Investigation of the two-photon induced fluorescence in Rb vapour excited by Ti:Sapphire femtosecond laser pulses

In this work we report the observation of the blue visible fluorescence at 420 nm in rubidium vapour as a result of two-photon absorption excited by femtosecond laser pulses 790 nm. After experimental investigation of the spa-tial and spectral characteristics of the obtained emission we can claim that mechanism of this coherent fluorescence at 420 nm was not caused by ampli-fied spontaneous emission, but represents the nondegenerate four-wave mixing. As a probable outcome of this investigation an opportunity of creation an ultrafast all-optical switcher might appear.

Cognitive Auditory Evoked Potentials in Investigation of Hearing Discrimination

Preattentive perception of occasional deviating stimuli in the stream of standard stimuli can be recorded with cognitive event-related potential (ERP) mismatch negativity (MMN). The earlier detection of stimuli at the auditory cortex can be examined with N1 and P2 ERPs. The MMN recording does not require co-operation, it correlates with perceptual threshold, and even complex sounds can be used as stimuli. The aim of this study was to examine different aspects that should be considered when measuring discrimination of hearing with ERPs. The MMN was found to be stimulusintensity- dependent. As the intensity of sine wave stimuli was increased from 40 to 80 dB HL, MMN mean amplitudes increased. The effect of stimulus frequency on the MMN was studied so that the pitch difference would be equal in each stimulus block according to the psychophysiological mel scale or the difference limen of frequency (DLF). However, the blocks differed from each other. The contralateral white noise masking (50 dB EML) was found to attenuate the MMN amplitude when the right ear was stimulated. The N1 amplitude was attenuated and, in contrast, P2 amplitude was not affected by contralateral white noise masking. The perception and production of vowels by four postlingually deafened patients with a cochlear implant were studied. The MMN response could be elicited in the patient with the best vowel perception abilities. The results of the studies show that concerning the MMN recordings, the stimulus parameters and recording procedure design have a great influence on the results.

Mathematical modeling of laboratory scale three-phase fixed bed reactors

Detta arbete fokuserar på modellering av katalytiska gas-vätskereaktioner som genomförs i kontinuerliga packade bäddar. Katalyserade gas-vätskereaktioner hör till de mest typiska reaktionerna i kemisk industri; därför behandlas här packade bäddreaktorer som ett av de populäraste alternativen, då kontinuerlig drift eftersträvas. Tack vare en stor katalysatormängd per volym har de en kompakt struktur, separering av katalysatorn behövs inte och genom en professionell design kan den mest fördelaktiga strömningsbilden upprätthållas i reaktorn. Packade bäddreaktorer är attraktiva p.g.a. lägre investerings- och driftskostnader. Även om packade bäddar används intensivt i industri, är det mycket utmanande att modellera. Detta beror på att tre faser samexisterar och systemets geometri är komplicerad. Existensen av flera reaktioner gör den matematiska modelleringen även mera krävande. Många förenklingar blir därmed nödvändiga. Modellerna involverar typiskt flera parametrar som skall justeras på basis av experimentella data. I detta arbete studerades fem olika reaktionssystem. Systemen hade studerats experimentellt i vårt laboratorium med målet att nå en hög produktivitet och selektivitet genom ett optimalt val av katalysatorer och driftsbetingelser. Hydrering av citral, dekarboxylering av fettsyror, direkt syntes av väteperoxid samt hydrering av sockermonomererna glukos och arabinos användes som exempelsystem. Även om dessa system hade mycket gemensamt, hade de också unika egenskaper och krävde därför en skräddarsydd matematisk behandling. Citralhydrering var ett system med en dominerande huvudreaktion som producerar citronellal och citronellol som huvudprodukter. Produkterna används som en citrondoftande komponent i parfymer, tvålar och tvättmedel samt som plattform-kemikalier. Dekarboxylering av stearinsyra var ett specialfall, för vilket en reaktionsväg för produktion av långkedjade kolväten utgående från fettsyror söktes. En synnerligen hög produktselektivitet var karakteristisk för detta system. Även processuppskalning modellerades för dekarboxylerings-reaktionen. Direkt syntes av väteperoxid hade som målsättning att framta en förenklad process att producera väteperoxid genom att låta upplöst väte och syre reagera direkt i ett lämpligt lösningsmedel på en aktiv fast katalysator. I detta system förekommer tre bireaktioner, vilka ger vatten som oönskad produkt. Alla dessa tre reaktioner modellerades matematiskt med hjälp av dynamiska massbalanser. Målet med hydrering av glukos och arabinos är att framställa produkter med en hög förädlingsgrad, nämligen sockeralkoholer, genom katalytisk hydrering. För dessa två system löstes ämnesmängd- och energibalanserna simultant för att evaluera effekter inne i porösa katalysatorpartiklar. Impulsbalanser som bestämmer strömningsbetingelser inne i en kemisk reaktor, ersattes i alla modelleringsstudier med semi-empiriska korrelationsuttryck för vätskans volymandel och tryckförlust och med axiell dispersionsmodell för beskrivning av omblandningseffekter. Genom att justera modellens parametrar kunde reaktorns beteende beskrivas väl. Alla experiment var genomförda i laboratorieskala. En stor mängd av kopplade effekter samexisterade: reaktionskinetik inklusive adsorption, katalysatordeaktivering, mass- och värmeöverföring samt strömningsrelaterade effekter. En del av dessa effekter kunde studeras separat (t.ex. dispersionseffekter och bireaktioner). Inverkan av vissa fenomen kunde ibland minimeras genom en noggrann planering av experimenten. På detta sätt kunde förenklingar i modellerna bättre motiveras. Alla system som studerades var industriellt relevanta. Utveckling av nya, förenklade produktionsteknologier för existerande kemiska komponenter eller nya komponenter är ett gigantiskt uppdrag. Studierna som presenterades här fokuserade på en av den teknisk-vetenskapliga utfärdens första etapper.

Mathematical modeling of level of anaesthesia from EEG measurements

Problem of modeling of anaesthesia depth level is studied in this Master Thesis. It applies analysis of EEG signals with nonlinear dynamics theory and further classification of obtained values. The main stages of this study are the following: data preprocessing; calculation of optimal embedding parameters for phase space reconstruction; obtaining reconstructed phase portraits of each EEG signal; formation of the feature set to characterise obtained phase portraits; classification of four different anaesthesia levels basing on previously estimated features. Classification was performed with: Linear and quadratic Discriminant Analysis, k Nearest Neighbours method and online clustering. In addition, this work provides overview of existing approaches to anaesthesia depth monitoring, description of basic concepts of nonlinear dynamics theory used in this Master Thesis and comparative analysis of several different classification methods.

Modeling of high pressure pretreatment process for gold leaching

Investigation of high pressure pretreatment process for gold leaching is the objective of the present master's thesis. The gold ores and concentrates which cannot be easily treated by leaching process are called "refractory". These types of ores or concentrates often have high content of sulfur and arsenic that renders the precious metal inaccessible to the leaching agents. Since the refractory ores in gold manufacturing industry take a considerable share, the pressure oxidation method (autoclave method) is considered as one of the possible ways to overcome the related problems. Mathematical modeling is the main approach in this thesis which was used for investigation of high pressure oxidation process. For this task, available information from literature concerning this phenomenon, including chemistry, mass transfer and kinetics, reaction conditions, applied apparatus and application, was collected and studied. The modeling part includes investigation of pyrite oxidation kinetics in order to create a descriptive mathematical model. The following major steps are completed: creation of process model by using the available knowledge; estimation of unknown parameters and determination of goodness of the fit; study of the reliability of the model and its parameters.

Chromatographic recovery of chemicals from acidic biomass hydrolysates

Lignocellulosic biomasses (e.g., wood and straws) are a potential renewable source for the production of a wide variety of chemicals that could be used to replace those currently produced by petrochemical industry. This would lead to lower greenhouse gas emissions and waste amounts, and to economical savings. There are many possible pathways available for the manufacturing of chemicals from lignocellulosic biomasses. One option is to hydrolyze the cellulose and hemicelluloses of these biomasses into monosaccharides using concentrated sulfuric acid as catalyst. This process is an efficient method for producing monosaccharides which are valuable platforn chemicals. Also other valuable products are formed in the hydrolysis. Unfortunately, the concentrated acid hydrolysis has been deemed unfeasible mainly due to high chemical consumption resulting from the need to remove sulfuric acid from the obtained hydrolysates prior to the downstream processing of the monosaccharides. Traditionally, this has been done by neutralization with lime. This, however, results in high chemical consumption. In addition, the by-products formed in the hydrolysis are not removed and may, thus, hinder the monosaccharide processing. In order to improve the feasibility of the concentrated acid hydrolysis, the chemical consumption should be decreased by recycling of sulfuric acid without neutralization. Furthermore, the monosaccharides and the other products formed in the hydrolysis should be recovered selectively for efficient downstream processing. The selective recovery of the hydrolysis by-products would have additional economical benefits on the process due to their high value. In this work, the use of chromatographic fractionation for the recycling of sulfuric acid and the selective recovery of the main components from the hydrolysates formed in the concentrated acid hydrolysis was investigated. Chromatographic fractionation based on the electrolyte exclusion with gel type strong acid cation exchange resins in acid (H+) form as a stationary phase was studied. A systematic experimental and model-based study regarding the separation task at hand was conducted. The phenomena affecting the separation were determined and their effects elucidated. Mathematical models that take accurately into account these phenomena were derived and used in the simulation of the fractionation process. The main components of the concentrated acid hydrolysates (sulfuric acid, monosaccharides, and acetic acid) were included into this model. Performance of the fractionation process was investigated experimentally and by simulations. Use of different process options was also studied. Sulfuric acid was found to have a significant co-operative effect on the sorption of the other components. This brings about interesting and beneficial effects in the column operations. It is especially beneficial for the separation of sulfuric acid and the monosaccharides. Two different approaches for the modelling of the sorption equilibria were investigated in this work: a simple empirical approach and a thermodynamically consistent approach (the Adsorbed Solution theory). Accurate modelling of the phenomena observed in this work was found to be possible using the simple empirical models. The use of the Adsorbed Solution theory is complicated by the nature of the theory and the complexity of the studied system. In addition to the sorption models, a dynamic column model that takes into account the volume changes of the gel type resins as changing resin bed porosity was also derived. Using the chromatography, all the main components of the hydrolysates can be recovered selectively, and the sulfuric acid consumption of the hydrolysis process can be lowered considerably. Investigation of the performance of the chromatographic fractionation showed that the highest separation efficiency in this separation task is obtained with a gel type resin with a high crosslinking degree (8 wt. %); especially when the hydrolysates contain high amounts of acetic acid. In addition, the concentrated acid hydrolysis should be done with as low sulfuric acid concentration as possible to obtain good separation performance. The column loading and flow rate also have large effects on the performance. In this work, it was demonstrated that when recycling of the fractions obtained in the chromatographic fractionation are recycled to preceding unit operations these unit operations should included in the performance evaluation of the fractionation. When this was done, the separation performance and the feasibility of the concentrated acid hydrolysis process were found to improve considerably. Use of multi-column chromatographic fractionation processes, the Japan Organo process and the Multi-Column Recycling Chromatography process, was also investigated. In the studied case, neither of these processes could compete with the single-column batch process in the productivity. However, due to internal recycling steps, the Multi-Column Recycling Chromatography was found to be superior to the batch process when the product yield and the eluent consumption were taken into account.

Magnetic properties of multi-walled nanotubes on polysterene substrate

Nanotubes are one of the most perspective materials in modern nanotechologies. It makes present investigation very actual. In this work magnetic properties of multi-walled nanotubes on polystyrene substrate are investigated by using quantum magnetometer SQUID. Main purpose was to obtain magnetic field and temperature dependences of magnetization and to compare them to existing theoretical models of magnetism in carbon-bases structures. During data analysis a mathematical algorithm for obtained data filtration was developed because measurement with quantum magnetometer assume big missives of number data, which contain accidental errors. Nature of errors is drift of SQUID signal, errors of different parts of measurement station. Nanotube samples on polystyrene substrate were studied with help of atomic force microscope. On the surface traces of nanotube were found contours, which were oriented in horizontal plane. This feature was caused by rolling method for samples. Detailed comparison of obtained dependences with information of other researches on this topic allows to obtain some conclusions about nature of magnetism in the samples. It emphasizes importance and actuality of this scientific work.

Understanding Online Game Players' Post-adoption Behavior: an Investigation of Social Network Games in China

Retaining players and re-attracting switching players has long been a central topic for SNG providers with regard to the post-adoption stage of playing an online game. However, there has not been much research which has explored players’ post-adoption behavior by incorporating the continuance intention and the switching intention. In addition, traditional IS continuance theories were mainly developed to investigate users’ continued use of utilitarian IS, and thus they may fall short when trying to explain the continued use of hedonic IS. Furthermore, compared to the richer literature on IS continuance, far too little attention has been paid to IS switching, leading to a dearth of knowledge on the subject, despite the increased incidence of the switching phenomenon in the IS field. By addressing the limitations of prior literature, this study seeks to examine the determinants of SNG players’ two different post-adoption behaviors, including the continuance intention and the switching intention. This study takes a positivist approach and uses survey research method to test five proposed research models based on Unified Theory of Acceptance and Use of Technology 2; Use and Gratification Theory; Push-Pull-Mooring model; Cognitive Dissonance Theory; and a self-developed model respectively with empirical data collected from the SNG players of one of the biggest SNG providers in China. A total of 3919 valid responses and 541 valid responses were used to examine the continuance intention and the switching intention, respectively. SEM is utilized as the data analysis method. The proposed research models are supported by the empirical data. The continuance intention is determined by enjoyment, fantasy, escapism, social interaction, social presence, social influence, achievement and habit. The switching intention is determined by enjoyment, satisfaction, subjective norms, descriptive norms, alternative attractiveness, the need for variety, change experience, and adaptation cost. This study contributes to IS theories in three important ways. Firstly, it shows IS switching should be included in IS post-adoption research together with IS continuance. Secondly, a modern IS is usually multi-functional and SNG players have multiple reasons for using a SNG, thus a player’s beliefs about the hedonic, social and utilitarian perceptions of their continued use of the SNG exert significant effects on the continuance intention. Thirdly, the determinants of the switch ing intention mainly exert push, pull, and mooring effects. Players’ beliefs about their current SNG and the available alternatives, as well as their individual characteristics are all significant determinants of the switching intention. SNG players combine these effects in order to formulate the switching intention. Finally, this study presents limitations and suggestions for future research.

Spontaneous Focusing on Numerosity in the Development of Early Mathematical Skills

The aim of the present set of longitudinal studies was to explore 3-7-year-old children.s Spontaneous FOcusing on Numerosity (SFON) and its relation to early mathematical development. The specific goals were to capture in method and theory the distinct process by which children focus on numerosity as a part of their activities involving exact number recognition, and individual differences in this process that may be informative in the development of more complex number skills. Over the course of conducting the five studies, fifteen novel tasks were progressively developed for the SFON assessments. In the tasks, confounding effects of insufficient number recognition, verbal comprehension, other procedural skills as well as working memory capacity were aimed to be controlled. Furthermore, how children.s individual differences in SFON are related to their development of number sequence, subitizing-based enumeration, object counting and basic arithmetic skills was explored. The effect of social interaction on SFON was tested. Study I captured the first phase of the 3-year longitudinal study with 39 children. It was investigated whether there were differences in 3-year-old children.s tendency to focus on numerosity, and whether these differences were related to the children.s development of cardinality recognition skills from the age of 3 to 4 years. It was found that the two groups of children formed on the basis of their amount of SFON tendency at the age of 3 years differed in their development of recognising and producing small numbers. The children whose SFON tendency was very predominant developed faster in cardinality related skills from the age of 3 to 4 years than the children whose SFON tendency was not as predominant. Thus, children.s development in cardinality recognition skills is related to their SFON tendency. Studies II and III were conducted to investigate, firstly, children.s individual differences in SFON, and, secondly, whether children.s SFON is related to their counting development. Altogether nine tasks were designed for the assessments of spontaneous and guided focusing on numerosity. The longitudinal data of 39 children in Study II from the age of 3.5 to 6 years showed individual differences in SFON at the ages of 4, 5 and 6 years, as well as stability in children.s SFON across tasks used at different ages. The counting skills were assessed at the ages of 3.5, 5 and 6 years. Path analyses indicated a reciprocal tendency in the relationship between SFON and counting development. In Study III, these results on the individual differences in SFON tendency, the stability of SFON across different tasks and the relationship of SFON and mathematical skills were confirmed by a larger-scale cross-sectional study of 183 on average 6.5-year-old children (range 6;0-7;0 years). The significant amount of unique variance that SFON accounted for number sequence elaboration, object counting and basic arithmetic skills stayed statistically significant (partial correlations varying from .27 to .37) when the effects of non-verbal IQ and verbal comprehension were controlled. In addition, to confirm that the SFON tasks assess SFON tendency independently from enumeration skills, guided focusing tasks were used for children who had failed in SFON tasks. It was explored whether these children were able to proceed in similar tasks to SFON tasks once they were guided to focus on number. The results showed that these children.s poor performance in the SFON tasks was not caused by their deficiency in executing the tasks but on lacking focusing on numerosity. The longitudinal Study IV of 39 children aimed at increasing the knowledge of associations between children.s long-term SFON tendency, subitizing-based enumeration and verbal counting skills. Children were tested twice at the age of 4-5 years on their SFON, and once at the age of 5 on their subitizing-based enumeration, number sequence production, as well as on their skills for counting of objects. Results showed considerable stability in SFON tendency measured at different ages, and that there is a positive direct association between SFON and number sequence production. The association between SFON and object counting skills was significantly mediated by subitizing-based enumeration. These results indicate that the associations between the child.s SFON and sub-skills of verbal counting may differ on the basis of how significant a role understanding the cardinal meanings of number words plays in learning these skills. The specific goal of Study V was to investigate whether it is possible to enhance 3-year old children.s SFON tendency, and thus start children.s deliberate practice in early mathematical skills. Participants were 3-year-old children in Finnish day care. The SFON scores and cardinality-related skills of the experimental group of 17 children were compared to the corresponding results of the 17 children in the control group. The results show an experimental effect on SFON tendency and subsequent development in cardinality-related skills during the 6-month period from pretest to delayed posttest in the children with some initial SFON tendency in the experimental group. Social interaction has an effect on children.s SFON tendency. The results of the five studies assert that within a child.s existing mathematical competence, it is possible to distinguish a separate process, which refers to the child.s tendency to spontaneously focus on numerosity. Moreover, there are significant individual differences in children.s SFON at the age of 3-7 years. Moderate stability was found in this tendency across different tasks assessed both at the same and at different ages. Furthermore, SFON tendency is related to the development of early mathematical skills. Educational implications of the findings emphasise, first, the importance of regarding focusing on numerosity as a separate, essential process in the assessments of young children.s mathematical skills. Second, the substantial individual differences in SFON tendency during the childhood years suggest that uncovering and modeling this kind of mathematically meaningful perceiving of the surroundings and tasks could be an efficient tool for promoting young children.s mathematical development, and thus prevent later failures in learning mathematical skills. It is proposed to consider focusing on numerosity as one potential sub-process of activities involving exact number recognition in future studies.

Mathematical modeling and optimal control of malaria

Malaria continues to infect millions and kill hundreds of thousands of people worldwide each year, despite over a century of research and attempts to control and eliminate this infectious disease. Challenges such as the development and spread of drug resistant malaria parasites, insecticide resistance to mosquitoes, climate change, the presence of individuals with subpatent malaria infections which normally are asymptomatic and behavioral plasticity in the mosquito hinder the prospects of malaria control and elimination. In this thesis, mathematical models of malaria transmission and control that address the role of drug resistance, immunity, iron supplementation and anemia, immigration and visitation, and the presence of asymptomatic carriers in malaria transmission are developed. A within-host mathematical model of severe Plasmodium falciparum malaria is also developed. First, a deterministic mathematical model for transmission of antimalarial drug resistance parasites with superinfection is developed and analyzed. The possibility of increase in the risk of superinfection due to iron supplementation and fortification in malaria endemic areas is discussed. The model results calls upon stakeholders to weigh the pros and cons of iron supplementation to individuals living in malaria endemic regions. Second, a deterministic model of transmission of drug resistant malaria parasites, including the inflow of infective immigrants, is presented and analyzed. The optimal control theory is applied to this model to study the impact of various malaria and vector control strategies, such as screening of immigrants, treatment of drug-sensitive infections, treatment of drug-resistant infections, and the use of insecticide-treated bed nets and indoor spraying of mosquitoes. The results of the model emphasize the importance of using a combination of all four controls tools for effective malaria intervention. Next, a two-age-class mathematical model for malaria transmission with asymptomatic carriers is developed and analyzed. In development of this model, four possible control measures are analyzed: the use of long-lasting treated mosquito nets, indoor residual spraying, screening and treatment of symptomatic, and screening and treatment of asymptomatic individuals. The numerical results show that a disease-free equilibrium can be attained if all four control measures are used. A common pitfall for most epidemiological models is the absence of real data; model-based conclusions have to be drawn based on uncertain parameter values. In this thesis, an approach to study the robustness of optimal control solutions under such parameter uncertainty is presented. Numerical analysis of the optimal control problem in the presence of parameter uncertainty demonstrate the robustness of the optimal control approach that: when a comprehensive control strategy is used the main conclusions of the optimal control remain unchanged, even if inevitable variability remains in the control profiles. The results provide a promising framework for the design of cost-effective strategies for disease control with multiple interventions, even under considerable uncertainty of model parameters. Finally, a separate work modeling the within-host Plasmodium falciparum infection in humans is presented. The developed model allows re-infection of already-infected red blood cells. The model hypothesizes that in severe malaria due to parasite quest for survival and rapid multiplication, the Plasmodium falciparum can be absorbed in the already-infected red blood cells which accelerates the rupture rate and consequently cause anemia. Analysis of the model and parameter identifiability using Markov chain Monte Carlo methods is presented.

Atomic Force Microscopy Investigation of NI Particles Deposited on Porous Silicon

In this thesis properties and influence of modification techniques of porous silicon were studied by Atomic Force Microscope (AFM). This device permits to visualize the surface topography and to study properties of the samples on atomic scale, which was necessary for recent investigation. Samples of porous silicon were obtained by electrochemical etching. Nickel particles were deposited by two methods: electrochemical deposition and extracting from NiCl2 ethanol solution. Sample growth was conducted in Saint-Petersburg State Electrotechnical University, LETI. Kelvin probe force microscopy (KPFM) and Magnetic force microscopy (MFM) were utilized for detailed information about surface properties of the samples. Measurements showed the difference in morphology correlating with initial growth conditions. Submicron size particles were clearly visible on surfaces of the treated samples. Although their nature was not clarified due to limitations of AFM technique. It is expected that surfaces were covered by nanometer scale Ni particles, which can be verified by implication of RAMAN device.