Defects in Persistent Luminescence Materials

Persistent luminescence materials can store energy from solar radiation or artificial lighting and release it over a period of several hours without a continuous excitation source. These materials are widely used to improve human safety in emergency and traffic signalization. They can also be utilized in novel applications including solar cells, medical diagnostics, radiation detectors and structural damage sensors. The development of these materials is currently based on methods based on trial and error. The tailoring of new materials is also hindered by the lack of knowledge on the role of their intrinsic and extrinsic lattice defects in the appropriate mechanisms. The goal of this work was to clarify the persistent luminescence mechanisms by combining ab initio density functional theory (DFT) calculations with selected experimental methods. The DFT approach enables a full control of both the nature of the defects and their locations in the host lattice. The materials studied in the present work, the distrontium magnesium disilicate (Sr₂MgSi₂O₇) and strontium aluminate (SrAl₂O₄) are among the most efficient persistent luminescence hosts when doped with divalent europium Eu²⁺ and co-doped with trivalent rare earth ions R³⁺ (R: Y, La-Nd, Sm, Gd-Lu). The polycrystalline materials were prepared with the solid state method and their structural and phase purity was confirmed by X-ray powder diffraction. Their local crystal structure was studied by high-resolution transmission electron microscopy. The crystal and electronic structure of the nondoped as well as Eu²⁺, R^2+/3+ and other defect containing materials were studied using DFT calculations. The experimental trap depths were obtained using thermoluminescence (TL) spectroscopy. The emission and excitation of Sr₂MgSi₂O₇:Eu²+,Dy³⁺ were also studied. Significant modifications in the local crystal structure due to the Eu²⁺ ion and lattice defects were found by the experimental and DFT methods. The charge compensation effects induced by the R³⁺ co-doping further increased the number of defects and distortions in the host lattice. As for the electronic structure of Sr₂MgSi₂O₇ and SrAl₂O₄, the experimental band gap energy of the host materials was well reproduced by the calculations. The DFT calculated Eu²⁺ and R^2+/3+ 4fn as well as 4f^n-15d¹ ground states in the Sr₂MgSi₂O₇ band structure provide an independent verification for an empirical model which is constructed using rather sparse experimental data for the R³⁺ and especially the R²⁺ ions. The intrinsic and defect induced electron traps were found to act together as energy storage sites contributing to the materials’ efficient persistent luminescence. The calculated trap energy range agreed with the trap structure of Sr₂MgSi₂O₇ obtained using TL measurements. More experimental studies should be carried out for SrAl₂O₄ to compare with the DFT calculations. The calculated and experimental results show that the electron traps created by both the rare earth ions and vacancies are modified due to the defect aggregation and charge compensation effects. The relationships between this modification and the energy storage properties of the solid state materials are discussed.

Mild Cognitive Impairment and Early Detection of Alzheimer`s Disease. A Positron Emission Tomography Study

Alzheimer`s disease (AD) is characterised neuropathologically by the presence of extracellular amyloid plaques, intraneuronal neurofibrillary tangles, and cerebral neuronal loss. The pathological changes in AD are believed to start even decades before clinical symptoms are detectable. AD gradually affects episodic memory, cognition, behaviour and the ability to perform everyday activities. Mild cognitive impairment (MCI) represents a transitional state between normal aging and dementia disorders, especially AD. The predictive accuracy of the current and commonly used MCI criteria devide this disorder into amnestic (aMCI) and non-amnestic (naMCI) MCI. It seems that many individuals with aMCI tend to convert to AD. However many MCI individuals will remain stable and some may even recover. At present, the principal drugs for the treatment of AD provide only symptomatic and palliative benefits. Safe and effective mechanism-based therapies are needed for this devastating neurodegenerative disease of later life. In conjunction with the development of new therapeutic drugs, tools for early detection of AD would be important. In future one of the challenges will be to detect at an early stage these MCI individuals who will convert to AD. Methods which can predict which MCI subjects will convert to AD will be much more important if the new drug candidates prove to have disease-arresting or even disease–slowing effects. These types of drugs are likely to have the best efficacy if administered in the early or even in the presymptomatic phase of the disease when the synaptic and neuronal loss has not become too widespread. There is no clinical method to determine with certainly which MCI individuals will progress to AD. However there are several methods which have been suggested as predictors of conversion to AD, e.g. increased [11C] PIB uptake, hippocampal atrophy in MRI, low CSF A beta 42 level, high CSF tau-protein level, apolipoprotein E (APOE) ε4 allele and impairment in episodic memory and executive functions. In the present study subjects with MCI appear to have significantly higher [¹¹C] PIB uptake vs healthy elderly in several brain areas including frontal cortex, the posterior cingulate, the parietal and lateral temporal cortices, putamen and caudate. Also results from this PET study indicate that over time, MCI subjects who display increased [¹¹C] PIB uptake appear to be significantly more likely to convert to AD than MCI subjects with negative [¹¹C] PIB retention. Also hippocampal atrophy seems to increase in MCI individuals clearly during the conversion to AD. In this study [¹¹C] PIB uptake increases early and changes relatively little during the AD process whereas there is progressive hippocampal atrophy during the disease. In addition to increased [¹¹C] PIB retention and hippocampal atrophy, the status of APOE ε4 allele might contribute to the conversion from MCI to AD.

Multifrequency VLBI Observations of Selected Active Galactic Nuclei

In this dissertation, active galactic nuclei (AGN) are discussed, as they are seen with the high-resolution radio-astronomical technique called Very Long Baseline Interferometry (VLBI). This observational technique provides very high angular resolution (_ 10−300 = 1 milliarcsecond). VLBI observations, performed at different radio frequencies (multi-frequency VLBI), allow to penetrate deep into the core of an AGN to reveal an otherwise obscured inner part of the jet and the vicinity of the AGN’s central engine. Multi-frequency VLBI data are used to scrutinize the structure and evolution of the jet, as well as the distribution of the polarized emission. These data can help to derive the properties of the plasma and the magnetic field, and to provide constraints to the jet composition and the parameters of emission mechanisms. Also VLBI data can be used for testing the possible physical processes in the jet by comparing observational results with results of numerical simulations. The work presented in this thesis contributes to different aspects of AGN physics studies, as well as to the methodology of VLBI data reduction. In particular, Paper I reports evidence of optical and radio emission of AGN coming from the same region in the inner jet. This result was obtained via simultaneous observations of linear polarization in the optical and in radio using VLBI technique of a sample of AGN. Papers II and III describe, in detail, the jet kinematics of the blazar 0716+714, based on multi-frequency data, and reveal a peculiar kinematic pattern: plasma in the inner jet appears to move substantially faster that that in the large-scale jet. This peculiarity is explained by the jet bending, in Paper III. Also, Paper III presents a test of the new imaging technique for VLBI data, the Generalized Maximum Entropy Method (GMEM), with the observed (not simulated) data and compares its results with the conventional imaging. Papers IV and V report the results of observations of the circularly polarized (CP) emission in AGN at small spatial scales. In particular, Paper IV presents values of the core CP for 41 AGN at 15, 22 and 43 GHz, obtained with the help of the standard Gain transfer (GT) method, which was previously developed by D. Homan and J.Wardle for the calibration of multi-source VLBI observations. This method was developed for long multi-source observations, when many AGN are observed in a single VLBI run. In contrast, in Paper V, an attempt is made to apply the GT method to single-source VLBI observations. In such observations, the object list would include only a few sources: a target source and two or three calibrators, and it lasts much shorter than the multi-source experiment. For the CP calibration of a single-source observation, it is necessary to have a source with zero or known CP as one of the calibrators. If the archival observations included such a source to the list of calibrators, the GT could also be used for the archival data, increasing a list of known AGN with the CP at small spatial scale. Paper V contains also calculation of contributions of different sourced of errors to the uncertainty of the final result, and presents the first results for the blazar 0716+714.

Teurasjätteiden jalostaminen liikennepolttoaineiksi

Työssä määritettiin luokan 2 eläinperäisistä sivutuotteista liikennekäyttöön tuotettujen biodieselin ja biometaanin elinkaaren aikaiset kasvihuonekaasupäästöt ja tuotantoprosessien energiankulutukset perustuen kirjallisuuslähteistä saatuihin lähtötietoihin. Tätä kautta tutkittiin yhdistelmäprosessia, jossa tuotetaan molempia polttoaineita ja selvitettiin onko tällaisella tuotantotavalla mahdollista vähentää päästöjä ja parantaa polttoaineiden tuotannon energiatehokkuutta. Kasvihuone-kaasupäästöjen laskentamenetelmä pohjautuu direktiivissä 2009/28/EY annettuun ohjeistukseen ja eri kasvihuonekaasupäästöjen karakterisointi IPCC:n sadan vuoden tarkastelumalliin. Käytännön laskenta suoritettiin standardien SFS-EN ISO 14040 ja 14044 määrittelemän elinkaariarviointiselvityksen muodossa. Työssä käytetyn laskentamenetelmän ja tarkasteluun valittujen tuotanto-teknologioiden perusteella lasketut tulokset osoittavat, että yhdistelmäprosessilla ei saavuteta suurempia päästövähenemiä eikä parempaa energiatehokkuutta kuin nykyisin käytössä olevilla tuotantotavoilla. Tulokset ovat kuitenkin hyvin herkkiä laskennassa tehtyjen oletusten ja käytettyjen lähtötietojen vaihtelulle sekä valittujen laskentamenetelmien muutoksille. Suurin päästöjä ja energiankulutusta aiheuttava yksittäinen tekijä on kaikissa tuotejärjestelmissä luokan 2 sivutuotteiden esikäsittelyssä vaadittavaan steri-lointiin tarvittavan lämmön tuotanto. Tutkituissa tuotejärjestelmissä lämpö tuotetaan kokonaan tai osittain fossiilisilla polttoaineilla. Kasvihuone-kaasupäästöjä olisi mahdollista alentaa merkittävästi siirtymällä lämmön tuotannossa kokonaan uusiutuviin polttoaineisiin. Sterilointi on lain edellyttämä käsittelytapa ja siksi energiankulutusta on vallitsevissa olosuhteissa hyvin vaikea pienentää merkittävästi.

Perspectives for the production and usage of wood chips as a source of energy in the North-West of Russia

The development of bioenergy on the basis of wood fuels has received considerable attention in the last decades. The combination of large forest resources and reliance on fossil fuels makes the issue of wood chips usage in Russia an actual topic for the analysis. The main objective of this study is to disclose the current state and perspectives for the production of wood chips and their usage as a source of energy in the North-West of Russia. The study utilizes an integrated approach to explore the market of wood chips on the basis of comprehensive analysis of documentation and expert opinions. The analysis of wood chips market was performed for eight regions of the North-West district of Russia within two major dimensions: its current state and perspectives in the nearest five years. The results of the study show a comprehensive picture of the wood chips market, including the potential for wood chips production, the specific features of production and consumption and the perspectives for the market development within the regions of the North-West district of Russia. The study demonstrated that the market of wood chips is underdeveloped in the North-West of Russia. The findings of the work may be used by forest companies for the strategic planning.

Lämpöpumppujärjestelmät integroidussa kylmä- ja lämpötehon tuotossa

Tässä työssä tutkittiin lämpöpumppujärjestelmiä, joilla tuotetaan samaan aikaan kylmä- ja lämpötehoa. Höyryn puristus lämpöpumppu on yleisimmin käytetty lämpöpumpputyyppi ja sen pääkomponentit ovat kompressori, lauhdutin, paisuntaventtiili ja höyrystin. Lämpöpumppu tuottaa samaan aikaan kylmätehoa höyrystimellä ja lämpötehoa lauhduttimella. Lämpöpumpun toiminta-arvoihin vaikuttaa valittujen lämpötilatasojen lisäksi voimakkaasti valitun kiertoaineen termodynaamiset ominaisuudet sekä kompressorin painesuhteeseen verrannollinen isentrooppihyötysuhde. Uusissa lämpöpumpuissa käytetään HFC yhdisteitä sekä sekoituksia kiertoaineina, mutta myös luonnolliset aineet, kuten ammoniakki, ovat lupaavia korvikkeita CFC yhdisteille. Sopivia sovelluskohteita kylmä- ja lämpötehon yhteistuotannolle ovat kauppa- ja asuinrakennukset, hotellit, toimistot, elintarviketeollisuus ja -myymälät sekä vierekkäiset jää- ja uimahallit ja hiihtoputket. Kylmä- ja lämpötehon yhteistuotannolla voitaisiin saavuttaa merkittäviä säästöjä ja päästövähennyksiä. Esimerkiksi jäähallien kylmäkoneiden lauhdelämmön hyödyntämisessä olisi Suomessa potentiaalia 6-10 miljoonan euron vuotuisiin säästöihin. Kylmä- ja lämpötehon yhteistuotanto voidaan toteuttaa hyödyntämällä kylmäkoneen lauhdelämpöä toisella lämpöpumpulla. Toinen vaihtoehto on käyttää eri tilojen samanaikaiseen lämmittämiseen ja jäähdyttämiseen HPS lämpöpumppua tai moniyksikköistä lämpöpumppua.

Temporal variability of soil CO2 emission after conventional and reduced tillage described by an exponential decay in time model

To study Assessing the impact of tillage practices on soil carbon losses dependents it is necessary to describe the temporal variability of soil CO2 emission after tillage. It has been argued that large amounts of CO2 emitted after tillage may serve as an indicator for longer-term changes in soil carbon stocks. Here we present a two-step function model based on soil temperature and soil moisture including an exponential decay in time component that is efficient in fitting intermediate-term emission after disk plow followed by a leveling harrow (conventional), and chisel plow coupled with a roller for clod breaking (reduced) tillage. Emission after reduced tillage was described using a non-linear estimator with determination coefficient (R²) as high as 0.98. Results indicate that when emission after tillage is addressed it is important to consider an exponential decay in time in order to predict the impact of tillage in short-term emissions.

In vivo imaging of vascular adhesion protein 1 - preclinical studies with positron emission tomography

The golden standard in nuclear medicine imaging of inflammation is the use of radiolabeled leukocytes. Although their diagnostic accuracy is good, the preparation of the leukocytes is both laborious and potentially hazardous for laboratory personnel. Molecules involved in leukocyte migration could serve as targets for the development of inflammation imaging agents. An excellent target would be a molecule that is absent or expressed at low level in normal tissues, but is induced or up-regulated at the site of inflammation. Vascular adhesion protein-1 (VAP-1) is a very promising target for in vivo imaging, since it is translocated to the endothelial cell surface when inflammation occurs. VAP-1 functions as an endothelial adhesion molecule that participates in leukocyte recruitment to inflamed tissues. Besides being an adhesion molecule, VAP-1 also has enzymatic activity. In this thesis, the targeting of VAP-1 was studied by using Gallium-68 (68Ga) labeled peptides and an Iodine-124 (124I) labeled antibody. The peptides were designed based on molecular modelling and phage display library searches. The new imaging agents were preclinically tested in vitro, as well as in vivo in animal models. The most promising imaging agent appeared to be a peptide belonging to the VAP-1 leukocyte ligand, Siglec-9 peptide. The 68Ga-labeled Siglec-9 peptide was able to detect VAP-1 positive vasculature in rodent models of sterile skin inflammation and melanoma by positron emission tomography. In addition to peptides, the 124I-labeled antibody showed VAP-1 specific binding both in vitro and in vivo. However, the estimated human radiation dose was rather high, and thus further preclinical studies in disease models are needed to clarify the value of this imaging agent. Detection of VAP-1 on endothelium was demonstrated in these studies and this imaging approach could be used in the diagnosis of inflammatory conditions as well as melanoma. These studies provide a proof-of-concept for PET imaging of VAP-1 and further studies are warranted.

Cyanobacteria from the Baltic Sea and Finnish lakes as an energy source and modulators of bioenergetic pathways

Cyanobacteria are a diverse group of oxygenic photosynthetic bacteria that inhabit in a wide range of environments. They are versatile and multifaceted organisms with great possibilities for different biotechnological applications. For example, cyanobacteria produce molecular hydrogen (H2), which is one of the most important alternatives for clean and sustainable energy. Apart from being beneficial, cyanobacteria also possess harmful characteristics and may become a source of threat to human health and other living organisms, as they are able to form surface blooms that are producing a variety of toxic or bioactive compounds. The University of Helsinki Culture Collection (UHCC) maintains around 1,000 cyanobacterial strains representing a large number of genera and species isolated from the Baltic Sea and Finnish lakes. The culture collection covers different life forms such as unicellular and filamentous, N2-fixing and non-N2-fixing strains, and planktonic and benthic cyanobacteria. In this thesis, the UHCC has been screened to identify potential strains for sustainable biohydrogen production and also for strains that produce compounds modifying the bioenergetic pathways of other cyanobacteria or terrestrial plants. Among the 400 cyanobacterial strains screened so far, ten were identified as high H2-producing strains. The enzyme systems involved in H2 metabolism of cyanobacteria were analyzed using the Southern hybridization approach. This revealed the presence of the enzyme nitrogenase in all strains tested, while none of them are likely to have contained alternative nitrogenases. All the strains tested, except for two Calothrix strains, XSPORK 36C and XSPORK 11A, were suggested to contain both uptake and bidirectional hydrogenases. Moreover, 55 methanol extracts of various cyanobacterial strains were screened to identify potent bioactive compounds affecting the photosynthetic apparatus of the model cyanobacterium, Synechocystis PCC 6803. The extract from Nostoc XPORK 14A was the only one that modified the photosynthetic machinery and dark respiration. The compound responsible for this effect was identified, purified, and named M22. M22 demonstrated a dual-action mechanism: production of reactive oxygen species (ROS) under illumination and an unknown mechanism that also prevailed in the dark. During summer, the Baltic Sea is occupied by toxic blooms of Nodularia spumigena (hereafter referred to as N. spumigena), which produces a hepatotoxin called nodularin. Long-term exposure of the terrestrial plant spinach to nodularin was studied. Such treatment resulted in inhibition of growth and chlorosis of the leaves. Moreover, the activity and amount of mitochondrial electron transfer complexes increased in the leaves exposed to nodularin-containing extract, indicating upregulation of respiratory reactions, whereas no marked changes were detected in the structure or function of the photosynthetic machinery. Nodularin-exposed plants suffered from oxidative stress, evidenced by oxidative modifications of various proteins. Plants initiated strategies to combat the stress by increasing the levels of alpha-tocopherol, mitochondrial alternative oxidase (AOX), and mitochondrial ascorbate peroxidase (mAPX).

Soil CO2 emission as related to incorporation of sugarcane crop residues and aggregate breaking after rotary tiller

Soil tillage is a process that accelerates soil organic matter decomposition transferring carbon to atmosphere, mainly in the CO2 form. In this study, the effect of rotary tillage on soil CO2 emission was investigated, including the presence of crop residues on the surface.Emissions were evaluated during 15 days after tillage in 3 plots: 1) non-tilled and without crop residues on soil surface (NTwo), 2) rotary tiller without the presence of crop residues on soil surface (RTwo), and 3) rotary tiller with the presence of crop residues in soil surface (RTw). Emissions from the RTw plot were higher than the other plots, (0.777 g CO2 m-2 h-1), with the lowest emissions recorded in the NTwo plot (0.414 g CO2 m-2 h-1). Total emission indicates that the difference of C-CO2 emitted to atmosphere corresponds to 3% of the total additional carbon in the crop residues in the RTw plot compared to RTwo. The increase in the RTwo emission in comparison to NTwo was followed by changes in the aggregate size distribution, especially those with average diameter lower than 2 mm. The increase in emission from the RTw plot in relation to RTwo was related to a decrease in crop residue mass on the surface, and its higher fragmentation and incorporation in soil. When the linear correlation between soil CO2 emission, and soil temperature and soil moisture is considered, only the RTw treatment showed significant correlation (p<0.05) with soil moisture.

Environmental adaptation of the source of the subbasin of Rico Stream, Monte Alto - SP, Brazil

The aim of this study was to define the photographic patterns that represent the use and occupation of the landcover of the "spring" of the Rico Stream subbasin, located at Monte Alto, state of São Paulo (SP), Brazil, for environmental adaptation regarding the Brazilian Forest Law. The mapping was performed using remote sensing techniques and visual interpretation of the World View image, followed by the digitalization of the net of drainage and vegetation (natural and agricultural) at the AutoCad software with documents and field work. The study area has 2141.53 ha and the results demonstrated that the main crop is sugarcane with 546.34 ha, followed by 251.22 ha of pastures, 191.71 ha of perennial crops, 57.31 ha of Eucalyptus and 49.52 ha of onion, confirming the advance of sugarcane culture in the region. The region has 375.04 ha of areas of permanent preservation (APPs), and of this area it was found that only 72.17 ha (19.24%) has arboreal vegetation or natural forest, and 302.87 ha of these areas need to be enriched and reforested with native vegetation from the region, according to the current legislation. The data of the area enable future proposals of models for environmental adaptation to the microbasin according to the current environmental legislation.

Alternative liquid biofuels for lime kilns

Causticizing plant is an important part of kraft pulp mill. It uses green liquor from recovery boiler as a raw material and consumes lime to produce white liquor, which is an important chemical used in pulping. Lime kiln is a part of the causticizing process. It is used to convert lime mud, a by-product obtained from the causticizing back to lime in high temperatures. This conversion requires a lot of energy. The most common fuels used as energy source for lime kiln are heavy fuel oil and natural gas. In a modern pulp mill lime kiln is the only user of significant amount of fossil fuels. Replacing fossil fuels with biofuels can have prominent economical and environmental benefits. Interest in using biofuels as energy source of lime kiln has become a worldwide issue in the recent years. However fuels used for lime kiln have a lot of certain requirements. The purpose of this work is to study the required characteristics from liquid fuels used in pulp mill lime kiln and to map suitable liquid biofuels already available in the markets. Also taxation of liquid biofuels compared to heavy fuel oil in Finland, Sweden and Germany is shortly introduced.

Corporate Social Responsibility in the Oil and Gas Industry: Environmental Management Systems as a Source of Sustainable Development

The environmental aspect of corporate social responsibility (CSR) expressed through the process of the EMS implementation in the oil and gas companies is identified as the main subject of this research. In the theoretical part, the basic attention is paid to justification of a link between CSR and environmental management. The achievement of sustainable competitive advantage as a result of environmental capital growth and inclusion of the socially responsible activities in the corporate strategy is another issue that is of special significance here. Besides, two basic forms of environmental management systems (environmental decision support systems and environmental information management systems) are explored and their role in effective stakeholder interaction is tackled. The most crucial benefits of EMS are also analyzed to underline its importance as a source of sustainable development. Further research is based on the survey of 51 sampled oil and gas companies (both publicly owned and state owned ones) originated from different countries all over the world and providing reports on sustainability issues in the open access. To analyze their approach to sustainable development, a specifically designed evaluation matrix with 37 indicators developed in accordance with the General Reporting Initiative (GRI) guidelines for non-financial reporting was prepared. Additionally, the quality of environmental information disclosure was measured on the basis of a quality – quantity matrix. According to results of research, oil and gas companies prefer implementing reactive measures to the costly and knowledge-intensive proactive techniques for elimination of the negative environmental impacts. Besides, it was identified that the environmental performance disclosure is mostly rather limited, so that the quality of non-financial reporting can be judged as quite insufficient. In spite of the fact that most of the oil and gas companies in the sample claim the EMS to be embedded currently in their structure, they often do not provide any details for the process of their implementation. As a potential for the further development of EMS, author mentions possible integration of their different forms in a single entity, extension of existing structure on the basis of consolidation of the structural and strategic precautions as well as development of a unified certification standard instead of several ones that exist today in order to enhance control on the EMS implementation.