Aspects of tautomerism. Part II. Reactions of the pseudo-acid chloride of o-benzoylbenzoic acid with nucleophiles

Reactions of fourteen nucleophiles with the pseudo-acid chloride of o-benzoylbenzoic acid in two solvents have been studied. The nucleophiles that react primarily at the tetrahedral carbon atom to give pseudo derivatives, are weaker than those that react at the carbonyl carbon atom causing opening of the lactone ring. An explanation for this phenomenon is advanced.

The subsidence rates of suspensions of lithium stearate in n-heptane with n-alcohols as additives

Suspensions of lithium stearate in n-heptane are highly unstable, undergoing gelation even at concentrations as low as 1 g./1. The rate of subsidence of these weakly gelled suspensions is decreased at first by the addition of n-alcohols, but passes through a minimum in some cases. The minimum subsidence rate occurs while the adsorption of the alcohol is still below its saturation value. One possible explanation of the effect is that the solvent layer between particles at the junction points in the gel becomes simultaneously more polar, tending toward an increased gel strength, and also thicker, tending toward a decreased gel strength.

The connection between on-farm assessed welfare (A-index) and production parameters of the sows

Tämän tutkimuksen tavoitteena oli selvittää tilalla määritetyn hyvinvoinnin yhteyttä emakoiden tuotantotuloksiin. Hyvinvointia arvioitiin suomalaisen hyvinvointi-indeksin, A-indeksi, avulla. Tuotantotuloksina käytettiin kahta erilaista tuotosaineistoa, jotka molemmat pohjautuivat kansalliseen tuotosseuranta aineistoon. Hyvinvointimääritykset tehtiin 30 porsastuotantosikalassa maaliskuun 2007 aikana. A-indeksi koostuu kuudesta kategoriasta ’liikkumismahdollisuudet’, ’alustan ominaisuudet’, ’sosiaaliset kontaktit’, ’valo, ilma ja melu’, ’ruokinta ja veden saanti’ sekä ’eläinten terveys ja hoidon taso’. Jokaisessa kategoriassa on 3-10 pääosin ympäristöperäistä muuttujaa, jotka vaihtelevat osastoittain. Maksimipistemäärä osastolle on 100. Hyvinvointimittaukset tehtiin porsitus-, tiineytys- ja joutilasosastoilla. Erillisten tiineytysosastojen pienen lukumäärän takia (n=7) tilakohtaiset tiineytys- ja joutilasosastopisteet yhdistettiin ja keskiarvoja käytettiin analyyseissä. Yhteyksiä tuotokseen tutkittiin kahden eri aineiston avulla 1) Tilaraportti aineisto (n=29) muodostuu muokkaamattomista tila- ja tuotostuloksista tilavierailua edeltävän vuoden ajalta, 2) POTSIaineisto (n=30) muodostuu POTSI-ohjelmalla (MTT) muokatusta tuotantoaineistosta, joka sisältää managementtiryhmän (tila, vuosi, vuodenaika) vaikutuksen ensikoiden ja emakoiden pahnuekohtaiseen tuotokseen. Yhteyksiä analysointiin korrelaatio- ja regressioanalyysien avulla. Vaikka osallistuminen tutkimukseen oli vapaaehtoista, molempien tuotantoaineistojen perusteella tutkimustilat edustavat keskituottoista suomalaista sikatilaa. A-indeksin kokonaispisteet vaihtelivat välillä 37,5–64,0 porsitusosastolla ja 39,5–83,5 joutilasosastolla. Tilaraporttiaineistoa käytettäessä paremmat pisteet porsitusosaston ’eläinten terveys ja hoidon taso’ -kategoriasta lyhensivät eläinten lisääntymissykliä, lisäsivät syntyvien pahnueiden ja porsaiden määrää sekä alensivat kuolleena syntyneiden lukumäärää. Regressiomallin mukaan ’eläinten terveys ja hoidon taso’ -kategoria selitti syntyvien porsaiden lukumäärän, porsimisvälin pituuden sekä keskiporsimiskerran vaihtelua. Paremmat pisteet joutilasosaston ’liikkumismahdollisuudet’ kategoriasta alensivat syntyneiden pahnueiden sekä syntyneiden että vieroitettujen porsaiden lukumäärää. Regressiomallin mukaan ensikkopahnueiden osuus ja ”liikkumismahdollisuudet” kategorian pisteet selittivät vieroitettujen porsaiden lukumäärän vaihtelua. POTSI-aineiston yhteydessä kuolleena syntyneiden porsaiden lukumäärän aleneminen oli ensikoilla yhteydessä parempiin porsitusosaston ’sosiaalisiin kontakteihin’ ja emakoilla puolestaan joutilasosaston parempiin ’eläinten terveys ja hoidon taso’ pisteisiin. Kahden eri tuotantoaineiston avulla saadut tulokset erosivat toisistaan. Seuraavissa tutkimuksissa onkin suositeltavampaa käyttää Tilaraporttiaineistoja, joissa tuotokset ilmoitetaan vuosikohtaisina. Tämän tutkimuksen perusteella hyvinvoinnilla ja tuotoksella on yhteyksiä, joilla on myös merkittävää taloudellista vaikutusta. Erityisesti hyvä eläinten hoito ja eläinten terveys lisäävät tuotettujen porsaiden määrää ja lyhentävät lisääntymiskiertoa. Erityishuomiota tulee kiinnittää vapaana olevien joutilaiden emakoiden sosiaaliseen stressiin ja rehunsaannin varmistamiseen kaikille yksilöille.

The Impact of the EMU on International Portfolio Investments

This paper analyses the impact of the launch of the European Monetary Union (EMU) on the allocation of international portfolio investments. The initiation of the EMU provides an opportunity for comparison of competing theoretical explanations for investment behavior. Models stressing the diversification motive would predict that the increased dependence between countries participating in the EMU should reduce the attractiveness of portfolio holdings in other EMU countries. Models based on asymmetric information would instead emphasize the increased intensity in the flow of information resulting from an increase in cross border transactions between the EMU countries. The consequent decline in information asymmetry should increase, rather than reduce portfolio holdings in other EMU countries. Our results based on the allocation of Finnish foreign portfolio investment support the information-based explanation against predictions based on the diversification motive.

Evaluating the Predictability of the Volatility Smile Using Return Distributions

In this paper, we examine the predictability of observed volatility smiles in three major European index options markets, utilising the historical return distributions of the respective underlying assets. The analysis involves an application of the Black (1976) pricing model adjusted in accordance with the Jarrow-Rudd methodology as proposed in 1982. Thereby we adjust the expected future returns for the third and fourth central moments as these represent deviations from normality in the distributions of observed returns. Thus, they are considered one possible explanation to the existence of the smile. The obtained results indicate that the inclusion of the higher moments in the pricing model to some extent reduces the volatility smile, compared with the unadjusted Black-76 model. However, as the smile is partly a function of supply, demand, and liquidity, and as such intricate to model, this modification does not appear sufficient to fully capture the characteristics of the smile.

Reklamsvenska i Finland speglad genom varuhuset Stockmanns tidningsannonser under det 20e seklet - Swedish Advertising Language in Finland Mirrored by the Newspaper Advertisements of the Stockmanns Department Store during the 20th Century

Reklam sägs använda ett modernt, gärna ett nyskapande språk. Detta är ett påstående som inte så lätt kan verifieras. Tidningsannonsen är troligen den skriftspråksgenre som har fått minst uppmärksamhet av språkforskare. De som skriver texten i en tidningsannons är personer som representerar det samtida språkbruket. Annonser som representerar olika tidsepoker skiljer sig därför från varandra inte bara genom att annonsen förändras i fråga om stil och form. Annonsens språk avspeglar också den språkliga förändringsprocess som kontinuerligt pågår i varje språksamhälle. Annonser, och marknadsföringsmaterial över huvud taget, läses också av många människor som i övrigt läser mycket litet eller kanske inte alls. Marknadsföraren, reklamskribenten (copywriter) och AD:n producerar m.a.o. texter som på ett omedvetet sätt kommer att vara språkmodeller för sina läsare. Förändringar i språket kreeras inte och drivs inte på av språkforskare, utan av vanliga språkbrukare i interaktion med andra språkbrukare. Sett ur ett sociolingvistiskt perspektiv har det vitt spridda reklamspråket därför inflytande på språket i samhället. Syftet med det reklamspråksprojekt som presenteras i föreliggande rapport är att analysera hur och när förändringar i svenskan som uppträder i Sverige dyker upp i annonser som skrivs på svenska i Finland. Reklam på svenska Finland under 1900-talet står i fokus, och tidningsannonser för Stockmanns varuhus i Helsingfors utgör primärmaterialet. Tidningsannonser för varuhuset Nordiska Kompaniet (NK) i Stockholm under motsvarande tid tjänar som jämförelsematerial. I denna rapport presenteras projektets syfte, de uppställda forskningsfrågorna, och resonemanget illustreras med exempel ur projektmaterialet. Rapporten innehåller också en beskrivning av projektets reklamdatabas och basfakta om material och metoder. -

Steric effects on the ultraviolet absorption of 1,2-enedioic and related systems

1,2-Enedioic systems, being sterically perturbed from planarity do not show the effect of the extended conjugation expected of a (formal) trienic entity. In the absence of a model which approximates to a uniplanar situation, the strategy of replacing an ester group in the enedioates by a cyano (for which less stringent steric demand may be presumed) and noting the correction concomitant to this replacement was adopted to arrive at a notional figure for the position of maximal absorption in the planar enedioates. From this the conclusion, subject to substantiation by molecular mechanical or quantum chemical calculations, was drawn that even the E-isomeric and comparatively less substituted enedioates are highly sterically perturbed. An alternative to an earlier explanation of the bathochromic shift of absorption maxima encountered in the 5-cyclic ene-ester and ene-nitrile, relative to the 6-cyclic analogues (observed also with the enedioates and cyanovinyl ester systems), seen later to have been based on unwarranted premises, has been advanced. A comment on the absorption characteristics of enedioic anhydrides has been appended.

Media Education in the Finnish School System : A Conceptual Analysis of the Subject Didactic Dimension of Media Education

The aim of the doctoral dissertation was to further our theoretical and empirical understanding of media education as practised in the context of Finnish basic education. The current era of intensive use of the Internet is recognised too. The doctoral dissertation presents the subject didactic dimension of media education as one of the main results of the conceptual analysis. The theoretical foundation is based on the idea of dividing the concept of media education into media and education (Vesterinen et al., 2006). As two ends of the dimension, these two can be understood didactically as content and pedagogy respectively. In the middle, subject didactics is considered to have one form closer to content matter (Subject Didactics I learning about media) and another closer to general pedagogical questions (Subject Didactics II learning with/through media). The empirical case studies of the dissertation are reported with foci on media literacy in the era of Web 2.0 (Kynäslahti et al., 2008), teacher reasoning in media educational situations (Vesterinen, Kynäslahti - Tella, 2010) and the research methodological implications of the use of information and communication technologies in the school (Vesterinen, Toom - Patrikainen, 2010). As a conclusion, Media-Based Media Education and Cross-Curricular Media Education are presented as two subject didactic modes of media education in the school context. Episodic Media Education is discussed as the third mode of media education where less organised teaching, studying and learning related to media takes place, and situations (i.e. episodes, if you like) without proper planning or thorough reflection are in focus. Based on the theoretical and empirical understanding gained in this dissertation, it is proposed that instead of occupying a corner of its own in the school curriculum, media education should lead the wider change in Finnish schools.

Theorizing the Nature of Reflection

For the past decades reflection has been the buzzword of adult and higher education. Reflection is facilitated in many practices and there is abundant research on the issue. Despite the popularity of the concept, the reasons why bringing about reflection in educational practices is difficult remain unclear. The prevailing theories inform of the process in its ideal form. However, to a great extent, they fail to offer conceptual tools for understanding and working with the actualities of reflection. The aim of the doctoral thesis was to explore the challenges and prerequisites of reflection in order to theorize the nature of reflection. By the term reflection it is here referred to becoming aware of and questioning the assumptions that orient our thinking, feelings and actions. The doctoral thesis consists of five studies that approach these questions from different viewpoints and within different contexts. The methods involve both a philosophical and an empirical approach. This multifaceted approach embodies the aim of both gaining a more thorough grasp of the phenomenon and to develop the methodology of researching reflection. The theory building is based on conceptual analysis and rational reconstruction (see Davia 1998; Habermas 1979; Rorty1984) of Mezirow s (1981; 1991; 2000; 2009) theory of transformative learning. In order to explore the aspects which, based on the analysis, appeared insufficiently considered within Mezirow s theory, Damasio s (1994; 1999; 2003; 2010) theory on emotions and consciousness as well as Clausewitz s (1985) view on friction are used as complementary theories. Empirical analyses are used in dialogue with the theoretical, in order to challenge and refine the emerging theorization. Reflection is examined in three different contexts; regarding university teachers pedagogical growth, involuntarily childless women recovering from a life-event crisis, and soldiers preparing to act in chaotic situations of the battlefield as well as recovering from it. The choice of these contexts is based on Mezirow s notion of disorienting dilemma as a trigger for reflection. This notion indicates that reflection may more naturally emerge in association to life-event crises or other cumulative sets of instances, which bring our worldview and beliefs under question. Nevertheless, reflection is often being promoted in educational contexts in which the trigger conditions may not readily prevail. These contextual issues as well as the differences between the facilitated and non-facilitated contexts have not, however, been considered in detail within the research on reflection (or transformative learning). The doctoral thesis offers a new perspective into reflection which, as a further development on Mezirow s transformative learning theory, theorizes the nature of reflection. The developed theory explicates the prerequisites and challenges to reflection. The theory suggests that the challenges of reflection are fundamentally connected to the way the biological life-support system affects our thinking through emotions. While depicting the mechanisms that function as a counterforce to reflection, the developed theory also opens a perspective for considering possibilities for carrying out reflection, and suggests ways to locate and deal with the assumptions to be reflected on. The basic dynamic of the challenges to reflection was explicated by conceptually bridging the gap between Mezirow s and Damasio s theories, through exploring the connections between the meaning perspective and the biological functions of emotions. The concepts of comfort zone and edge-emotions were formed so as to depict the emotional orientation of our thinking, as part of the explanation of the nature of reflection.

A hypothesis on a specific sequence-dependent conformation of DNA and its relation to the binding of the lac-repressor protein

The structure and properties of the double-helical form of the alternating copolymer poly(dA-dT) are considered. Different lines of evidence are interpreted in terms of a structure in which every second phosphate-diester linkage has a conformation different from that of the normal B form. A rationale for this “alternating-B” structure is given which provides an explanation for the effects of chemical modifications of the T residues on the binding of the poly(dA-dT)· poly(dA-dT) to the lac repressor of Escherichia coli.

Behaviour of the curve of critical exponents near and away from a double critical point

To investigate the nature of the curve of critical exponents (as a function of the distance from a double critical point), we have combined our measurements of the osmotic compressibility with all published data for quasibinary liquid mixtures. This curve has a parabolic shape. An explanation of this result is advanced in terms of the geometry of the coexistence dome, which is contained in a triangular prism.

The dynamics of the Ramdas layer

A little more than sixty years ago, the late L. A. Ramdas discovered a curious atmospheric phenomenon which had not been satisfactorily explained till recently. The phenomenon is the observation of a temperature minimum some 20-50 cm above bare soil on calm, clear nights. The first reports of these observations were treated with much scepticism, as the prevailing view was that the nocturnal temperature minimum always occurs at ground. In the present address the history of work on the lifted temperature minimum is traced and a new explanation is offered. It is emphasized that in this as well as many other phenomena, it is important to account for surfaces that are not perfectly black radiatively, i.e. those whose emissivity is not unity.

Social selection and the evolution of cooperative groups: The example of the cellular slime moulds

In social selection the phenotype of an individual depends on its own genotype as well as on the phenotypes, and so genotypes, of other individuals. This makes it impossible to associate an invariant phenotype with a genotype: the social context is crucial. Descriptions of metazoan development, which often is viewed as the acme of cooperative social behaviour, ignore or downplay this fact. The implicit justification for doing so is based on a group-selectionist point of view. Namely, embryos are clones, therefore all cells have the same evolutionary interest, and the visible differences between cells result from a common strategy. The reasoning is flawed, because phenotypic heterogeneity within groups can result from contingent choices made by cells from a flexible repertoire as in multicellular development. What makes that possible is phenotypic plasticity, namely the ability of a genotype to exhibit different phenotypes. However, co-operative social behaviour with division of labour requires that different phenotypes interact appropriately, not that they belong to the same genotype, or have overlapping genetic interests. We sketch a possible route to the evolution of social groups that involves many steps: (a) individuals that happen to be in spatial proximity benefit simply by virtue of their number; (b) traits that are already present act as preadaptations and improve the efficiency of the group; and (c) new adaptations evolve under selection in the social context-that is, via interactions between individuals-and further strengthen group behaviour. The Dictyostelid or cellular slime mould amoebae (CSMs) become multicellular in an unusual way, by the aggregation of free-living cells. In nature the resulting group can be genetically homogeneous (clonal) or heterogeneous (polyclonal); in either case its development, which displays strong cooperation between cells (to the extent of so-called altruism) is not affected. This makes the CSMs exemplars for the study of social behaviour.

Microscopic origin of the chirality driven morphologies of the amphiphilic monolayers and bilayers

It is widely known that the compressed monolayers and bilayers of chiral lipids or fatty acids form helical morphologies, while the corresponding racemic modification gives only flat platelets without twist. No molecular explanation of this phenomenon is yet available, although subtle interactions at the chiral centers have often been proposed as the driving force behind the morphology of the aggregate to form a particular shape. In the present study, the morphologies of the chiral amphiphilic assemblies have been predicted on the basis of an effective pair potential between the molecules, which depends on the relative sizes of the groups attached to the chiral centers, the orientation of the amphiphilic molecules and also on the distance between them. It is shown that fur a pair of same kind of enantiomers, the minimum energy conformation favours a twist angle between them. This twist between the neighbouring molecules gives rise to the helicity of the aggregate. The present theory also shows from the molecular considerations that for a pair of mirror-image isomers (i.e. the racemic modification) the minimum energy conformation corresponds to the zero angle between the molecules, thus giving rise to flat platelets as observed in experiments. Another fascinating aspect of such chirality driven helical structures is that the sense (or the handedness) of the helix is highly specific about the chirality of the monomer concerned. The molecular theory shows, for the first time, that the sense of the helical structures in many cases is determined by the sizes of the groups attached to the chiral centers and the effective potential between them. The predicted senses of the helical structures are in complete agreement with the experimental results.

Some aspects of the solitary waves in a relativistic inhomogeneous plasma

In contrast to earlier observations on various solitary wave propagations, especially those bifurcated by the compressive and rarefactive solitary waves, the existence of spiky and explosive solitary waves is here believed to arise because of the presence of free and trapped electrons. So far, very few studies have been carried out to satisfactorily explain the presence of the solitary waves in space as observed by satellites. It is also attempted to highlight the probable impact on the various solitary wave propagations in a generalized multi-component, inhomogeneous plasma upon consideration of a relativistic treatment. It is expected that such a treatment will prove the existence of the solitary waves most expeditiously and exhibit the presence of chaos therein, thus giving a suitable explanation to the observations of various forms of spiky and explosive solitary waves in space-plasma. Copyright (C) 1996 Elsevier Science Ltd