Combined experimental powder X-ray diffraction and DFT data to obtain the lowest energy molecular conformation of friedelin

Friedelin molecular conformers were obtained by Density Functional Theory (DFT) and by ab initio structure determination from powder X-ray diffraction. Their conformers with the five rings in chair-chair-chair-boat-boat, and with all rings in chair, are energy degenerated in gas-phase according to DFT results. The powder diffraction data reveals that rings A, B and C of friedelin are in chair, and rings D and E in boat-boat, conformation. The high correlation values among powder diffraction data, DFT and reported single-crystal data indicate that the use of conventional X-ray diffractometer can be applied in routine laboratory analysis in the absence of a single-crystal diffractometer.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

Development of Collaborative Product Structure Management

The purpose of this thesis is to develop an environment or network that enables effective collaborative product structure management among stakeholders in each unit, throughout the entire product lifecycle and product data management. This thesis uses framework models as an approach to the problem. Framework model methods for development of collaborative product structure management are proposed in this study, there are three unique models depicted to support collaborative product structure management: organization model, process model and product model. In the organization model, the formation of product data management system (eDSTAT) key user network is specified. In the process model, development is based on the case company’s product development matrix. In the product model framework, product model management, product knowledge management and design knowledge management are defined as development tools and collaboration is based on web-based product structure management. Collaborative management is executed using all these approaches. A case study from an actual project at the case company is presented as an implementation; this is to verify the models’ applicability. A computer assisted design tool and the web-based product structure manager, have been used as tools of this collaboration with the support of the key user. The current PDM system, eDSTAT, is used as a piloting case for key user role. The result of this development is that the role of key user as a collaboration channel is defined and established. The key user is able to provide one on one support for the elevator projects. Also the management activities are improved through the application of process workflow by following criteria for each project milestone. The development shows effectiveness of product structure management in product lifecycle, improved production process by eliminating barriers (e.g. improvement of two-way communication) during design phase and production phase. The key user role is applicable on a global scale in the company.

Oliopohjainen konenäkösovelluskehys

Monet teollisuuden konenäkö- ja hahmontunnistusongelmat ovat hyvin samantapaisia, jolloin prototyyppisovelluksia suunniteltaessa voitaisiin hyödyntää pitkälti samoja komponentteja. Oliopohjaiset sovelluskehykset tarjoavat erinomaisen tavan nopeuttaa ohjelmistokehitystä uudelleenkäytettävyyttä parantamalla. Näin voidaan sekä mahdollistaa konenäkösovellusten laajempi käyttö että säästää kustannuksissa. Tässä työssä esitellään konenäkösovelluskehys, joka on perusarkkitehtuuriltaan liukuhihnamainen. Ylätason rakenne koostuu sensorista, datankäsittelyoperaatioista, piirreirrottimesta sekä luokittimesta. Itse sovelluskehyksen lisäksi on toteutettu joukko kuvankäsittely- ja hahmontunnistusoperaatioita. Sovelluskehys nopeuttaa selvästi ohjelmointityötä ja helpottaa uusien kuvankäsittelyoperaatioiden lisää mistä.

Analysis of the structure and vibrational spectra of glucose and fructose

Molecular modelling using semiempirical methods AM1, PM3, PM5 and, MINDO as well as the Density Functional Theory method BLYP/DZVP respectively were used to calculate the structure and vibrational spectra of d-glucose and d-fructose in their open chain, alpha-anomer and beta-anomer monohydrate forms. The calculated data show that both molecules are not linear; ground state and the number for the point-group C is equal to 1. Generally, the results indicate that there are similarities in bond lengths and vibrational modes of both molecules. It is concluded that DFT could be used to study both the structural and vibrational spectra of glucose and fructose.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

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.

Diameter structure of stratum and ecological groups of a Semideciduous Forest area in Dionísio-MG

The objective of this study was to obtain homogeneous groups of species and information on their density, dominance and volume, in terms of ecological group and diameter structure of an area of Submontane Semideciduous forest (Mata do Mumbaça) in Dionísio, MG. This work was conducted with data of the diameter distribution per species from floristic and phytosociological (Mata do Mumbaça) survey of 120 plots with 10 x 10 m each one. The 120 plots were contiguous and corresponding to a total sample area of 12,000 m² distributed over the topographic units (Low Ramp, Lower Slope, Upper Slope and Hill Top). The topographic units Low Ramp, Lower Slope and Upper Slope were in the middle stage of succession as they presented incipient stratification into two strata (canopy and understory) i.e. canopy ranging from 5 to 12 m high. However, the stratum Hill Top was classified as intermediate/advanced succession because it had a total height equal to or greater than 12 m. The distribution of individual trees of the four strata on diameter classes showed a typical J-inverted pattern that is, high concentration of individuals in smaller diameter classes and a sharp reduction towards the larger classes. In relation to absolute dominance and total volume of species, the ecological group that stood out in the four strata (Low Ramp, Lower Slope, Upper Slope and Hill Top) was the initial secondary, which were in the intermediate stage of secondary, rapidly developing into the mature phase.

Possibilities and challenges of longitudinal studies in operations management

Longitudinal studies are quite rare in the area of Operations Management. One reason might be the time needed to conduct such studies, and then the lack of experience and real-life examples and results. The aim of the thesis is to examine longitudinal studies in the area of OM and the possible advantages, challenges and pitfalls of such studies. A longitudinal benchmarking study, Made in Finland, was analyzed in terms of the study methodology and its outcomes. The timeline of this longitudinal study is interesting. The first study was made in 1993, the second in 2004 and the third in 2010. Between these studies some major changes occurred in the Finnish business environment. Between the first and second studies, Finland joined the ETA and the EU, and globalization started with the rise of the Internet era, while between the second and third studies financial turmoil started in 2007. The sample and cases used in this study were originally 23 manufacturing sites in Finland. These sites were interviewed in 1993, in 2004 and 2010. One important and interesting aspect is that all the original sites participated in 2004, and 19 sites were still able to participate in 2010. Four sites had been closed and/or moved abroad. All of this gave a good opportunity to study the changes that occurred in the Finnish manufacturing sites and their environment, and how they reacted to these changes, and the effects on their performance. It is very seldom, if ever, that the same manufacturing sites have been studied in a longitudinal setting by using three data points. The results of this study are thus unique, and the experience gained is valuable for practitioners.

DYNAMICS AND PREDICTION OF DIAMETRIC STRUCTURE IN TWO ATLANTIC FOREST FRAGMENTS IN NORTHEASTERN BRAZIL

ABSTRACT Monitoring analyses aim to understand the processes that drive changes in forest structure and, along with prediction studies, may assist in the management planning and conservation of forest remnants. The objective of this study was to analyze the forest dynamics in two Atlantic rainforest fragments in Pernambuco, Brazil, and to predict their future forest diameter structure using the Markov chain model. We used continuous forest inventory data from three surveys in two forest fragments of 87 ha (F1) and 388 ha (F2). We calculated the annual rates of mortality and recruitment, the mean annual increment, and the basal area for each of the 3-year periods. Data from the first and second surveys were used to project the third inventory measurements, which were compared to the observed values in the permanent plots using chi-squared tests (a = 0.05). In F1, a decrease in the number of individuals was observed due to mortality rates being higher than recruitment rates; however, there was an increase in the basal area. In this fragment, the fit to the Markov model was adequate. In F2, there was an increase in both the basal area and the number of individuals during the 6-year period due to the recruitment rate exceeding the mortality rate. For this fragment, the fit of the model was unacceptable. Hence, for the studied fragments, the demographic rates influenced the stem density more than the floristic composition. Yet, even with these intense dynamics, both fragments showed active growth.

A decision support system for cost determination in grain storage facility operations

Many research works have being carried out on analyzing grain storage facility costs; however a few of them had taken into account the analysis of factors associated to all pre-processing and storage steps. The objective of this work was to develop a decision support system for determining the grain storage facility costs and utilization fees in grain storage facilities. The data of a CONAB storage facility located in Ponta Grossa - PR, Brazil, was used as input of the system developed to analyze its specific characteristics, such as amount of product received and stored throughout the year, hourly capacity of drying, cleaning, and receiving, and dispatch. By applying the decision support system, it was observed that the reception and expedition costs were exponentially reduced as the turnover rate of the storage increased. The cleaning and drying costs increased linearly with grain initial moisture. The storage cost increased exponentially as the occupancy rate of the storage facility decreased.

Probabilistic structure of an annual extreme rainfall series of a coastal area of the State of São Paulo, Brazil

This study aimed to describe the probabilistic structure of the annual series of extreme daily rainfall (Preabs), available from the weather station of Ubatuba, State of São Paulo, Brazil (1935-2009), by using the general distribution of extreme value (GEV). The autocorrelation function, the Mann-Kendall test, and the wavelet analysis were used in order to evaluate the presence of serial correlations, trends, and periodical components. Considering the results obtained using these three statistical methods, it was possible to assume the hypothesis that this temporal series is free from persistence, trends, and periodicals components. Based on quantitative and qualitative adhesion tests, it was found that the GEV may be used in order to quantify the probabilities of the Preabs data. The best results of GEV were obtained when the parameters of this function were estimated using the method of maximum likelihood. The method of L-moments has also shown satisfactory results.

Streamlining Launch Support Operations in a Product Platform

The new product development process is a massive investment to a company that aims to reduce their products’ time-to-market. Capability to shorter time-to market allows longer life-cycle to products which are introduced to market earlier but also give advantage to start product launch later while simultaneously learning from customer behavior and competitors. The product launch support operations are the last ramp-up activities before the product launching. This study defines what these operations mean in a product platform and how they can be streamlined to be more efficient. The methodology includes interviews, innovative group brainstorming and regular working group meetings. The challenges concerning the current situation of product launch support operations are allocated into four categories: General, Process, Project Resources and Project Management including altogether ten sub challenges. The challenges include issues related to technology and marketing management, branding strategy, organizing the global platform structure, harmonizing processes and clarifying handovers between shareholders in the process. The study makes a suggestion of a new Product Launch Support organization and clarification of its roles, responsibilities and tasks. In addition a new project management tool and Lessons Learned are suggested to improve the project management. The study can be seen as a pre-study when having an aim at combining technological and marketing know-how in the product ramp-up process before actual production. The future proceedings are suggested to include more detailed specifications and implementation in order to reach the long range target, reduced the time-to-market.

E-PORT. Improving efficiency of Finnish port community by intelligent systems Final report of the Mobile Port project

The management of port-related supply chains is challenging due to the complex and heterogeneous operations of the ports with several actors and processes. That is why the importance of information sharing is emphasised in the ports. However, the information exchange between different port-related actors is often cumbersome and it still involves a lot of manual work and paper. Major ports and port-related actors usually have advanced information systems in daily use but these systems are seldom interoperable with each other, which prevents economies of scale to be reached. Smaller ports and companies might not be equipped with electronic data transmission at all. This is the final report of the Mobile port (MOPO) project, which has sought ways to improve the management and control of port-related sea and inland traffic with the aid of ICT technologies. The project has studied port community systems (PCS) used worldwide, evaluated the suitability of a PCS for the Finnish port operating environment and created a pilot solution of a Finnish PCS in the port of HaminaKotka. Further, the dry port concept and its influences on the transportation system have been explored. The Mobile Port project comprised of several literature reviews, interviews of over 50 port-related logistics and/or ICT professionals, two different kinds of simulation models as well as designing and implementing of the pilot solution of the Finnish PCS. The results of these multiple studies are summarised in this report. Furthermore, recommendations for future actions and the topics for further studies are addressed in the report. The study revealed that the information sharing in a typical Finnish port-related supply chain contains several bottlenecks that cause delays in shipments and waste resources. The study showed that many of these bottlenecks could be solved by building a port community system for the Finnish port community. Almost 30 different kinds of potential services or service entities of a Finnish PCS were found out during the study. The basic requirements, structure, interfaces and operation model of the Finnish PCS were also defined in the study. On the basis of the results of the study, a pilot solution of the Finnish PCS was implemented in the port of HaminaKotka. The pilot solution includes a Portconnect portal for the Finnish port community system (available at https://www.portconnect.fi) and two pilot applications, which are a service for handling the information flows concerning the movements of railway wagons and a service for handling the information flows between Finnish ports and Finland-Russian border. The study also showed that port community systems can be used to improve the environmental aspects of logistics in two different ways: 1) PCSs can bring direct environmental benefits and 2) PCSs can be used as an environmental tool in a port community. On the basis of the study, the development of the Finnish port community system should be continued by surveying other potential applications for the Finnish PCS. It is also important to study if there is need and resources to extend the Finnish PCS to operate in several ports or even on a national level. In the long run, it could be reasonable to clarify whether there would be possibilities to connect the Finnish PCS as a part of Baltic Sea wide, European-wide or even worldwide maritime and port-related network in order to get the best benefit from the system

Immigration Strategy for Northern Ostrobothnia 2015

A strategy process was completed in the ESF project “Promotion of Work-related Immigration”, which was implemented at Centre for Economic Development, Transport and the Environment for North Ostrobothnia, and an immigration strategy was drawn up for Northern Ostrobothnia on the basis of the process. Information was collected about the situation in Northern Ostrobothnia from the point of view of immigration and the future availability of labour. The intention was to use the information as background material for the strategy. Employers’ need for support in recruiting foreign labour was investigated with a broad inquiry, to which 1000 respondents replied. The strategy process was carried out together with an outside consultant (Net Effect Oy) by arranging three workshops and a seminar where the workshop results were summarised. A large number of companies, authorities, municipalities, associations, project actors and immigrants engaged in immigration issues participated in the workshops. The draft strategy is based on their experiences about immigration and on statistical data, background inquiries and surveys. To ensure the accuracy of the draft strategy, comments were requested from several parties and received from 64 organisations. The core of the immigration strategy consists of an initial analysis, values, a vision and priorities. The strategy is composed of three priorities. The key aim of the priority Internationalisation and Supporting Diversity is to support diversity in schools, workplaces and people’s everyday lives e.g. through attitude development and by promoting internationalisation in companies and education institutions. The aim of the priority Supporting Entrepreneurship and Recruiting Foreign Labour is to promote entrepreneurship among immigrants and the recruitment of foreign labour and to develop the forecasting of educational needs. The priority Developing Integration Services, Regional Cooperation and Networks, in turn, seeks to develop the service structure and policies of immigrant integration and to increase cooperation and exchange of information between regional actors engaged in integration issues. The aim is to use the strategy as a guideline document for immigration issues in Northern Ostrobothnia. The strategy is used to coordinate the existing organisations and operations dealing with immigration issues. In addition, it contains a future-oriented focus and underlines the management of new immigration projects and operations. The main party responsible for the implementation of the strategy is the Immigration Committee. In addition, responsible parties have been assigned to each measure. The implementation of the immigration strategy will be monitored annually on the basis of indicators.