Computational chemistry studies of wood-derived lignans

This thesis is based on computational chemistry studies on lignans, focusing on the naturally occurring lignan hydroxymatairesinol (HMR) (Papers I II) and on TADDOL-like conidendrin-based chiral 1,4-diol ligands (LIGNOLs) (Papers III V). A complete quantum chemical conformational analysis on HMR was previously conducted by Dr. Antti Taskinen. In the works reported in this thesis, HMR was further studied by classical molecular dynamics (MD) simulations in aqueous solution including torsional angle analysis, quantum chemical solvation e ect study by the COnductorlike Screening MOdel (COSMO), and hydrogen bond analysis (Paper I), as well as from a catalytic point of view including protonation and deprotonation studies at di erent levels of theory (Paper II). The computational LIGNOL studies in this thesis constitute a multi-level deterministic structural optimization of the following molecules: 1,1-diphenyl (2Ph), two diastereomers of 1,1,4-triphenyl (3PhR, 3PhS), 1,1,4,4-tetraphenyl (4Ph) and 1,1,4,4-tetramethyl (4Met) 1,4-diol (Paper IV) and a conformational solvation study applying MD and COSMO (Paper V). Furthermore, a computational study on hemiketals in connection with problems in the experimental work by Docent Patrik Eklund's group synthesizing the LIGNOLs based on natural products starting from HMR, is shortly described (Paper III).

Muutosjohtaminen liikkeenjohdon konsultointiyrityksissä, Case: Kolme konsultointiyritystä

Tutkielma tutkii konsultointiyritysten harjoittamaa muutosjohtamista. Tutkielman tavoitteena on selvittää millaisia menetelmiä konsultointiyritykset käyttävät muutoksen johtamiseen. Tutkielma esittää organisaatiomuutoksen ilmiönä ja selvittää miten muutosta johdetaan. Tutkielma keskittyy konsultointiyritysten muutoksen johtamisessa käyttämiin muutosmalleihin ja -palveluihin. Tutkimusmetodologiana tutkielmassa käytettiin laadullista tapaustutkimusta ja tutkimusaineistonakonsultointiyritysten internet - sivuja. Tutkielmassa havaittiin kirjallisuudessa esiteltyjen muutosmallien identtisyys konsultointiyritysten käyttämien mallien kanssa. Tutkielman tuloksena luotiin synteesi muutosjohtamisen malleista. Tutkielmassa selvisi myös muutospalveluiden kehittyminen laajaksi, kaikkia palveluita tukevaksi funktioksi liikkeenjohdon konsultointiyrityksissä.

Innovation – from individual intuition to collaborative innovation. The role of individual key actor in facilitation of innovation in large organization context

The objective of this research was to study the role of key individuals in facilitation of technology enabled bottom-up innovation in large organization context. The development of innovation was followed from the point of view of individual actor (key individual) in two cases, through three levels: individual, team and organization, by using knowledge creation and innovation models. This study provides theoretical synthesis and framework through which the study is driven. The results of the study indicate, that in bottom-up initiated innovations the role of key individuals is still crucial, but innovation today is collective effort and there acts several entrepreneurial key individuals: innovator, user champion and organizational sponsor, whose collaboration and developing interaction drives innovation further. The team work is functional and fluent, but it meets great problems in interaction with organization. The large organizations should develop its practices and ability to react on emerging bottom-up initiations, in order to embed innovation to organization and gain sustainable innovation. In addition, bottom-up initiated innovations are demonstrations of peoples knowing, tacit knowledge and therefore renewing of an organization.

The third transformation of Japan: An institutional narrative on agglomeration economies in abenomics

Objective of the study The aim of this study is to understand the institutional implications in Abenomics in a spatial context, the contemporary economic reform taking place in Japan, which is to finally end over two decades of economic malaise. For theoretical perspective of choice, this study explores a synthesis of institutionalism as the main approach, complemented by economies of agglomeration in spatial economics, or New Economic Geography (NEG). The outcomes include a narrative with implications for future research, as well as possible future implications for the economy of Japan, itself. The narrative seeks to depict the dialogue between public discourse and governmental communication in order to create a picture of how this phenomenon is being socially constructed. This is done by studying the official communications by the Cabinet along with public media commentary on respective topics. The reform is studied with reference to historical socio-cultural, economic evolution of Japan, which in turn, is explored through a literature review. This is to assess the unique institutional characteristics of Japan pertinent to reform. Research method This is a social and exploratory qualitative study – an institutional narrative case study. The methodological approach was kept practical: in addition to literature review, a narrative, thematic content analysis with structural emphasis was used to construct the contemporary narrative based on the Cabinet communication. This was combined with practical analytic tools borrowed from critical discourse analysis, which were utilized to assess the implicit intertextual agenda within sources. Findings What appears to characterize the discourse is status quo bias that comes in multiple forms. The bias is also coded in the institutions surrounding the reform, wherein stakeholders have vested interests in protecting the current state of affairs. This correlates with uncertainty avoidance characteristic to Japan. Japan heeds the international criticism to deregulate on a rhetorical level, but consistent with history, the Cabinet solutions appear increasingly bureaucratic. Hence, the imposed western information-age paradigm of liberal cluster agglomeration seems ill-suited to Japan which lacks risk takers and a felicitous entrepreneur culture. The Japanese, however, possess vast innovative potential ascribed to some institutional practices and traits, but restrained by others. The derived conclusion is to study the successful intrapreneur cases in Japanese institutional setting as a potential benchmark for Japan specific cluster agglomeration, and a solution to its structural problems impeding growth.

Safety study of hydrogen peroxide direct synthesis

Kandidaatintyön johdantokappaleessa esitellään vetyperoksidi ja mihin sitä käytetään teollisuudessa. Työssä vertaillaan antrakinoniprosessia ja suoraa prosessia sekä selvitetään nykyisin enemmän vetyperoksidituotantoon käytetyn antrakinoniprosessin ongelmakohdat ja osoitetaan, miksi suora synteesi vetyperoksidin tuotannossa olisi parempi vaihtoehto. Kandidaatintyön käsittelee suurilta osin turvallisuusongelmia, joita esiintyy suoran synteesin yhteydessä. Kirjallisuudesta on etsitty ratkaisuja näihin ongelmiin, kuten membraaniprosessin käyttöä räjähdysvaaran välttämiseksi. Pienemmän reaktorin eli ns. mikroreaktorin käyttö tuo mukanaan monia etuja vetyperoksidin tuotantoon. Tällöin prosessi on turvallisempi ja sitä on helpompi hallita. Mikroreaktorissa voidaan käyttää korkeampia lämpötiloja ja paineita kuin makroreaktorilla ilman, että räjähdysvaara prosessissa kasvaisi. Mikroreaktorin sisällä olevat mikrokanavat luovat turvallisen ympäristön synteesille. Aspen plus – simulointiohjelmalla mallinnettiin ja simulointiin suoran prosessin kriittisiä virtoja mikroreaktorissa. Tarkoituksena oli löytää virrat, joissa kulkee mahdollisesti räjähtävä kaasuseos. Kaasumaiset prosessivirrat ovat kriittisimmät vetyperoksidin suorassa synteesissä, koska ne aiheuttavat todennäköisemmin räjähdyksen kuin nestemäiset prosessivirrat. Kaikkein eniten prosessiturvallisuutta uhkaavat ainevirrat ennen ja jälkeen mikroreaktoria.

Computational modeling of the properties of TiO2 nanoparticles

In this study we discuss the electronic, structural, and optical properties of titanium dioxide nanoparticles, and also the properties of Ni(II) diimine dithiolato complexes as dyes in dye-sensitized TiO2 based solar cells. The abovementioned properties have been modeled by using computational codes based on the density functional theory. The results achieved show slight evidence on the structure-dependent band gap broadening, and clear blue-shifts in absorption spectra and refractive index functions of ultra-small TiO2 particles. It is also shown that these properties are strongly dependent on the shape of the nanoparticles. Regarding the Ni(II) diimine dithiolato complexes as dyes in dye-sensitized TiO2 based solar cells, it is shown that based on the experimental electrochemical investigation and DFT studies all studied diimine derivatives could serve as potential candidates for the light harvesting, but the e ciencies of the dyes studied are not very promising.

Computational and Experimental Analysis of Flow Field in the Diffusers of Centrifugal Compressors

Centrifugal compressors are widely used for example in process industry, oil and gas industry, in small gas turbines and turbochargers. In order to achieve lower consumption of energy and operation costs the efficiency of the compressor needs to be improve. In the present work different pinches and low solidity vaned diffusers were utilized in order to improve the efficiency of a medium size centrifugal compressor. In this study, pinch means the decrement of the diffuser flow passage height. First different geometries were analyzed using computational fluid dynamics. The flow solver Finflo was used to solve the flow field. Finflo is a Navier-Stokes solver. The solver is capable to solve compressible, incompressible, steady and unsteady flow fields. Chien's k-e turbulence model was used. One of the numerically investigated pinched diffuser and one low solidity vaned diffuser were studied experimentally. The overall performance of the compressor and the static pressure distribution before and after the diffuser were measured. The flow entering and leaving the diffuser was measured using a three-hole Cobra-probe and Kiel-probes. The pinch and the low solidity vaned diffuser increased the efficiency of the compressor. Highest isentropic efficiency increment obtained was 3\% of the design isentropic efficiency of the original geometry. It was noticed in the numerical results that the pinch made to the hub and the shroud wall was most beneficial to the operation of the compressor. Also the pinch made to the hub was better than the pinchmade to the shroud. The pinch did not affect the operation range of the compressor, but the low solidity vaned diffuser slightly decreased the operation range.The unsteady phenomena in the vaneless diffuser were studied experimentally andnumerically. The unsteady static pressure was measured at the diffuser inlet and outlet, and time-accurate numerical simulation was conducted. The unsteady static pressure showed that most of the pressure variations lay at the passing frequency of every second blade. The pressure variations did not vanish in the diffuser and were visible at the diffuser outlet. However, the amplitude of the pressure variations decreased in the diffuser. The time-accurate calculations showed quite a good agreement with the measured data. Agreement was very good at the design operation point, even though the computational grid was not dense enough inthe volute and in the exit cone. The time-accurate calculation over-predicted the amplitude of the pressure variations at high flow.

Flow phenomena, heat and mass transfer in microchannel reactors

The studies of flow phenomena, heat and mass transfer in microchannel reactors are beneficial to estimate and evaluate the ability of microchannel reactors to be operated for a given process reaction such as Fischer-Tropsch synthesis. The flow phenomena, for example, the flow regimes and flow patterns in microchannel reactors for both single phase and multiphase flow are affected by the configuration of the flow channel. The reviews of the previous works about the analysis of related parameters that affect the flow phenomena are shown in this report. In order to predict the phenomena of Fischer-Tropsch synthesis in microchannel reactors, the 3-dimensional computational fluid dynamic simulation with commercial software package FLUENT was done to study the flow phenomena and heat transfer for gas phase Fischer-Tropsch products flow in rectangular microchannel with hydraulic diameter 500 ¿m and length 15 cm. Numerical solution with slip boundary condition was used in the simulation and the flowphenomena and heat transfer were determined.

Computational Analysis and Optimization of Real Gas Flow In Small Centrifugal Compressors

Small centrifugal compressors are more and more widely used in many industrialsystems because of their higher efficiency and better off-design performance comparing to piston and scroll compressors as while as higher work coefficient perstage than in axial compressors. Higher efficiency is always the aim of the designer of compressors. In the present work, the influence of four partsof a small centrifugal compressor that compresses heavy molecular weight real gas has been investigated in order to achieve higher efficiency. Two parts concern the impeller: tip clearance and the circumferential position of the splitter blade. The other two parts concern the diffuser: the pinch shape and vane shape. Computational fluid dynamics is applied in this study. The Reynolds averaged Navier-Stokes flow solver Finflo is used. The quasi-steady approach is utilized. Chien's k-e turbulence model is used to model the turbulence. A new practical real gas model is presented in this study. The real gas model is easily generated, accuracy controllable and fairly fast. The numerical results and measurements show good agreement. The influence of tip clearance on the performance of a small compressor is obvious. The pressure ratio and efficiency are decreased as the size of tip clearance is increased, while the total enthalpy rise keeps almost constant. The decrement of the pressure ratio and efficiency is larger at higher mass flow rates and smaller at lower mass flow rates. The flow angles at the inlet and outlet of the impeller are increased as the size of tip clearance is increased. The results of the detailed flow field show that leakingflow is the main reason for the performance drop. The secondary flow region becomes larger as the size of tip clearance is increased and the area of the main flow is compressed. The flow uniformity is then decreased. A detailed study shows that the leaking flow rate is higher near the exit of the impeller than that near the inlet of the impeller. Based on this phenomenon, a new partiallyshrouded impeller is used. The impeller is shrouded near the exit of the impeller. The results show that the flow field near the exit of the impeller is greatly changed by the partially shrouded impeller, and better performance is achievedthan with the unshrouded impeller. The loading distribution on the impeller blade and the flow fields in the impeller is changed by moving the splitter of the impeller in circumferential direction. Moving the splitter slightly to the suction side of the long blade can improve the performance of the compressor. The total enthalpy rise is reduced if only the leading edge of the splitter ismoved to the suction side of the long blade. The performance of the compressor is decreased if the blade is bended from the radius direction at the leading edge of the splitter. The total pressure rise and the enthalpy rise of thecompressor are increased if pinch is used at the diffuser inlet. Among the fivedifferent pinch shape configurations, at design and lower mass flow rates the efficiency of a straight line pinch is the highest, while at higher mass flow rate, the efficiency of a concave pinch is the highest. The sharp corner of the pinch is the main reason for the decrease of efficiency and should be avoided. The variation of the flow angles entering the diffuser in spanwise direction is decreased if pinch is applied. A three-dimensional low solidity twisted vaned diffuser is designed to match the flow angles entering the diffuser. The numerical results show that the pressure recovery in the twisted diffuser is higher than in a conventional low solidity vaned diffuser, which also leads to higher efficiency of the twisted diffuser. Investigation of the detailed flow fields shows that the separation at lower mass flow rate in the twisted diffuser is later than in the conventional low solidity vaned diffuser, which leads to a possible wider flow range of the twisted diffuser.

Comprehensive Study of Crystal Growth from Solution

Crystal growth is an essential phase in crystallization kinetics. The rate of crystal growth provides significant information for the design and control of crystallization processes; nevertheless, obtaining accurate growth rate data is still challenging due to a number of factors that prevail in crystal growth. In industrial crystallization, crystals are generally grown from multi-componentand multi-particle solutions under complicated hydrodynamic conditions; thus, it is crucial to increase the general understanding of the growth kinetics in these systems. The aim of this work is to develop a model of the crystal growth rate from solution. An extensive literature review of crystal growth focuses on themodelling of growth kinetics and thermodynamics, and new measuring techniques that have been introduced in the field of crystallization. The growth of a singlecrystal is investigated in binary and ternary systems. The binary system consists of potassium dihydrogen phosphate (KDP, crystallizing solute) and water (solvent), and the ternary system includes KDP, water and an organic admixture. The studied admixtures, urea, ethanol and 1-propanol, are employed at relatively highconcentrations (of up to 5.0 molal). The influence of the admixtures on the solution thermodynamics is studied using the Pitzer activity coefficient model. Theprediction method of the ternary solubility in the studied systems is introduced and verified. The growth rate of the KDP (101) face in the studied systems aremeasured in the growth cell as a function of supersaturation, the admixture concentration, the solution velocity over a crystal and temperature. In addition, the surface morphology of the KDP (101) face is studied using ex situ atomic force microscopy (AFM). The crystal growth rate in the ternary systems is modelled on the basis of the two-step growth model that contains the Maxwell-Stefan (MS) equations and a surface-reaction model. This model is used together with measuredcrystal growth rate data to develop a new method for the evaluation of the model parameters. The validation of the model is justified with experiments. The crystal growth rate in an imperfectly mixed suspension crystallizer is investigatedusing computational fluid dynamics (CFD). A solid-liquid suspension flow that includes multi-sized particles is described by the multi-fluid model as well as by a standard k-epsilon turbulence model and an interface momentum transfer model. The local crystal growth rate is determined from calculated flow information in a diffusion-controlled crystal growth regime. The calculated results are evaluated experimentally.

CFD study of penetration and mixing of fuel in a circulating fluidized bed furnace

The aim of this thesis is to study the mixing of fuel and, also to some extent, the mixing of air in a circulating fluidized bed boiler. In the literature survey part of this thesis, a review is made of the previous experimental studies related to the fuel and air mixing in the circulating fluidized beds. In the simulation part of it the commercial computational fluid dynamics software (FLUENT) is used with the Eulerian multiphase model for studying the fuel mixing in the two and three-dimensional furnace geometries. The results of the three-dimensional simulations are promising and, therefore suggestions are made for the future simulations. The two-dimensional studies give new information of the effects of the fluidization velocity, fuel particle size and fuel density on the fuel mixing. However, the present results show that three-dimensional models produce more realistic representation of the circulating fluidized bed behavior.

Large Break Blowdown Test Facility Study

Työn tarkoituksena on kerätä yhteen tiedot kaikista maailmalta löytyvistä ison LOCA:n ulospuhallusvaiheen tutkimiseen käytetyistä koelaitteistoista. Työn tarkoituksena on myös antaa pohjaa päätökselle, onko tarpeellista rakentaa uusi koelaitteisto nesterakenne-vuorovaikutuskoodien laskennan validoimista varten. Ennen varsinaisen koelaitteiston rakentamista olisi tarkoituksenmukaista myös rakentaa pienempi pilottikoelaitteisto, jolla voitaisiin testata käytettäviä mittausmenetelmiä. Sopivaa mittausdataa tarvitaan uusien CFD-koodien ja rakenneanalyysikoodien kytketyn laskennan validoimisessa. Näitä koodeja voidaan käyttää esimerkiksi arvioitaessa reaktorin sisäosien rakenteellista kestävyyttä ison LOCA:n ulospuhallusvaiheen aikana. Raportti keskittyy maailmalta löytyviin koelaitteistoihin, uuden koelaitteiston suunnitteluperusteisiin sekä aiheeseen liittyviin yleisiin asioihin. Raportti ei korvaa olemassa olevia validointimatriiseja, mutta sitä voi käyttää apuna etsittäessä validointitarkoituksiin sopivaa ison LOCA:n ulospuhallusvaiheen koelaitteistoa.

Computational visual quality of digitally printed images

The problem of understanding how humans perceive the quality of a reproduced image is of interest to researchers of many fields related to vision science and engineering: optics and material physics, image processing (compression and transfer), printing and media technology, and psychology. A measure for visual quality cannot be defined without ambiguity because it is ultimately the subjective opinion of an “end-user” observing the product. The purpose of this thesis is to devise computational methods to estimate the overall visual quality of prints, i.e. a numerical value that combines all the relevant attributes of the perceived image quality. The problem is limited to consider the perceived quality of printed photographs from the viewpoint of a consumer, and moreover, the study focuses only on digital printing methods, such as inkjet and electrophotography. The main contributions of this thesis are two novel methods to estimate the overall visual quality of prints. In the first method, the quality is computed as a visible difference between the reproduced image and the original digital (reference) image, which is assumed to have an ideal quality. The second method utilises instrumental print quality measures, such as colour densities, measured from printed technical test fields, and connects the instrumental measures to the overall quality via subjective attributes, i.e. attributes that directly contribute to the perceived quality, using a Bayesian network. Both approaches were evaluated and verified with real data, and shown to predict well the subjective evaluation results.

Simulation of hydrogen peroxide direct synthesis in a microreactor

A set of models in Aspen plus was built to simulate the direct synthesis process of hydrogen peroxide in a micro-reactor system. This process model can be used to carry out material balance calculation under various experimental conditions. Three thermodynamic property methods were compared by calculating gas solubility and Uniquac-RK method was finally selected for process model. Two different operation modes with corresponding operation conditions were proposed as the starting point of future experiments. Simulations for these two modes were carried out to get the information of material streams. Moreover, some hydrodynamic parameters such as gas/liquid superficial velocity, gas holdup were also calculated with improved process model. These parameters proved the proposed experimental conditions reasonable to some extent. The influence of operation conditions including temperature, pressure and circulation ratio was analyzed for the first operation mode, where pure oxygen was fed into dissolving tank and hydrogen-carbon dioxide mixture was fed into microreactor directly. The preferred operation conditions for the system are low temperature (2°C) and high pressure (30 bar) in dissolving tank. High circulation ratio might be good in the sense that more oxygen could be dissolved and fed into reactor for reactions, but meanwhile hydrodynamics of microreactor should be considered. Furthermore, more operation conditions of reactor gas/liquid feeds in both of two operation modes were proposed to provide guidance for future experiment design and corresponding hydrodynamic parameters were also calculated. Finally, safety issue was considered from thermodynamic point of view and there is no explosion danger at given experimental plan since the released reaction heat will not cause solvent vaporization inside the microchannels. The improvement of process model still needs further study based on the future experimental results.

Methods for construction and analysis of computational models in systems biology : applications to the modelling of the heat shock response and the self-assembly of intermediate filaments

Systems biology is a new, emerging and rapidly developing, multidisciplinary research field that aims to study biochemical and biological systems from a holistic perspective, with the goal of providing a comprehensive, system- level understanding of cellular behaviour. In this way, it addresses one of the greatest challenges faced by contemporary biology, which is to compre- hend the function of complex biological systems. Systems biology combines various methods that originate from scientific disciplines such as molecu- lar biology, chemistry, engineering sciences, mathematics, computer science and systems theory. Systems biology, unlike “traditional” biology, focuses on high-level concepts such as: network, component, robustness, efficiency, control, regulation, hierarchical design, synchronization, concurrency, and many others. The very terminology of systems biology is “foreign” to “tra- ditional” biology, marks its drastic shift in the research paradigm and it indicates close linkage of systems biology to computer science. One of the basic tools utilized in systems biology is the mathematical modelling of life processes tightly linked to experimental practice. The stud- ies contained in this thesis revolve around a number of challenges commonly encountered in the computational modelling in systems biology. The re- search comprises of the development and application of a broad range of methods originating in the fields of computer science and mathematics for construction and analysis of computational models in systems biology. In particular, the performed research is setup in the context of two biolog- ical phenomena chosen as modelling case studies: 1) the eukaryotic heat shock response and 2) the in vitro self-assembly of intermediate filaments, one of the main constituents of the cytoskeleton. The range of presented approaches spans from heuristic, through numerical and statistical to ana- lytical methods applied in the effort to formally describe and analyse the two biological processes. We notice however, that although applied to cer- tain case studies, the presented methods are not limited to them and can be utilized in the analysis of other biological mechanisms as well as com- plex systems in general. The full range of developed and applied modelling techniques as well as model analysis methodologies constitutes a rich mod- elling framework. Moreover, the presentation of the developed methods, their application to the two case studies and the discussions concerning their potentials and limitations point to the difficulties and challenges one encounters in computational modelling of biological systems. The problems of model identifiability, model comparison, model refinement, model inte- gration and extension, choice of the proper modelling framework and level of abstraction, or the choice of the proper scope of the model run through this thesis.