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.

Potentiometric quantification and speciation of oxygenated groups in humic substances using BEST7 software

In this study the BEST7 software was employed to quantify different classes of functional groups and to model the proton titration behavior of humic substances. To illustrate the process, the Suwannee River fulvic acid of the IHSS (International Humic Substances Society) was used. Five categories - two classes of phenolic groups (phenol and cathecol), two classes of carboxylic groups (benzoic and phtalic) and the combination between them (salicylic) - of oxygenated groups were considered as being responsible for the potentiometric behavior of the sample and were quantitatively determined. The most and the least abundant groups were cathecol (3.300 ± 0.010 mmol g-1) and phenol (1.225 ± 0.070 mmol g-1), respectively. The estimated equilibrium constants were also determined and were in good agreement with the literature values for phenol and cathecol groups and for benzoic, phtalic and salicylic acids. Distribution diagrams of the species were generated with the software SPE and SPEPLOT.

Considering Target Groups in the Creation of a Comprehensive City Branding Process

The aim of the research was to create a comprehensive city branding process. This was done by identifying the key target groups of the city and considering them in the city branding process. Also key stakeholders were identified and taken into consideration when creating the branding process. As an empirical study, three first stages of the city branding process were implemented for the city of Lappeenranta having "students" as the case target group. An interview with the city officials was conducted, as well as a student survey on the current city image of Lappeenranta. Quantitative research methods were used to analyze the results of the survey. A comprehensive city branding process with eight stages was created in the research. Target groups were considered in the process by identifying the target group dependent stages. The empirical study revealed that the current city image held by the students consists of six dimensions. These dimensions were analyzed from the viewpoint of Lappeenranta with the help of an importance performance analysis.

Towards input/output-free modelling of linear infinite-dimensional systems in continuous time

This dissertation describes a networking approach to infinite-dimensional systems theory, where there is a minimal distinction between inputs and outputs. We introduce and study two closely related classes of systems, namely the state/signal systems and the port-Hamiltonian systems, and describe how they relate to each other. Some basic theory for these two classes of systems and the interconnections of such systems is provided. The main emphasis lies on passive and conservative systems, and the theoretical concepts are illustrated using the example of a lossless transfer line. Much remains to be done in this field and we point to some directions for future studies as well.

Lean -työkalujen käyttöönoton suunnittelu VR Groupin kunnossapitoyksikölle

Lean –filosofia on ollut 1990 lähtien esillä yritysten toiminnan kehittämisessä niin laadun kuin tuottavuuden kehittämisen osalla. Filosofia on rakennettu Toyotan kehittämän Toyota Production Systemin (TPS) pohjalta ja sisältää useita eri menetelmiä yrityksen toimintojen jatkuvaan kehittämiseen yrityksen eri vaiheissa. Lean –filosofiassa yritystä kehitetään koko yrityksen olemassa olon ajan, voidaankin sanoa kyseessä olevan yrityksen elämäntapa. VR Group:n kunnossapitopalveluissa kehitetään parhaillaan VR Groupin laitteiden kunnossapitoa vastaamaan tulevaisuudessa avautuvaan kilpailuun. Kehittämishankkeen yhtenä kohteena on lean –ajattelun käyttöönottaminen kunnossapitopalvelun toiminnassa. Työssä selvitettiin leanin sisältämien menetelmien käyttöönottoa yhdelle VR Groupin kunnossapitoyksikölle, pääpainona virtauttaminen sekä jatkuva parantaminen. Työssä laadittiin kaksi virtauttamissuunnitelmaa VR Groupin kunnossapitoyksikölle, sekä esitellään vaihtoehtoja lean -työkaluista, joita kohdeyksikön kehittämisohjelmassa voitaisiin käyttää.

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.

Non-Markovian Dynamics in Continuous Variable Quantum Systems

The present manuscript represents the completion of a research path carried forward during my doctoral studies in the University of Turku. It contains information regarding my scientific contribution to the field of open quantum systems, accomplished in collaboration with other scientists. The main subject investigated in the thesis is the non-Markovian dynamics of open quantum systems with focus on continuous variable quantum channels, e.g. quantum Brownian motion models. Non-Markovianity is here interpreted as a manifestation of the existence of a flow of information exchanged by the system and environment during the dynamical evolution. While in Markovian systems the flow is unidirectional, i.e. from the system to the environment, in non-Markovian systems there are time windows in which the flow is reversed and the quantum state of the system may regain coherence and correlations previously lost. Signatures of a non-Markovian behavior have been studied in connection with the dynamics of quantum correlations like entanglement or quantum discord. Moreover, in the attempt to recognisee non-Markovianity as a resource for quantum technologies, it is proposed, for the first time, to consider its effects in practical quantum key distribution protocols. It has been proven that security of coherent state protocols can be enhanced using non-Markovian properties of the transmission channels. The thesis is divided in two parts: in the first part I introduce the reader to the world of continuous variable open quantum systems and non-Markovian dynamics. The second part instead consists of a collection of five publications inherent to the topic.

Kolme näkökulmaa julkisen suun terveydenhuollon toimintaan – Jyväskylän asukkaiden, päättäjien ja työntekijöiden odotukset, käsitykset ja kokemukset

Tutkimuksessa selvitettiin Jyväskylän asukkaiden, päättäjien ja suun terveydenhuollon työntekijöiden palveluodotuksia sekä niiden toteutumista Jyväskylän julkisessa suun terveydenhuollossa sekä verrattuna ympäristökuntiin. Toiseksi tutkittiin päättäjien ja suun terveydenhuollon työntekijöiden käsityksiä alan työmotivaatioon vaikuttavista tekijöistä Jyväskylässä ja ympäristökunnissa. Kolmas tutkimuskohde oli työhyvinvointi, jota selvitettiin Jyväskylässä ja seitsemässä muussa julkisessa suun terveydenhuollossa sekä Jyväskylän yksityishammaslääkäreiden vastaanotoilla. Tutkimuksen tiedot kerättiin postikyselynä, johon vastasi 1 151 asukasta, 125 päättäjää ja 388 suun terveydenhuollon työntekijää. Tulokset osoittivat, että Jyväskylän julkisen suun terveydenhuollon palvelujen järjestämisessä ei kuultu tarpeeksi kuntalaisia eikä alan ammattilaisia. Palvelut toteutuivat useammin päättäjien kuin asukkaiden ja työntekijöiden odotusten mukaisesti. Asukkaiden odotukset olivat lähempänä työntekijöiden kuin päättäjien odotuksia. Suurimmat erot olivat päättäjien ja alan ammattilaisten välillä. Jyväskylän päättäjät eivät tunteneet tarpeeksi julkisessa suun terveydenhuollossa tehtävän työn vaatimuksia eivätkä sen erityispiirteitä. Jyväskylän ja ympäristökuntien välillä asukkaiden, päättäjien ja alan ammattilaisten odotukset suun terveydenhuollon palveluista erosivat vain vähän. Sen sijaan palveluiden toteutumisessa erot olivat suuremmat. Palvelut toimivat monilta osin paremmin ympäristökunnissa kuin Jyväskylässä. Jyväskylän suun terveydenhuollon työelämän laadussa oli ongelmia ja ne olivat suuremmat kuin verrokkiterveyskeskuksissa ja Jyväskylän yksityishammaslääkäreiden vastaanotoilla. Hyvä fyysinen työympäristö sekä hyvä työajan hallinta olivat voimavaratekijöitä, jotka Jyväskylän suun terveydenhuollossa suojasivat työntekijöitä työn kuormittavuuden haitallisilta vaikutuksilta. Työelämän laadun parantaminen vaatisi erityisesti näiden voimavarojen vahvistamista. Päättäjien tulisi tiedostaa niiden vaikutus työntekijöiden työmotivaatioon ja resursoida julkista suun terveydenhuoltoa riittävästi siellä tehtävän työn vaatimuksiin nähden. Kaiken kaikkiaan suun terveydenhuollon merkitys kuntalaisten hyvinvoinnille ja elämänlaadulle pitäisi paremmin ottaa huomioon Jyväskylän julkisessa terveydenhuollossa resursseja jaettaessa sekä toimintatapoja ja palvelurakenteita uudistettaessa. Tuloksellisuus suun terveydenhuollossa edellyttäisi, että palveluja kehitettäisiin vastaamaan mahdollisimman hyvin sekä kuntalaisten että työelämän tarpeita resurssien antamissa rajoissa. Jyväskylässä tarvittaisiin asukkaiden, päättäjien ja suun terveydenhuollon työntekijöiden välillä jatkuvaa vuoropuhelua ja parempaa tiedon välittymistä. Monipuolisen tiedon perusteella päättäjät pystyisivät palveluja järjestäessään sovittamaan paremmin yhteen eri osapuolten tarpeet ja tavoitteet sekä ratkaisemaan intressiristiriitoja.

LONG-TERM EFFECTS OF SWINE wastewater AND MINERAL FERTILIZER ASSOCIATION ON SOIL MICROBIOTA

ABSTRACT Swine wastewater (SW) application in agricultural soils may affect its microbial community in a long term. The objective of this study was to evaluate prospective changes in soil bacterial community after eight years continuous application of swine wastewater. The wastewater doses tested were 0; 100; 200 and 300 m3 ha-1, being applied from the beginning of the experiment and with or without recommended fertilization. Three soil samples were taken from each plot for determinations of basal respiration, microbial biomass and metabolic quotient. We also performed DGGE analysis and made a correlation between soil chemical conditions and microbial activity. Microbial community underwent significant structural changes from swine wastewater applications. Higher SW doses (200 and 300 m3 ha-1) influenced significantly (p <0.05) and benefitted certain bacteria groups.

Improving product profitability control in continuous IT-services

The target of the thesis is to improve product profitability control in continuous IT-services. Accurate product cost accounting and correctly allocated revenues are a necessity for good product profitability control. The focus of the study is on costs and revenues that are not traced directly to services. The thesis is focused on revenue allocations as revenue allocation methods have not been used in the case company before. In order to achieve the target revenue allocation methods, which improve the product profitability accounting and control, are presented. The research methods used in the thesis are literature review and empirical case study. The research approach is constructive. The theoretical part is composed of literature and articles that create a base for the empirical part. Internal interviews describe the current situation in the company and based on it development actions are planned. The part of the empirical case study is seen mostly in the limitations as the research is limited to concern only one department in the company. Problems in the revenue tracing are caused by customer specific services and lack of service definitions because of which the revenues are not traced correctly. Methods to allocate revenues are presented in the thesis and stand-alone revenue allocation method is the most suitable one because it is fair and it can be modified. Approximate product profitability analysis is done in the thesis and the results of it indicate that some services are profitable and some unprofitable.

Atenolol prevents the formation of expansive hematoma after rhytidoplasty

Objective: To evaluate the perioperative use of atenolol in reducing the incidence of hematoma after rhytidoplasty.Methods: Between January 2007 and February 2013, 80 patients were randomized into two groups: Group A (n = 26) received perioperative atenolol in order to maintain heart rate (PR) around 60 per minute; Group B (n = 54) did not receive atenolol. Both groups underwent the same anesthetic and surgical technique. We monitored blood pressure (BP), HR, hematoma formation and the need for drainage. Patients were followed-up until the 90th postoperative day. The variables were compared between the groups using the ANOVA test. Continuous variables were presented as mean ± standard deviation and the differences were compared with the Student's t test. Values of p d" 0.05 were considered significant.Results: In group A the mean BP (110-70mmHg ± 7.07) and HR (64 / min ± 5) were lower (p d" 0.05) than in group B (135-90mmHg ± 10.6) and (76 / min ± 7.5), respectively. There were four cases of expansive hematoma in group B, all requiring reoperation for drainage, and none in group A (p d" 0,001).Conclusion: The perioperative use of atenolol caused a decrease in blood pressure and heart rate and decreased the incidence of expanding hematoma after rhytidectomy.

Scintigraphic study of the splenic circulation in rats

Objective: To evaluate the splenic parenchymal blood distribution through scintigraphic study.Methods: Thirty Wistar rats were randomly divided into six groups (n = 5). Group 1 (spleen - 30 minutes) and Group 2 (spleen - 90 minutes) underwent laparotomy with direction of blood flow to the spleen by ligature of the aorta near the iliac bifurcation and splanchnic vessels, keeping blood flow only in the splenic artery; Group 3 (spleen and stomach - 30 minutes) and Group 4 (spleen and stomach - 90 minutes) underwent laparotomy with direction of blood flow to the spleen and stomach by ligature of the aorta near the iliac bifurcation and splanchnic vessels, maintaining the flow through the splenic, gastric and splenogastric vessels; Group 5 (control - 30 minutes) and Group 6 (control - 90 minutes) underwent laparotomy and ligation of the aorta near the iliac bifurcation, keeping the flow to the abdominal organs. After arterial ligation, the animals received an injection of 0.2 ml of sodium pertechnetate in the aorta. Scintigraphic images were taken and the animals had their spleens removed for radioactivity counting with an automatic counter device.Results: There was no difference in the amounts of radiation from the spleen between groups, indicating retention of the radioisotope by the spleen, even after the period of 90 minutes.Conclusion: The blood flow through the spleen is not continuous. The blood diffuses through the splenic parenchyma and its venous drainage is slow, not following a predictable sequence.

Ultrasonografic changes in the axillary vein of patients with lymphedema after mastectomy

OBJECTIVE: To determine the prevalence of sonographic abnormalities (SA) in the axillary vein of patients with and without post-mastectomy lymphedema. METHODS: We studied a sample of 80 women, divided into two equal groups, with and without lymphedema, with B mode ultrasound, color and pulsed Doppler. The primary variable, SA, is defined as change in the venous diameter, parietal thickening, intraluminal images, compressibility, parietal collapse at inspiration and feature of the axillary venous flow on the operated side. Secondary variables were: stage of lymphedema, surgical technique, number of radio and chemotherapy sessions, limb volume, weight and age. The differences between the proportions in the groups were determined using the Chi-square test and / or Fisher's test. For continuous variables, we used the Mann-Whitney Test. To estimate the magnitude of the associations, we used the prevalence rate of SA in both groups as a measure of frequency, and as a measure of association, the prevalence ratio (PR) obtained as a function of relative risk (RR) and estimated by the test Mantel-Haenszel homogeneity test. We adopted the statistical significance level of 5% (p < 0.05). RESULTS: only the criterion "parietal thickening" was strongly associated with the lymphedema group (p = 0.001). The prevalence of SA was 55% in patients with lymphedema and 17.5% in the group without it, with difference in prevalence of 37.5%. CONCLUSION: the prevalence of SA was higher in patients undergoing mastectomy with lymphedema than in those without lymphedema.