofic one.

Analysis of Phase Separator Design Criteria Using Computational Fluid Dynamics

Gravitational phase separation is a common unit operation found in most large-scale chemical processes. The need for phase separation can arise e.g. from product purification or protection of downstream equipment. In gravitational phase separation, the phases separate without the application of an external force. This is achieved in vessels where the flow velocity is lowered substantially compared to pipe flow. If the velocity is low enough, the denser phase settles towards the bottom of the vessel while the lighter phase rises. To find optimal configurations for gravitational phase separator vessels, several different geometrical and internal design features were evaluated based on simulations using OpenFOAM computational fluid dynamics (CFD) software. The studied features included inlet distributors, vessel dimensions, demister configurations and gas phase outlet configurations. Simulations were conducted as single phase steady state calculations. For comparison, additional simulations were performed as dynamic single and two-phase calculations. The steady state single phase calculations provided indications on preferred configurations for most above mentioned features. The results of the dynamic simulations supported the utilization of the computationally faster steady state model as a practical engineering tool. However, the two-phase model provides more truthful results especially with flows where a single phase does not determine the flow characteristics.

Computational models for and from biology : simple gene assembly and reaction systems

The advancement of science and technology makes it clear that no single perspective is any longer sufficient to describe the true nature of any phenomenon. That is why the interdisciplinary research is gaining more attention overtime. An excellent example of this type of research is natural computing which stands on the borderline between biology and computer science. The contribution of research done in natural computing is twofold: on one hand, it sheds light into how nature works and how it processes information and, on the other hand, it provides some guidelines on how to design bio-inspired technologies. The first direction in this thesis focuses on a nature-inspired process called gene assembly in ciliates. The second one studies reaction systems, as a modeling framework with its rationale built upon the biochemical interactions happening within a cell. The process of gene assembly in ciliates has attracted a lot of attention as a research topic in the past 15 years. Two main modelling frameworks have been initially proposed in the end of 1990s to capture ciliates’ gene assembly process, namely the intermolecular model and the intramolecular model. They were followed by other model proposals such as templatebased assembly and DNA rearrangement pathways recombination models. In this thesis we are interested in a variation of the intramolecular model called simple gene assembly model, which focuses on the simplest possible folds in the assembly process. We propose a new framework called directed overlap-inclusion (DOI) graphs to overcome the limitations that previously introduced models faced in capturing all the combinatorial details of the simple gene assembly process. We investigate a number of combinatorial properties of these graphs, including a necessary property in terms of forbidden induced subgraphs. We also introduce DOI graph-based rewriting rules that capture all the operations of the simple gene assembly model and prove that they are equivalent to the string-based formalization of the model. Reaction systems (RS) is another nature-inspired modeling framework that is studied in this thesis. Reaction systems’ rationale is based upon two main regulation mechanisms, facilitation and inhibition, which control the interactions between biochemical reactions. Reaction systems is a complementary modeling framework to traditional quantitative frameworks, focusing on explicit cause-effect relationships between reactions. The explicit formulation of facilitation and inhibition mechanisms behind reactions, as well as the focus on interactions between reactions (rather than dynamics of concentrations) makes their applicability potentially wide and useful beyond biological case studies. In this thesis, we construct a reaction system model corresponding to the heat shock response mechanism based on a novel concept of dominance graph that captures the competition on resources in the ODE model. We also introduce for RS various concepts inspired by biology, e.g., mass conservation, steady state, periodicity, etc., to do model checking of the reaction systems based models. We prove that the complexity of the decision problems related to these properties varies from P to NP- and coNP-complete to PSPACE-complete. We further focus on the mass conservation relation in an RS and introduce the conservation dependency graph to capture the relation between the species and also propose an algorithm to list the conserved sets of a given reaction system.

Water chemistry management for future large experimental facilities

The thesis focuses on the water chemistry of the experimental test facilities and their reference VVER reactors. The main objective of the thesis is to provide recommendations for water chemistry management for laboratory facilities (VEERA, PACTEL) simulating the VVERs and for the large future facilities of the Lappeenranta University of Technology. In the beginning, the concept of nuclear power generation and the applicability of the nuclear power usage is discussed. Next, different water chemistry and water purification systems in primary and secondary circuits currently used at the power plant have been outlined. Also the construction geometry and design of test facilities PACTEL and VEERA, as well as the operation principles of their main equipment has been described. Finally, the appropriate water chemistry and water treatment system have been proposed for the existing and future experimental facilities of LUT.

Internet-markkinoinnin kehittäminen: Case Outotec HSC Chemistry

Kandidaatintyö käsittelee ohjelmistojen markkinointia internetissä ja markkinoinnin mittaamista. Työssä esitellään internetin eri markkinointikanavat käsitellen niiden toteutustapoja, vahvuuksia ja heikkouksia sekä kustannuksia. Internet-markkinoinnin mittaamisesta käsitellään erilaisia tunnuslukuja sekä mittaamisen käyttökohteita. Työ on pääasiassa kirjallisuuskatsaus, mutta samalla myös case: työssä käsitellään Outotecin toimeksiannosta sen kehittämän HSC Chemistry -ohjelmiston markkinointia internetissä. Työn tuloksissa suositellaan HSC Chemistrylle sopivia markkinointikanavia ja niiden kustannuksia. Lisäksi arvioidaan käsiteltyjen mittaamistapojen soveltuvuutta ohjelmiston tapauksessa.

Computational Market Dynamics of Virtual Economies

The last two decades have provided a vast opportunity to live and explore the compulsive imaginary world or virtual world through massively multiplayer online role-playing games (MMORPGs). MMORPG gives a wide range of opportunities to its users to participate with multi-players on the same platform, to communicate and to do real time actions. There is a virtual economy in these games which is largely player-driven. In-game currency provides its users to build up their Avatars, to buy or sell the necessary goods to play, survive in the games and so on. As a part of virtual economies generated through EVE Online, this thesis mainly focuses on how the prices of the minerals in EVE Online behave by applying the Jabłonska- Capasso-Morale (JCM) mathematical simulation model. It is to verify up to what degree the model can reproduce the virtual economy behavior. The model is applied to buy and sell prices of two minerals namely, isogen and morphite. The simulation results demonstrate that JCM model ts reasonably well to the mineral prices, which lets us conclude that virtual economies behave similarly to the real ones.