New approximation to the third-order density : application to the calculation of correlated multicenter indices

In this work we present the formulas for the calculation of exact three-center electron sharing indices (3c-ESI) and introduce two new approximate expressions for correlated wave functions. The 3c-ESI uses the third-order density, the diagonal of the third-order reduced density matrix, but the approximations suggested in this work only involve natural orbitals and occupancies. In addition, the first calculations of 3c-ESI using Valdemoro's, Nakatsuji's and Mazziotti's approximation for the third-order reduced density matrix are also presented for comparison. Our results on a test set of molecules, including 32 3c-ESI values, prove that the new approximation based on the cubic root of natural occupancies performs the best, yielding absolute errors below 0.07 and an average absolute error of 0.015. Furthemore, this approximation seems to be rather insensitive to the amount of electron correlation present in the system. This newly developed methodology provides a computational inexpensive method to calculate 3c-ESI from correlated wave functions and opens new avenues to approximate high-order reduced density matrices in other contexts, such as the contracted Schrödinger equation and the anti-Hermitian contracted Schrödinger equation

Improved Privacy-Preserving P2P Multimedia Distribution Based on Recombined Fingerprints

Peer-reviewed

Critical behavior of a water monolayer under hydrophobic confinement

The properties of water can have a strong dependence on the confinement. Here, we consider a water monolayer nanoconfined between hydrophobic parallel walls under conditions that prevent its crystallization. We investigate, by simulations of a many-body coarse-grained water model, how the properties of the liquid are affected by the confinement. We show, by studying the response functions and the correlation length and by performing finite-size scaling of the appropriate order parameter, that at low temperature the monolayer undergoes a liquid-liquid phase transition ending in a critical point in the universality class of the two-dimensional (2D) Ising model. Surprisingly, by reducing the linear size L of the walls, keeping the walls separation h constant, we find a 2D-3D crossover for the universality class of the liquid-liquid critical point for L/h=~50, i.e. for a monolayer thickness that is small compared to its extension. This result is drastically different from what is reported for simple liquids, where the crossover occurs for , and is consistent with experimental results and atomistic simulations. We shed light on these findings showing that they are a consequence of the strong cooperativity and the low coordination number of the hydrogen bond network that characterizes water.

Performance characteristics of high performance liquid chromatography, first order derivative UV spectrophotometry and bioassay for fluconazole determination in capsules

The bioassay, first order derivative UV spectrophotometry and chromatographic methods for assaying fluconazole capsules were compared. They have shown great advantages over the earlier published methods. Using the first order derivative, the UV spectrophotometry method does not suffer interference of excipients. Validation parameters such as linearity, precision, accuracy, limit of detection and limit of quantitation were determined. All methods were linear and reliable within acceptable limits for antibiotic pharmaceutical preparations being accurate, precise and reproducible. The application of each method as a routine analysis should be investigated considering cost, simplicity, equipment, solvents, speed, and application to large or small workloads.

Influence of the Al content on the phase transformations in Cu-Al-Ag alloys

The influence of the Al content on the phase transformations in Cu-Al-Ag alloys was studied by classical differential thermal analysis (DTA), optical microscopy (OM) and X-ray diffractometry (XRD). The results indicated that the increase in the Al content and the presence of Ag decrease the rate of the b1 phase decomposition reaction and contribute for the raise of this transition temperature, thus decreasing the stability range of the perlitic phase resulted from the b1 decomposition reaction.

The relationship between first-order capabilities and online innovations. A comparative case study on the publishing sector.

The objective of this thesis was to study the relationship between firstorder capabilities and online innovations. First-order capabilities can be divided into market and technology capabilities, and they play an important role in the production of innovations. The study was carried out in publishing industry, where many changes have taken place in the online environment during the last few years. In the empirical research, four companies were studied, two magazine publishers and two newspaper publishers. The analysis was done in two phases; first every case was analyzed alone and then the cases were compared in cross-case analysis. The most important finding was the positive impact of market capability to the production of online innovations. The study also increased understanding about the relationship between market and technology capabilities and online innovations in general.

Customer Driven Order-to-Delivery Process

This thesis was made for a large forest industry company’s business segment. The purpose of the study was to improve the performance of the order-to-delivery process of the business segment. The study proceeded in three phases. The first phase was to define customer expectations in the market. The second phase was to analyse the performance and the operations of the order-to-delivery process, and to define any challenges or problems in serving the customers. The third and final phase was improving the performance of the order-to-delivery process, within the scope defined by the first two phases. The analysis showed that the delivery reliability is an essential but a challenging issue in the case company’s markets. On delivery reliability standpoint, the most challenging factors were the detected information flow distortions within the company as well as in the whole supply chain, and the lack of horizontal control over the multi-stage process.

Catalytic transformations of fatty acid derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

Växtoljor som utgör en förnybar naturresurs används som sådana eller i modifierade former i många industriella processer, som är av stor betydelse för vårt vardagliga liv. Växtoljor används i livsmedel, i kemiska och farmaceutiska produkter, i textilindustrin, för framställning av färgämnen och beläggningsmaterial samt som miljövänliga bränslekomponenter. Fetter och oljor hör till de äldsta kemiska komponenterna som utnyttjas av människan. De består huvudsakligen av glycerolestrar och fettsyror. Fetter och oljor har typiskt en kolkedja med kol-koldubbelbindningar samt karboxyl- och estergrupper, som kan genom hydrering eller dekarboxylering konverteras till nyttiga och miljövänliga produkter med hjälp av ädelmetallkatalysatorer. Aktivt kol (C) används som bärare på katalysatorerna. Väteaddition, d.v.s. hydrering av växtoljor har varit föremål för omfattande forskning i över hundra års tid. Hydreringen är en viktig process, för den tillämpas på produktion av fetter och margarin. Omättade fettsyror hydreras traditionellt på nickelbaserade heterogena katalysatorer. Samtidigt med en partiell hydrering av fettsyrorna och fettsyraestrarna som har två dubbelbindningar pågår också isomeringsreaktioner, vilka ger cis- och transisomerer av reaktantmolekylerna. Den största nackdelen med nickelkatalysatorerna är deras giftighet samt bildning av ohälsosamma transisomerer i reaktionsprodukterna. Dessutom deaktiveras nickelkatalysatorn snabbt p.g.a. att nickeltvålar bildas i reaktionsblandningen. Platinabaserade katalysatorer lider däremot inte av dessa begränsningar. Metaller i platinagruppen i det periodiska systemet studerades i detalj för att avslöja kinetiska effekter i hydreringen av cis-metyloleat. Palladium, rutenium, rhodium, platina och iridium användes som katalytiska metaller. Metallhalten på aktivkolbärare var 1 vikt-%. De olika platinametallerna undersöktes för att kartlägga konkurrerande hydrerings- och isomeringsrutter på metallerna. Det visade sig att metallerna i andra raden av det periodiska systemet (Ru, Rh, Pd) är aktivare i isomeringsprocesserna, medan metallerna i tredje raden (Ir, Pt) har en lägre aktivitet. Pd/C valdes bland platinametallerna, för att den är attraktiv ur ekonomisk synvinkel och den är mycket aktiv och selektiv, speciellt jämfört med nickel. Tyngdpunkten i arbetet var utvecklingen av en alternativ, palladiumbaserad hydreringsteknologi som skulle ersätta den traditionella teknologin som är baserad på användningen av nickelkatalysatorer. Palladiumbaserade katalysatorer kan återcirkuleras, de är aktivare och mera resistenta mot syror och de bildar mindre mängder av skadliga transisomerer. För att denna teknologi skall bli ekonomiskt hållbar och konkurrenskraftig, måste den basera sig på de bästa möjliga katalysatorerna, vilket innebär att en optimal kombination av hög aktivitet och selektivitet samt en lång livstid för katalysatorn krävs. Därför inkluderades teknologiska aspekter kraftigt i forskningen. Mycket arbete satsades på design av palladium på en mesoporös kolbärare och undersökning av korrelationerna mellan katalysatorns egenskaper och dess aktivitet i isomeriseringsreaktionerna och i hydreringen av kol-koldubbelbindningarna i reaktantmolekylen. Katalysatorerna karakteriserades med många fysikaliska och kemiska metoder (transmissionselektronmikroskopi (TEM), röntgendiffraktion (XRD), röntgenfotoelektronspektroskopi (XPS), temperaturprogrammerad reduktion (TPR), temperaturprogrammerad desorption (TPD) av kolmonoxid, kemisorption av kolmonoxid, fysisorption av kväve). Temperaturens, vätetryckets och katalysatorkoncentrationens inverkan på fettsyra- och isomersammansättningen hos de hydrerade oljorna bestämdes under kinetiska betingelser, i frånvaro av massöverföringseffekter. Syreavspjälkning genom fullständig dekarboxylering av karboxylgruppen i fettsyramolekylen är det hittills bästa sättet att framställa miljövänlig dieselolja, eftersom linjära paraffiner fås som reaktionsprodukter och en tillsats av dyr vätgas undviks. Deoxygeneringen undersöktes systematiskt på en Pd/C-katalysator (Sibunit) genom att använda mättade fettsyror C16-C20 och C22 som råvara. Produktmolekylen blev en dieselliknande kolvätemolekyl, med en kolatom färre än i utgångsmolekylen. Lika stora dekarboxyleringshastigheter observerades för rena, mättade fettsyror. En jämförelse av deoxygenereringshastigheterna för stearin-, olein- och linolsyra som råvara vid 300oC i närvaro av 1-volymprocent väte på mesoporös Pd/C (Sibunit) avslöjade att katalysatorns aktivitet och selektivitet ökade med en ökande mättningsgrad av reaktantmolekylen. Då stearinsyra användes som utgångsmolekyl, bestod huvudprodukterna av önskade C17-kolväten, medan mängden av aromatiska C17-komponenter ökade, då olein- och linolsyra användes som utgångsmolekyler. Katalysatordeaktiveringen var relativt påfallande vid deoxygeneringen av linolsyra så att endast 3% av fettsyrorna omsattes till produkter i 330 min. Deaktiveringen orsakades av aromatiska C17-komponenter samt av fettsyradimerer, som bildades via en Diels-Alderreaktion. Hydreringen av omättade fettsyror kan därför rekommenderas som ett primärt kemiskt steg i framställningen av miljövänliga dieselprodukter. Målet var också att öka förståelsen av palladiummetallernas roll i nanoskala, speciellt effekten av metallpartiklarna i katalytisk hydrering och deoxygenering. Pd/C-katalysatorer med lika stora halter av Pd syntetiserades och metallens dispersion på bärarmaterialet varierades systematiskt genom en kontrollerad uppväxt av palladiumnanopartiklar på aktiv kolbärare. Metalldispersionens effekt på hydrerings-hastigheten och cis-transförhållandet undersöktes i detalj. En optimal metalldispersion som gav den högsta dekarboxyleringshastigheten hittades. Massöverföringens inverkan på reaktionens hastighet studerades experimentellt och temperaturprogrammerad desorption av kolmonoxid från katalysatorytan undersöktes ingående. Hydrering av växtoljor genomfördes under satsvisa och kontinuerliga betingelser. Både finfördelat Pd/C och katalysatorgranulat användes i experimenten. Ett av målen med arbetet var uppskalningen av hydreringsprocesserna. Med tanke på stora produktionsvolymer var det logiskt att undersöka kontinuerliga hydrerings- och dekarboxyleringsteknologier. En kontinuerlig packad bäddreaktor studerades i laboratorieskala, vilket gav viktig information om katalysatorns långtidsstabilitet och deaktivering. Effekten av rena fettsyror och triglycerider som råvara samt metallpartikelstorleken och palladiumhalten studerades med hjälp av den kontinuerliga reaktorn. Produktionskapaciteten som erhölls med satsvis och kontinuerlig drift jämfördes. Dekarboxyleringen av stearinsyra undersöktes också i en kontinuerlig packad bädd. Omsättningsgraden blev 15% för en stabil katalysator.

The figure of the earth, determined from observations made by order of the French King, at the polar circle: by Messrs de Maupertuis, Camus, Clairaut, Le Monnier, members of the Royal Academy of Sciences, the abbé Outhier, correspondent of the Academy, and Mr. Celsius, professor of astronomy at Upsal : translated from the French of M. de Maupertuis.

Digital reproduction, The National Library of Finland, Centre for Preservation and Digitisation, Mikkeli

Evaluating multidimensional visualization techniques in data mining tasks

Visual data mining (VDM) tools employ information visualization techniques in order to represent large amounts of high-dimensional data graphically and to involve the user in exploring data at different levels of detail. The users are looking for outliers, patterns and models – in the form of clusters, classes, trends, and relationships – in different categories of data, i.e., financial, business information, etc. The focus of this thesis is the evaluation of multidimensional visualization techniques, especially from the business user’s perspective. We address three research problems. The first problem is the evaluation of projection-based visualizations with respect to their effectiveness in preserving the original distances between data points and the clustering structure of the data. In this respect, we propose the use of existing clustering validity measures. We illustrate their usefulness in evaluating five visualization techniques: Principal Components Analysis (PCA), Sammon’s Mapping, Self-Organizing Map (SOM), Radial Coordinate Visualization and Star Coordinates. The second problem is concerned with evaluating different visualization techniques as to their effectiveness in visual data mining of business data. For this purpose, we propose an inquiry evaluation technique and conduct the evaluation of nine visualization techniques. The visualizations under evaluation are Multiple Line Graphs, Permutation Matrix, Survey Plot, Scatter Plot Matrix, Parallel Coordinates, Treemap, PCA, Sammon’s Mapping and the SOM. The third problem is the evaluation of quality of use of VDM tools. We provide a conceptual framework for evaluating the quality of use of VDM tools and apply it to the evaluation of the SOM. In the evaluation, we use an inquiry technique for which we developed a questionnaire based on the proposed framework. The contributions of the thesis consist of three new evaluation techniques and the results obtained by applying these evaluation techniques. The thesis provides a systematic approach to evaluation of various visualization techniques. In this respect, first, we performed and described the evaluations in a systematic way, highlighting the evaluation activities, and their inputs and outputs. Secondly, we integrated the evaluation studies in the broad framework of usability evaluation. The results of the evaluations are intended to help developers and researchers of visualization systems to select appropriate visualization techniques in specific situations. The results of the evaluations also contribute to the understanding of the strengths and limitations of the visualization techniques evaluated and further to the improvement of these techniques.

Catalysis by gold for biomass transformations

The development of new technologies to supplement fossil resources has led to a growing interest in the utilization of alternative routes. Biomass is a rich renewable feedstock for producing fine chemicals, polymers, and a variety of commodities replacing petroleumderived chemicals. Transformation of biomass into diverse valuable chemicals is the key concept of a biorefinery. Catalytic conversion of biomass, which reduces the use of toxic chemicals is one of the important approaches to improve the profitability of biorefineries. Utilization of gold catalysts allows conducting reactions under environmentally-friendly conditions, with a high catalytic activity and selectivity. Gold-catalyzed valorization of several biomass-derived compounds as an alternative approach to the existing technologies was studied in this work. Isomerization of linoleic acid via double bond migration towards biologically active conjugated linoleic acid isomers (CLA) was investigated. The activity and selectivity of various gold catalysts towards cis-9,trans-11-CLA and trans-10,cis-12-CLA were investigated in a semi-batch reactor, showing that the yield of the desired products varied, depending on the catalyst support. The structure sensitivity in the selective oxidation of arabinose was demonstrated using a series of gold catalysts with different Au cluster sizes in a shaker reactor operating in a semibatch mode. The gas-phase selective oxidation of ethanol was studied and the influence of the catalyst support on the catalytic performance was investigated. The selective oxidation of the lignan hydroxymatairesinol (HMR), extracted from the Norway spruce (Picea abies) knots, to the lignan oxomatairesinol (oxoMAT) was extensively investigated. The influence of the reaction conditions and catalyst properties on the yield of oxoMAT was evaluated. In particular, the structure sensitivity of the reaction was demonstrated. The catalyst deactivation and regeneration procedures were studied. The reaction kinetics and mechanism were advanced.

Project Master Document adaption in order fulfillment process

This thesis discusses adaption of new project management tool at ABB Oy Motors and Generators business unit, Synchronous Machines profit centre. Thesis studies project modeling in general and buries in the Gate Model used at ABB Synchronous Machines. It is essential to understand Gate Model because this new project management tool, called Project Master Document, is created on the base of the existing project model. Thesis also analyzes goals and structure of Project Master Document in order to ease implementation of this new tool. Project Master Document aims to improved customer order fulfillment by clearing order handover interface. Office process, especially responsibilities and target dates, become also clearer after Master Document implementation. The document is built to be frame for whole order fulfillment process including check points for each gate of project model and updated memos from all project meetings. Furthermore, project progress will be clearly stated by status markings and visualized with colors.

Developing raster bands computed from LiDAR to improve forest

This study examines the use of di erent features derived from remotely sensed data in segmentation of forest stands. Surface interpolation methods were applied to LiDAR points in order to represent data in the form of grayscale images. Median and mean shift ltering was applied to the data for noise reduction. The ability of di erent compositions of rasters obtained from LiDAR data and an aerial image to maximize stand homogeneity in the segmentation was evaluated. The quality of forest stand delineations was assessed by the Akaike information criterion. The research was performed in co-operation with Arbonaut Ltd., Joensuu, Finland.