SYNTHESIS AND CHARACTERIZATION OF HDTMA-ORGANOCLAYS: INSIGHTS INTO THEIR STRUCTURAL PROPERTIES

This study aims to synthesize and characterize organoclays developed from an Argentinian montmorillonite (Bent) using hexadecyltrimethylammonium bromide (HDTMA-Br) as the intercalation agent. Subsequently, an adsorption mechanism is proposed. The obtained organoclays were more hydrophobic than the starting clay. Surfactant molecules were adsorbed initially through cation exchange in sites placed in the interlayer space of the clay. Adsorption in such sites continued until the interlayer space was saturated. Depending on the surfactant loading introduced during the intercalation process, different organizations of surfactant in the interlayer were obtained. Further adsorption of surfactant occurred in the mesopores generated by tactoids in the "house of cards" organization. This process kept surfactant molecules relatively free and out of the interlayer space.

Social competence and loneliness during the school years - Issues in assessment, interrelations and intergenerational transmission

Väitöskirjassa tarkastellaan kouluikäisten lasten ja nuorten sosiaalisen kompetenssin ja yksinäisyyden mittaamista, yhteyksiä ja periytyvyyttä vanhemmilta heidän lapsilleen. Alakouluikäisten lasten tutkimusaineisto (n=985) koostuu lapsilta itseltään, heidän luokkatovereiltaan, opettajiltaan ja vanhemmiltaan vuosina 2000 - 2004 osana Merkitystä etsimässä – tutkimusprojektia (M. Vauras) kerätystä aineistosta. Mukana on itse-, toveri-, opettaja- ja vanhempien arviot lasten sosiaalisesta kompetenssista, seuranta-aineisto lasten yksinäisyydestä, opettajien arviot lasten motivationaalisesta orientaatiosta, standardoiduin testisarjoin arvioidut akateemiset taidot sekä lasten äitien ja isien arviot omasta yksinäisyydestään ja koetusta kyvykkyydestään toimia vanhempana. Yläkouluikäisten nuorten (n=386) aineisto koostuu vuosina 2006 – 2007 osana Sosioemotionaalinen oppiminen ja hyvinvointi yläkouluyhteisössä (P. M. Niemi) kerätystä nuorten yksinäisyyden, sosiaalisen ahdistuneisuuden ja sosiaalisen fobian seuranta-aineistosta. Mitattavuutta (päätavoite 1) tutkittiin erityisesti monitahoarviointien rakenteiden yhtenäisyyksiä, subjektiivisten arvioiden ajallista pysyvyyttä sekä mittareiden validiteettia ja reliabiliteettia testaamalla. Sosiaalisen kompetenssin ja yksinäisyyden keskinäisten yhteyksien lisäksi tarkasteltiin näiden yhteyttä alakoululaisten oppimiseen sekä yläkou¬lulaisten psykososiaaliseen hyvinvointiin (päätavoite 2). Kolmantena päätavoitteena oli selvittää yksinäisyyden mahdollista periytymistä vanhemmilta lapsille. Osana ensimmäistä päätavoitetta kehitettiin Monitahoarviointi sosiaalisesta kompetenssista (MASK) -arviointimenetelmä (artikkeli 1). Konfirmatorisen faktorianalyysin tulosten perusteella nelifaktorinen rakenne (prososiaalisuus sisältäen yhteistyötaidot ja empatiakyvyn sekä antisosiaalisuus sisältäen impulsiivisuuden ja häiritsevyyden) sopi sekä lasten itsensä, heidän luokkatovereidensa, opettajiensa että vanhempiensa tekemiin arviointeihin. Eri tahojen arviointien väliset korrelaatiot olivat tilastollisesti merkitseviä, joskin suhteellisen matalia, ts. eri tahojen näkökulmat lapsen sosiaalisesta kompetenssista ovat toisistaan eriäviä. Täten eri arvioitsijatahojen käyttäminen on kokonaisuuden tutkimisen kannalta tärkeää. Toisena mittaamiseen liittyvänä tavoitteena oli validoida Hozan, Bukowskin ja Beeryn (2000) sosiaalisen ja emotionaalisen yksinäisyyden mittari suomalaisille lapsille (artikkeli 3) ja nuorille (artikkeli 4) soveltuvaksi sekä tutkia, ovatko lasten ja nuorten arviot omasta yksinäisyydestään ajallisesti pysyviä. Alakoululaisten lasten osalta yksinäisyys, erityisesti sosiaalinen yksinäisyys osoittautui suhteellisen pysyväksi, mutta vahvistui entisestään yläkouluikäisten nuorten aineistoa tarkasteltaessa. Huomionarvoista sekä ala- että yläkoululaisten aineistoissa oli poikien kokema vahva emotionaalinen yksinäisyys. Molempien mittareiden osalta sekä validiteetti että reliabiliteetti todettiin hyväksyttäväksi ja niitä voidaan suositella lasten ja nuorten sosiaalisen kompetenssin ja yksinäisyyden arviointimenetelmiksi. Toisena päätavoitteena oli rakenneyhtälömallinnuksen keinoin tarkastella sosiaalisen kompetenssin ja yksinäisyyden yhteyksiä sekä keskenään (artikkelit 2 ja 3) että suhteessa lasten oppimiseen (artikkeli 2) ja nuorten psykososiaaliseen hyvinvointiin (artikkeli 4). Alakouluikäisten lasten osalta sosiaalinen kompetenssi oli yhteydessä pait¬si yksinäisyyteen myös opettajien oppilaistaan tekemiin motivationaalisen orientaation arvioihin sekä standardoiduin testien arvioituihin akateemisiin taitoihin. Yläkouluikäisten nuorten osalta yksinäisyys oli yhteydessä sosiaaliseen ahdistuneisuuteen ja sosiaaliseen fobiaan. Täten sosiaalisen kompetenssin voidaan katsoa olevan koululaisten hyvinvointia ja oppimista vahvistava, ja toisaalta yksinäisyyden nuorten psykososiaalista hyvinvointia heikentävä tekijä. Viimeisenä päätavoitteena mallinnettiin yksinäisyyden mahdollista periytyvyyttä. Ensimmäisessä vaiheessa periytyvyyttä tarkasteltiin koko perheen sisällä, vanhempien tai lasten sukupuolta erottelematta (artikkeli 2). Tässä rakenneyhtälömallissa vanhempien kokema yksinäisyys ennusti heikompaa kyvykkyydentunnetta vanhemmuudesta, joka edelleen ennusti lapsen heikompaa toveriarvioitua sosiaalista kompetenssia koulussa ja tätä kautta vahvempaa yksinäisyyden kokemusta. Toisessa mallissa eroteltiin äitien ja isien sekä tyttöjen ja poikien aineistot, jotta periytyvyyttä voitiin tarkastella äiti-tytär, äiti-poika, isä-tytär ja isä-poika dyadisuhteissa. Rakenneyhtälömallinnuksen tulosten perusteella sekä äitien että isien kokema yksinäisyys ennusti

Structural bioinformatics study of cyclin-dependent kinases complexed with inhibitors

The present work describes molecular models for the binary complexes CDK9, CDK5 and CDK1 complexed with Flavopiridol and Roscovitine. These structural models indicate that the inhibitors strongly bind to the ATP-binding pocket of CDKs and the structural comparison with the complexes CDK2:Flavopiridol and CDK2:Roscovitine correlates the structural differences with differences in inhibition of these CDKs by the inhibitors. These structures open the possibility of testing new inhibitor families, in addition to new substituents for the already known lead structures such as flavones and adenine derivatives.

Synthesis, structural and morphological characterization of CeO2-ZnO nanosized powder systems from Pechini's method

This work reports on the investigation of nanosized CeO2-ZnO systems prepared by Pechini's method. The structural and morphological characterization of CeO2-ZnO systems as well as the characterization of CeO2 and ZnO separately, showed that the employed method result in powders with spheroidal particles whose size are in the range 30 - 200 nm, which is appropriate to provide homogeneous suspensions. The ZnO present in the prepared mixed oxides seems to increase particle size distribution and to influence the arrangement of the particles after powder dispersion.

Analysis of the structural and electronic properties of 1-(5-Hydroxymethyl - 4 -[ 5 - (5-oxo-5-piperidin-1-yl-penta-1,3dienyl)-benzo[1,3]dioxol-2-yl] -tetrahydro-furan-2-yl)-5-methyl-1H-pyrimidine-2,4dione molecule

The structural and electronic properties of 1-(5-Hydroxymethyl - 4 -[ 5 - (5-oxo-5-piperidin- 1 -yl-penta- 1,3 -dienyl)-benzo [1,3] dioxol- 2 -yl]-tetrahydro -furan-2 -yl)-5-methy l-1Hpyrimidine-2,4dione (AHE) molecule have been investigated theoretically by performing density functional theory (DFT), and semi empirical molecular orbital calculations. The geometry of the molecule is optimized at the level of Austin Model 1 (AM1), and the electronic properties and relative energies of the molecules have been calculated by density functional theory in the ground state. The resultant dipole moment of the AHE molecule is about 2.6 and 2.3 Debyes by AM1 and DFT methods respectively, This property of AHE makes it an active molecule with its environment, that is AHE molecule may interacts with its environment strongly in solution.

Estimation of standard enthalpy of formation of alkanes in gaseous state by calculating size, structural and electronic parameters in the molecules

A quantitative analysis is made on the correlation ship of thermodynamic property, i.e., standard enthalpy of formation (ΔH fº) with Kier's molecular connectivity index(¹Xv),vander waal's volume (Vw) electrotopological state index (E) and refractotopological state index (R) in gaseous state of alkanes. The regression analysis reveals a significant linear correlation of standard enthalpy of formation (ΔH fº) with ¹Xv, Vw, E and R. The equations obtained by regression analysis may be used to estimate standard enthalpy of formation (ΔH fº) of alkanes in gaseous state.

Structural studies on enzymes of biotechnological and biomedical interest

Structural studies of proteins aim at elucidating the atomic details of molecular interactions in biological processes of living organisms. These studies are particularly important in understanding structure, function and evolution of proteins and in defining their roles in complex biological settings. Furthermore, structural studies can be used for the development of novel properties in biomolecules of environmental, industrial and medical importance. X-ray crystallography is an invaluable tool to obtain accurate and precise information about the structure of proteins at the atomic level. Glutathione transferases (GSTs) are amongst the most versatile enzymes in nature. They are able to catalyze a wide variety of conjugation reactions between glutathione (GSH) and non-polar components containing an electrophilic carbon, nitrogen or sulphur atom. Plant GSTs from the Tau class (a poorly characterized class) play an important role in the detoxification of xenobiotics and stress tolerance. Structural studies were performed on a Tau class fluorodifen-inducible glutathione transferase from Glycine max (GmGSTU4-4) complexed with GSH (2.7 Å) and a product analogue Nb-GSH (1.7 Å). The three-dimensional structure of the GmGSTU4-4-GSH complex revealed that GSH binds in different conformations in the two subunits of the dimer: in an ionized form in one subunit and a non-ionized form in the second subunit. Only the ionized form of the substrate may lead to the formation of a catalytically competent complex. Structural comparison between the GSH and Nb-GSH bound complexes revealed significant differences with respect to the hydrogen-bonding, electrostatic interaction pattern, the upper part of -helix H4 and the C-terminus of the enzyme. These differences indicate an intrasubunit modulation between the G-and Hsites suggesting an induced-fit mechanism of xenobiotic substrate binding. A novel binding site on the surface of the enzyme was also revealed. Bacterial type-II L-asparaginases are used in the treatment of haematopoietic diseases such as acute lymphoblastic leukaemia (ALL) and lymphomas due to their ability to catalyze the conversion of L-asparagine to L-aspartate and ammonia. Escherichia coli and Erwinia chrysanthemi asparaginases are employed for the treatment of ALL for over 30 years. However, serious side-effects affecting the liver and pancreas have been observed due to the intrinsic glutaminase activity of the administered enzymes. Structural studies on Helicobacter pylori L-asparaginase (HpA) were carried out in an effort to discover novel L-asparaginases with potential chemotherapeutic utility in ALL treatment. Detailed analysis of the active site geometry revealed structurally significant differences between HpA and other Lasparaginases that may be important for the biological activities of the enzyme and could be further exploited in protein engineering efforts.

Intercultural bridges in teenagers' theatrical events : performing self and constructing cultural identity through a creative drama process

The overriding aim of this drama educational case study is to deepen the understanding of meaning making in a creative intercultural youth theatre process and to examine it in the context of the 10th European Children's TheatreEncounter. The research task is to give a theoretical description of some key features of a creative drama process as the basis for theory about meaning makingin physical theatre. The first task is to illuminate the culture-historical connections of the multilayered practice of the EDERED-association. The second taskis to analyse and interpret theatrical meaning making. The ethnographical research site is regarded as a theatrical event. The analysis of the theatrical eventis divided into four segments: cultural contexts, contextual theatricality, theatrical playing and playing culture. These segments are connected with four research questions: What are the cultural contexts of a creative drama process? How can the organisation of the Encounter, genres, aesthetic codes and perception ofcodes be seen to influence the lived experiences of the participants? What are some of the key phases and characteristics in a creative practice? What kind of cultural learning can be interpreted from the performance texts? The interpretative question concerns identity and community (re)construction. How are the categories, `community´ and `child´ constructed in the Encounter culture? In this drama educational case study the research material (transcribed interviews, coded questionnaire answers, participant drawings, videotaped process text and performance texts) are examined in a multi-method analysis in the meta-theoretical framework of Dewey's naturalistic pragmatism. A three-dimensional research interest through a combination of lived experiences, social contexts and cultural-aesthetical practices compared with drama-educational practices required the methodological project of cultural studies. Furthermore, the critical interpretation of cultural texts is divided into three levels of analyses which are called description, structural analysis and theoretical interpretation. Dialogic validity (truthfulness, self-reflexivity and polyvocality) is combined with contextual validity (sensitivity to social context and awareness of historicity) and with deconstructive validity (awareness of the social discourses). My research suggests that itis possible, by means of physical theatre, to construct symbolic worlds where questions about intercultural identity and multilingual community are examined and where provisional answers are constructed in social interaction.

Dynamical and structural properties of dendrimer macromolecules

This work is devoted to the study of the dynamical and structural properties of dendrimers. Different approaches were used: analytical theory, computer simulation results and experimental NMR studies. The theory of the relaxation spectrum of dendrimer macromolecules was developed. Relaxation processes which are manifest in the local orientational mobility of dendrimer macromolecules were established and studied in detail. Theoretical results and conclusions were used for experimental studies of carbosilane dendimers.

The Structural Basis for inorganic Pyrophosphatase Catalysis and Regulation

Inorganic pyrophosphatases (PPases) are essential enzymes for every living cell. PPases provide the necessary thermodynamic pull for many biosynthetic reactions by hydrolyzing pyrophosphate. There are two types of PPases: integral membrane-bound and soluble enzymes. The latter type is divided into two non-homologous protein families, I and II. Family I PPases are present in all kingdoms of life, whereas family II PPases are only found in prokaryotes, including archae. Family I PPases, particularly that from Saccharomyces cerevisiae, are among the most extensively characterized phosphoryl transfer enzymes. In the present study, we have solved the structures of wild-type and seven active site variants of S. cerevisiae PPase bound to its natural metal cofactor, magnesium ion. These structures have facilitated derivation of the complete enzyme reaction scheme for PPase, fulfilling structures of all the reaction intermediates. The main focus in this study was on a novel subfamily of family II PPases (CBSPPase) containing a large insert formed by two CBS domains and a DRTGG domain within the catalytic domain. The CBS domain (named after cystathionine beta-synthase in which it was initially identified) usually occurs as tandem pairs with two or four copies in many proteins in all kingdoms of life. The structure formed by a pair of CBS domains is also known as a Bateman domain. CBS domains function as regulatory units, with adenylate ligands as the main effectors. The DRTGG domain (designated based on its most conserved residues) occurs less frequently and only in prokaryotes. Often, the domain co-exists with CBS domains, but its function remains unknown. The key objective of the current study was to explore the structural rearrangements in the CBS domains induced by regulatory adenylate ligands and their functional consequences. Two CBS-PPases were investigated, one from Clostridium perfringens (cpCBS-PPase) containing both CBS and DRTGG domains in its regulatory region and the other from Moorella thermoacetica (mt CBS-PPase) lacking the DRTGG domain. We additionally constructed a separate regulatory region of cpCBS-PPase (cpCBS). Both full-length enzymes and cpCBS formed homodimers. Two structures of the regulatory region of cpCBS-PPase complexed with the inhibitor, AMP, and activator, diadenosine tetraphosphate, were solved. The structures were significantly different, providing information on the structural pathway from bound adenylates to the interface between the regulatory and catalytic parts. To our knowledge, these are the first reported structures of a regulated CBS enzyme, which reveal large conformational changes upon regulator binding. The activator-bound structure was more open, consistent with the different thermostabilities of the activator- and inhibitor-bound forms of cpCBS-PPase. The results of the functional studies on wild-type and variant CBS-PPases provide support for inferences made on the basis of structural analyses. Moreover, these findings indicate that CBS-PPase activity is highly sensitive to adenine nucleotide distribution between AMP, ADP and ATP, and hence to the energy level of the cell. CBS-PPase activity is markedly inhibited at low energy levels, allowing PPi energy to be used for cell survival instead of being converted into heat.

Environmental inFluences on the Adoption of Open Innovation: Analysis of Structural, Institutional and Cultural Impacts

The concept of open innovation has recently gained widespread attention, and is particularly relevant now as many firms endeavouring to implement open innovation, face different sets of challenges associated with managing it. Prior research on open innovation has focused on the internal processes dealing with open innovation implementation and the organizational changes, already taking place or yet required in companies order to succeed in the global open innovation market. Despite the intensive research on open innovation, the question of what influences its adoption by companies in different contexts has not received much attention in studies. To fill this gap, this thesis contribute to the discussion on open innovation influencing factors by bringing in the perspective of environmental impacts, i.e. gathering data on possible sources of external influences, classifying them and testing their systemic impact through conceptual system dynamics simulation model. The insights from data collection and conceptualization in modelling are used to answer the question of how the external environment affects the adoption of open innovation. The thesis research is presented through five research papers reflecting the method triangulation based study (conducted at initial stage as case study, later as quantitative analysis and finally as system dynamics simulation). This multitude of methods was used to collect the possible external influence factors and to assess their impact (on positive/negative scale rather than numerical). The results obtained throughout the thesis research bring valuable insights into understanding of open innovation influencing factors inside a firm’s operating environment, point out the balance required in the system for successful open innovation performance and discover the existence of tipping point of open innovation success when driven by market dynamics and structures. The practical implications on how firms and policy-makers can leverage environment for their potential benefits are offered in the conclusions.

Structural aspects and floristic similarity among tropical dry forest fragments with different management histories in northern Minas Gerais, Brazil

In order to produce useful knowledge to the initiatives of protection and management of forest fragments, more specifically for tropical dry forests which suffer with frequent anthropic activities, and due to the lack of specific studies, this article aimed describe the structure and the floristic similarity among three areas of dry forest with different management histories. The study was developed in Capitão Enéas municipality, Northern Minas Gerais, Brazil, where three fragments were evaluated, being one in regeneration for 30 years, another submitted to occasional fire and the third with selective cut in small scale. The sampling was developed through the point quarter method considering all the alive phanerophyte individuals with circumference at breast height (CBH) > 15 cm. In the three fragments, 512 individuals, distributed in 60 species, 47 genera, and 23 families were sampled. The most representative families were Fabaceae (26), Anacardiaceae (4), Bignoniaceae (3) and Combretaceae (3). However, fourteen families were represented by only one species. Only eight species were common to all fragments - Myracrodruon urundeuva standed out with 26.9% of all sampled individuals - while a great number of species were exclusive of each fragment. The floristic and structural differences between the fragments are possibly related to the history and intensity of management in each area besides the topography variations and the presence or absence of limestone outcrops. These results show the importance of each fragment, indicating that the loss of anyone would cause negative impacts on the regional flora and consequently to the associated biodiversity.

Conventional and novel cardiovascular risk factors in young Finns and their associations with structural and functional vascular changes of subclinical atherosclerosis. The Cardiovascular Risk in Young Finns Study

Background: Atherosclerosis begins in early life progressing from asymptomatic to symptomatic as we age. Although substantial progress has been made in identifying the determinants of atherosclerosis in middle to older age adults at increased cardiovascular risk, there is lack of data examining determinants and prediction of atherosclerosis in young adults. Aims: The current study was designed to investigate levels of cardiovascular risk factors in young adults, subclinical measures of atherosclerosis, and prediction of subclinical arterial changes with conventional risk factor measures and novel metabolic profiling of serum samples. Subjects and Methods: This thesis utilised data from the follow-ups performed in 2001 and 2007 in the Cardiovascular Risk in Young Finns study, a Finnish population-based prospective cohort study that examined 2,204 subjects who were aged 30-45 years in 2007. Subclinical atherosclerosis was studied using noninvasive ultrasound measurements of carotid intima-media thickness (IMT), carotid arterial distensibility (CDist) and brachial flow-mediated dilation (FMD). Measurements included conventional risk factors and metabolic profiling using highthroughput nuclear magnetic resonance (NMR) methods that provided data on 42 lipid markers and 16 circulating metabolites. Results: Trends in lipids were favourable between 2001 and 2007, whereas waist circumference, fasting glucose, and blood pressure levels increased. To study the stability of noninvasive ultrasound markers, 6-year tracking (the likelihood to maintain the original fractile over time) in 6 years was examined. IMT tracked more strongly than CDist and FMD. Cardiovascular risk scores (Framingham, SCORE, Finrisk, Reynolds and PROCAM) predicted subclinical atherosclerosis equally. Lipoprotein subclass testing did not improve the prediction of subclinical atherosclerosis over and above conventional risk factors. However, circulating metabolites improved risk stratification. Tyrosine and docosahexaenoic acid were found to be novel biomarkers of high IMT. Conclusions: Prediction of cardiovascular risk in young Finnish adults can be performed with any of the existing risk scores. The addition of metabonomics to risk stratification improves prediction of subclinical changes and enables more accurate targeting of prevention at an early stage.

DPS-Like Peroxide Resistance Protein: Structural and Functional Studies on a Versatile Nanocontainer

Oxidative stress is a constant threat to almost all organisms. It damages a number of biomolecules and leads to the disruption of many crucial cellular functions. It is caused by reactive oxygen species (ROS), such as hydrogen peroxide (H2O₂), superoxide (•O₂ -), and hydroxyl radical (•OH). The most harmful of these compounds is •OH, which is only formed in cells in the presence of redox-cycling transition metals, such as iron and copper. Bacteria have developed a number of mechanisms to cope with ROS. One of the most widespread means employed by bacteria is the DNA-binding proteins from starved cells (Dps). Dps proteins protect the cells by binding and oxidizing Fe2+, thus greatly reducing the production of •OH. The oxidized iron is stored inside the protein as an iron core. In addition, Dps proteins bind directly to DNA forming a protective coating that shields DNA from harmful agents. Moreover, Dps proteins have been found to elicit other protective functions in cells and to participate in bacterial virulence. Dps proteins are of special importance to Streptococci owing to the lack of catalase in this genus of bacteria.This study was focused on structural and functional characterization of streptococcal Dpslike peroxide resistance (Dpr) proteins. Initially, crystal structures of Streptococcus pyogenes Dpr were determined. The data confirmed the presence of a di-metal ferroxidase center (FOC) in Dpr proteins and revealed the presence of a novel N-terminal helix as well as a surface metal-binding site. The crystal structures of Streptococcus suis Dpr complexed with transition metals demonstrated the metal specificity of the FOC. Solution binding studies also indicated the presence of a di-metal FOC. These results suggested a possible role for Dpr in the detoxification of various metals. Iron was found to mineralize inside the protein as ferrihydrite based on X-ray absorption spectroscopy data. The iron core was found to exhibit clear superparamagnetic behaviour using magnetic and Mössbauer measurements. The results from this study are expected to further increase our understanding on the binding, oxidation, and mineralization of iron and other metals in Dpr proteins. In particular, the structural and magnetic properties of the iron core can form a basis for potential new applications in nanotechnology. From the streptococcal viewpoint, the results would help in understanding better the complicated picture of bacterial pathogenesis. Dpr proteins may also provide a novel target for drug design due to their tight involvement in bacterial virulence.