Electron paramagnetic resonance evidence for Jahn-Teller glasses

Single crystal E.P.R. studies of copper as a dopant in lithium potassium sulphate, lithium ammonium sulphate and lithium sodium sulphate have been carried out from room temperature down to 77K. The three Jahn-Teller (JT) systems behave very similarly to one another. The room temperature dynamic JT spectra with giso = 2·19 ± 0·01 and Aiso = ±(33 ± 4) times 10-4 cm-1 transform around 247 K to spectra characterized by randomly frozen-in axial strains with g‖ = 2·4307 ± 0·0005, g⊥ = 2·083 ± 0·001, A‖ = ±(116 ± 2) times 10-4 cm-1 and A⊥ = ∓(14 ± 4) times 10-4 cm-1. We proposed that the low temperature phase (below 247 K) of each of these systems provides an example of a Jahn-Teller glass.

Evidence for double valence fluctuation in metallic oxides of lead

The possible role of double valence fluctuation in both lead and oxide ions with reference to metallization in oxides of lead is examined by x-ray-photoemission spectroscopy, ultraviolet-photoemission spectroscopy (UPS), and 207Pb NMR studies. The double valence fluctuations may be viewed as Pb4++2O2-⇄Pb2+O22-. While the insulating oxides PbO, Pb3O4, and Sr2PbO4 show a single oxide ion, O2- characterized by O(1s) at 529.7 eV, the insulating peroxide BaO2 is characterized by the ion O22- with a single O(1s) at 533 eV. The metallic PbO2, BaPbO3, BaBiPbO3, and SrPbO3 showed the occurrence of both O2- and O22- ions. The valence band in these compounds has also been studied by UPS, and clear evidence for the coexistence of O2- and O22- is seen in PbO2. A simultaneous study of 207Pb NMR suggests that the Pb ion could also exist in mixed-valence states. Qualitative arguments are presented to rationalize the existence of such mixed valences of the anion in metal oxides in general and their role in superconductivity.

Corporate Governance Mechanisms and Firm Performance:Evidence from Finland

This paper examines the association between corporate governance attributes and firm performance of Finnish firms during 1990 – 2000. The empirical results suggest that corporate governance matters for firm performance. First, univariate test results indicate that firms characterized by a high (efficient) level of corporate governance have delivered greater stock returns, are higher valued based on the measure of Tobin’s Q, and exhibit higher ratios of cash flow to assets, on average, in comparison to their counterparts characterized by a low (inefficient) level of corporate governance. Second, controlling for a number of well-known determinants of stock returns, we find evidence that firms categorized by inefficient corporate governance have delivered inferior returns to shareholders during the investigation period. Finally, after controlling for several common determinants of firm value, we find that firms characterized by efficient corporate governance have been valued higher during the investigation period, measured by Tobin’s Q.

High-pressure studies on Ge-Te glasses. Evidence for a critical composition in IV-VI chalcogenide glassy systems

The electrical resistivity of bulk GexTe100-x glasses has been measured as a function of temperature and pressure. Under high pressure, all the glasses were found to undergo sharp discontinuous transitions from glassy semiconductors to crystalline metal. Several of the observed properties such as the transition pressure, conductivity activation energy and pre-exponential factor, exhibit anomalous trends at a composition x = 20. These results suggest that the x = 20 composition in the Ge-Te system should possess salient structural features. A model based on the unusual stability of structural units is proposed for explaining the anomaly at 20 at.% Ge concentration.

XPS evidence for molecular charge-transfer doping of graphene

By employing X-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G-bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping. (C) 2010 Elsevier B.V. All rights reserved.

Associations of interleukin-1 (IL-1) gene variation and IL-1 receptor antagonist phenotypes with immunological responses, metabolic dysregulation and type 2 diabetes

The upstream proinflammatory interleukin-1 (IL-1) cytokines, together with a naturally occurring IL-1 receptor antagonist (IL-1Ra), play a significant role in several diseases and physiologic conditions. The IL-1 proteins affect glucose homeostasis at multiple levels contributing to vascular injuries and metabolic dysregulations that precede diabetes. An association between IL-1 gene variations and IL-1Ra levels has been suggested, and genetic studies have reported associations with metabolic dysregulation and altered inflammatory responses. The principal aims of this study were to: 1) examine the associations of IL-1 gene variation and IL-1Ra expression in the development and persistence of thyroid antibodies in subacute thyroiditis; 2) investigate the associations of common variants in the IL-1 gene family with plasma glucose and insulin concentrations, glucose homeostasis measures and prevalent diabetes in a representative population sample; 3) investigate genetic and non-genetic determinants of IL-1Ra phenotypes in a cross-sectional setting in three independent study populations; 4) investigate in a prospective setting (a) whether variants of the IL-1 gene family are predictors for clinically incident diabetes in two population-based observational cohort studies; and (b) whether the IL-1Ra levels predict the progression of metabolic syndrome to overt diabetes during the median follow-up of 10.8 and 7.1 years. Results from on patients with subacte thyroiditis showed that the systemic IL-1Ra levels are elevated during a specific proinflammatory response and they correlated with C-reactive protein (CRP) levels. Genetic variation in the IL-1 family seemed to have an association with the appearance of thyroid peroxidase antibodies and persisting local autoimmune responses during the follow-up. Analysis of patients suffering from diabetes and metabolic traits suggested that genetic IL-1 variation and IL-1Ra play a role in glucose homeostasis and in the development of type 2 diabetes. The coding IL-1 beta SNP rs1143634 was associated with traits related to insulin resistance in cross-sectional analyses. Two haplotype variants of the IL-1 beta gene were associated with prevalent diabetes or incident diabetes in a prospective setting and both of these haplotypes were tagged by rs1143634. Three variants of the IL-1Ra gene and one of the IL-1 beta gene were consistently identified as significant, independent determinants of the IL-1Ra phenotype in two or three populations. The proportion of the phenotypic variation explained by the genetic factors was modest however, while obesity and other metabolic traits explained a larger part. Body mass index was the strongest predictor of systemic IL-1Ra concentration overall. Furthermore, the age-adjusted IL-1Ra concentrations were elevated in individuals with metabolic syndrome or diabetes when compared to those free of metabolic dysregulation. In prospective analyses the systemic IL-1Ra levels were found as independent predictors for the development of diabetes in people with metabolic syndrome even after adjustment for multiple other factors, including plasma glucose and CRP levels. The predictive power of IL-1Ra was better than that of CRP. The prospective results also provided some evidence for a role of common IL-1 alpha promoter SNP rs1800587 in the development of type 2 diabetes among men and suggested that the role may be gender specific. Likewise, common variations in the IL-1 beta coding region may have a gender specific association with diabetes development. Further research on the potential benefits of IL-1Ra measurements in identifying individuals at high risk for diabetes, who then could be targeted for specific treatment interventions, is warranted. It has been reported in the recent literature that IL-1Ra secreted from adipose tissue has beneficial effects on glucose homeostasis. Furthermore, treatment with recombinant human IL-1Ra has been shown to have a substantial therapeutic potential. The genetic results from the prospective analyses performed in this study remain inconclusive, but together with the cross-sectional analyses they suggest gender-specific effects of the IL-1 variants on the risk of diabetes. Larger studies with more extensive genotyping and resequencing may help to pinpoint the exact variants responsible and to further elucidate the biological mechanisms for the observed associations. This would improve our understanding of the pathways linking inflammation and obesity with glucose and insulin metabolism.

“Aivan sama vaikkei ne olis edes pelannut” – Jalkapallo elämyskulutuksen kohteena

Tutkielmassa tarkastellaan jalkapallon seuraamista elämyskuluttamisen näkökulmasta. Elämyskulutuksella tarkoitetaan tässä yhteydessä tapahtumia ja hetkiä, jolloin ihminen kokee tavallisuudesta poikkeavan ja mieleenpainuvan tunnetilan. Elämyksiä tarjoavat palvelut ovat lisänneet jatkuvasti suosiotaan, kun arjessa rationaalisuus ylikorostuu ja sille halutaan vastapainoa. Aihetta taustoitetaan elämysyhteiskunnan, yhteisöllisyyden ja kuluttajaheimojen käsitteiden avulla. Erityishuomion saavat kulttuuritapahtumat elämystuotteina, penkkiurheilu yhteiskunnallisena ilmiönä sekä erilaiset jalkapalloon liittyvät kulutustavat. Tutkielma on luonteeltaan fenomenologis-etnografinen kuvaileva tutkimus. Tutkimusmenetelminä on käytetty osallistuvaa havainnointia ja haastatteluita. Tutkimusperinteen mukaisesti ilmiön ymmärtäminen, kuvaaminen ja kirjoittaminen ovat tärkeässä osassa. Havainnointiaineisto on kerätty kolmessa eri tapahtumassa seuraamalla katsojien käyttäytymistä ja tunnelman syntymiseen vaikuttavia tekijöitä. Haastateltavat on valittu harkinnanvaraisesti jalkapalloa aktiivisesti seuraavista henkilöistä ja menetelmänä on käytetty avoimia teemahaastatteluita. Urheilun vetovoima ajanvietteenä perustuu vahvojen tunteiden herättämiseen, joten penkkiurheilu on elämyskulutusta puhtaimmillaan. Urheilu elämystuotteena on oivallinen, sillä sen lukuisten kulutustapojen lisäksi tapahtumat muodostavat päättymättömän jatkumon. Myös oman aineistoni perusteella osoittautui, että menneiden tapahtumien avulla ankkuroidutaan yhteisöön ja tulevien tapahtumien avulla pidetään innostusta yllä. Pettymysten hetkelläkään koukusta ei haluta irti, sillä jokainen kokemus lisää tunteita omaa urheilulajia ja yhteisöä kohtaan. Urheilutapahtumissa katsojan elämys syntyy subjektiivisen kokemuksen kautta, mutta yhteisö luo elämyksen toteutumisen välttämättömät edellytykset. Jalkapalloyleisöön kuuluvissa henkilöissä yhdistyvät halu kuulua ryhmään ja olla samaan aikaan sen ulkopuolella. Peliä voidaan tarkkailla itsekseen ja keskittyneesti suuren joukon keskellä tai hurrata muiden mukana. Aineistoni perusteella jalkapallofanin innostus pulppuaa kahdesta lähteestä: yhteisöllisyydestä ja kiinnostuksesta lajiin. Yhteisöllisyyden tunne syntyy kuulumisesta globaaliin jalkapalloyhteisöön, oman suosikkijoukkueen kannattajiin ja samaa lajia seuraavien kaverien muodostamaan lähipiiriin. Urheilullinen puoli innostuksesta syntyy kiinnostuksesta jalkapalloa kohtaan lajina, aktiivisesti seuratuista säännöllisistä tapahtumista ja oman joukkueen kannattamisesta. Jalkapallon seuraajiin teoria jatkuvasti muuttuvista uusyhteisöistä pätee melko huonosti, sillä lajille ja seuralle ollaan hyvin uskollisia. Faneille on tärkeää sitoutua pieneen lähiyhteisöön, jonka kanssa heillä on yhteinen historia ja mahdollisuus jakaa kokemuksia keskustelemalla ja muistelemalla.

Thermodynamics of Cobalt (II, III) Oxide (Co3O4): Evidence of Phase Transition

The Gibbs' energy change for the reaction, 3CoO (r.s.)+1/2O2(g)→Co3O4(sp), has been measured between 730 and 1250 K using a solid state galvanic cell: Pt, CuO+Cu2O|(CaO)ZrO2|CoO+Co3O4,Pt. The emf of this cell varies nonlinearly with temperature between 1075 and 1150 K, indicating a second or higher order phase transition in Co3O4around 1120 (±20) K, associated with an entropy change of ∼43 Jmol-1K-1. The phase transition is accompanied by an anomalous increase in lattice parameter and electrical conductivity. The cubic spinel structure is retained during the transition, which is caused by the change in CO+3 ions from low spin to high spin state. The octahedral site preference energy of CO+3 ion in the high spin state has been evaluated as -24.8 kJ mol-1. This is more positive than the value for CO+2 ion (-32.9 kJ mol-1). The cation distribution therefore changes from normal to inverse side during the phase transition. The transformation is unique, coupling spin unpairing in CO+3 ion with cation rearrangement on the spinel lattice, DTA in pure oxygen revealed a small peak corresponding to the transition, which could be differentiated from the large peak due to decomposition. TGA showed that the stoichiometry of oxide is not significantly altered during the transition. The Gibbs' energy of formation of Co3O4 from CoO and O2 below and above phase transition can be represented by the equations:ΔG0=-205,685+170.79T(±200) J mol-1(730-1080 K) and ΔG0=-157,235+127.53T(±200) J mol-1(1150-1250 K).

Do Households Have Rational Expectations on Future Consumption? Evidence from the Finnish Consumer Survey

Ever since its initial introduction some fifty years ago, the rational expectations paradigm has dominated the way economic theory handles uncertainty. The main assertion made by John F. Muth (1961), seen by many as the father of the paradigm, is that expectations of rational economic agents should essentially be equal to the predictions of relevant economic theory, since rational agents should use information available to them in an optimal way. This assumption often has important consequences on the results and interpretations of the models where it is applied. Although the rational expectations assumption can be applied to virtually any economic theory, the focus in this thesis is on macroeconomic theories of consumption, especially the Rational Expectations–Permanent Income Hypothesis proposed by Robert E. Hall in 1978. The much-debated theory suggests that, assuming that agents have rational expectations on their future income, consumption decisions should follow a random walk, and the best forecast of future consumption level is the current consumption level. Then, changes in consumption are unforecastable. This thesis constructs an empirical test for the Rational Expectations–Permanent Income Hypothesis using Finnish Consumer Survey data as well as various Finnish macroeconomic data. The data sample covers the years 1995–2010. Consumer survey data may be interpreted to directly represent household expectations, which makes it an interesting tool for this particular test. The variable to be predicted is the growth of total household consumption expenditure. The main empirical result is that the Consumer Confidence Index (CCI), a balance figure computed from the most important consumer survey responses, does have statistically significant predictive power over the change in total consumption expenditure. The history of consumption expenditure growth itself, however, fails to predict its own future values. This indicates that the CCI contains some information that the history of consumption decisions does not, and that the consumption decisions are not optimal in the theoretical context. However, when conditioned on various macroeconomic variables, the CCI loses its predictive ability. This finding suggests that the index is merely a (partial) summary of macroeconomic information, and does not contain any significant private information on consumption intentions of households not directly deductible from the objective economic variables. In conclusion, the Rational Expectations–Permanent Income Hypothesis is strongly rejected by the empirical results in this thesis. This result is in accordance with most earlier studies conducted on the topic.

Evidence in European Asylum Procedures

This thesis explores the particular framework of evidentiary assessment of three selected appellate national asylum procedures in Europe and discusses the relationship between these procedures, on the one hand, and between these procedures and other legal systems, including the EU legal order and international law, on the other. A theme running throughout the thesis is the EU strivings towards approximation of national asylum procedures and my study analyses the evidentiary assessment of national procedures with the aim of pinpointing similarities and differences, and the influences which affect these distinctions. The thesis first explores the frames construed for national evidentiary solutions by studying the object of decision-making and the impact of legal systems outside the national. Second, the study analyses the factual evidentiary assessment of three national procedures - German, Finnish and English. Thirdly, the study explores the interrelationship between these procedures and the legal systems influencing them and poses questions in relation to the strivings of EU and methods of convergence. The thesis begins by stating the framework and starting points for the research. It moves on to establish keys of comparison concerning four elements of evidentiary assessment that are of importance to any appellate asylum procedure, and that can be compared between national procedures, on the one hand, and between international, regional and national frameworks, on the other. Four keys of comparison are established: the burden of proof, demands for evidentiary robustness, the standard of proof and requirements for the methods of evidentiary assessment. These keys of comparison are then identified in three national appellate asylum procedures, and in order to come to conclusions on the evidentiary standards of the appellate asylum procedures, relevant elements of the asylum procedures in general are presented. Further, institutional, formal and procedural matters which have an impact on the evidentiary standards in the national appellate procedures are analysed. From there, the thesis moves on to establish the relationship between national evidentiary standards and the legal systems which affect them, and gives reasons for similarities and divergences. Further, the thesis studies the impact of the national frameworks on the regional and international level. Lastly, the dissertation makes a de lege ferenda survey of the relationship between EU developments, the goal of harmonization in relation to national asylum procedures and the particular feature of evidentiary standards in national appellate asylum procedures. Methodology The thesis follows legal dogmatic methods. The aim is to analyse legal norms and legal constructions and give them content and context. My study takes as its outset an understanding of the purposes for legal research also regarding evidence and asylum to determine the contents of valid law through analysis and systematization. However, as evidentiary issues traditionally are normatively vaguely defined, a strict traditional normative dogmatic approach is not applied. For the same reason a traditionalist and strict legal positivism is not applied. The dogmatics applied to the analysis of the study is supported by practical analysis. The aim is not only to reach conclusions concerning the contents of legal norms and the requirements of law, but also to study the use and practical functioning of these norms, giving them a practcial context. Further, the study relies on a comparative method. A functionalist comparative method is employed and keys of comparison are found in evidentiary standards of three selected national appellate asylum procedures. The functioning equivalences of German, Finnish and English evidentiary standards of appellate asylum procedures are compared, and they are positioned in an European and international legal setting. Research Results The thesis provides results regarding the use of evidence in national appellate asylum procedures. It is established that evidentiary solutions do indeed impact on the asylum procedure and that the results of the procedure are dependent on the evidentiary solutions made in the procedures. Variations in, amongst other things, the interpretation of the burden of proof, the applied standard of proof and the method for determining evidentiary value, are analysed. It is established that national impacts play an important role in the adaptation of national appellate procedures to external requirements. Further, it is established that the impact of national procedures on as well the international framework as on EU law varies between the studied countries, partly depending on the position of the Member State in legislative advances at the EU level. In this comparative study it is, further, established that the impact of EU requirements concerning evidentiary issues may be have positive as well as negative effects with regard to the desired harmonization. It is also concluded that harmonization using means of convergence that primaly target legal frameworks may not in all instances be optimal in relation to evidentiary standards, and that more varied and pragmatic means of convergence must be introduced in order to secure harmonization also in terms of evidence. To date, legal culture and traditions seem to prevail over direct efforts at procedural harmonization.

Conformations of synthetic alamethicin fragments. Evidence for 310 helical folding from 270-MHz hydrogen-1 nuclear magnetic resonance and circular dichroism studies

IH NMR studies at 270 MHz on the synthetic alamethicin fragments Z-Aib-Pro-Aib-Ala-Aib-Ala-OMe (1-6), Boc-Gln-Aib-Val-Aib-Gly-Leu-Aib-OMe (7-1 3), Boc-Leu-Aib-Pro-Val-Aib-OMe (1 2-16), and Boc-Gly-Leu- Aib-Pro-Val-Aib-OMe (1 1-16) have been carried out in CDC13 and (CD3)2S0. The intramolecularly hydrogen bonded amide hydrogens in these peptides have been delineated by using solvent titration experiments and temperature coefficientsof NH chemical shifts in (CD3)+30. All the peptides adopt highly folded structures, characterized by intramolecular 4 - 1 hydrogen bonds. The 1-6 fragment adopts a 310 helical conformation with four hydrogen bonds, in agreement with earlier studies (Rao, Ch. P., Nagaraj, R., Rao, C. N. R., & Balaram, P. (1980) Biochemistry 19, 425-4311. The 7-13