Reversible Insertion of Methyl Isothiocyanate into Copper(I)Aryloxides

MeNCS undergoes insertion into the copper(I)-aryloxide bond to form [N-methylimino(aryloxy)methanethiolato]-copper(I) complexes. This insertion occurs in the absence of ancillary ligands unlike the analogous insertion of PhNCS. The reaction with 4-methylphenoxide results in the formation of hexakis[[N-methylimino(4-methylphenoxy) methanethiolato]copper(I)] (1), which has been characterized by X-ray crystallography. Crystal data for 1: hexagonal , a = 12.365(3) Angstrom, c = 36.734(16) Angstrom, gamma = 120 degrees, Z = 3, V = 4863(3) Angstrom(3), R = 0.0306. Reactions of 2,6-dimethyl- and 4-chlorophenoxides also result in analogous copper(I) complexes 2 and 3. Addition of stochiometric amounts of PPh(3) to the oligomeric complexes typically results in the extrusion of MeNCS. The ease of extrusion is dependent on the substituents on the aryloxide, and this deinsertion is accelerated by water. However, the extrusion reaction is slow enough in the case of the N-methylimino(2,6-dimethylphenoxy)-methanethiolate complex and the isolation of an intermediate monomeric product bis(triphenylphosphine)[N-methylimino(2, 6-dimethylphenoxy)methanethiolato] copper(I) (4) is possible. Crystal data for 4: triclinic , a = 10.088(2) Angstrom, b = 11.302(1) Angstrom, c = 17.990(2) Angstrom, alpha = 94.06(1)degrees, beta = 95.22(2)degrees, gamma = 103.94(1)degrees, Z = 2, V = 1974.4(7) Angstrom(3), R = 0.0361. In the presence of of PPh(3), the insertion reaction becomes reversible. This allows the exchange of the heterocumulene MeNCS or the aryloxy group in these molecules with another heterocumulene or a phenol, respectively, when catalytic amounts of PPh(3) are added. Oligomers with exchanged heterocumulmes and phenols could be characterized by independent synthesis.

Interaction of Co, Mn, Mg and AI with d(GCGTACGC): a spectroscopic study

Spectroscopic study on the interactions of trace elements Co, Mn, Mg and Al with d(GCGTACGC) indicated the following: Al and Mg did not alter T-m values. Mn enhanced T-m at lower concentration and decreased it at higher concentrations. Interestingly Co at higher concentration elevated the T-m. These studies also showed lower concentrations of Mn displaced EtBr, whereas Al could displace it at higher ionic strength. Mg and Co displaced EtBr fluorescence at moderate concentrations. The binding constant values and CD spectra clearly indicated strong binding of these elements to DNA.

A Doubly curved Quadrilateral finite-element for the analysis of laminated anisotropic thin shells of revoution

The details of development of the stiffness matrix for a doubly curved quadrilateral element suited for static and dynamic analysis of laminated anisotropic thin shells of revolution are reported. Expressing the assumed displacement state over the middle surface of the shell as products of one-dimensional first order Hermite polynomials, it is possible to ensure that the displacement state for the assembled set of such elements, is geometrically admissible. Monotonic convergence of total potential energy is therefore possible as the modelling is successively refined. Systematic evaluation of performance of the element is conducted, considering various examples for which analytical or other solutions are available.

Honey flows through fertile valleys : The cognitive and evolutionary foundations of paradise representations

The aim of the study is to explain how paradise beliefs are born from the viewpoint of mental functions of the human mind. The focus is on the observation that paradise beliefs across the world are mutually more similar than dissimilar. By using recent theories and results from the cognitive and evolutionary study of religion as well as from studies of environmental preferences, I suggest that this is because pan-human unconscious motivations, the architecture of mind, and the way the human mind processes information constrain the possible repertoire of paradise beliefs. The study is divided into two parts, theoretical and empirical. The arguments in the theoretical part are tested with data in the empirical part with two data sets. The first data set was collected using an Internet survey. The second data set was derived from literary sources. The first data test the assumption that intuitive conceptions of an environment of dreams generally follow the outlines set by evolved environmental preferences, but that they can be tweaked by modifying the presence of desirable elements. The second data test the assumption that familiarity is a dominant factor determining the content of paradise beliefs. The results of the study show that in addition to the widely studied belief in supernatural agents, belief in supernatural environments wells from the natural functioning of the human mind attesting the view that religious thinking and ideas are natural for human species and are produced by the same mental mechanisms as other cultural information. The results also help us to understand that the mental structures behind the belief in the supernatural have a wider scope than has been previously acknowledged.

Japanese Video Game Localization : A Case Study of Sony's Sairen Series

This thesis is a comparative case study in Japanese video game localization for the video games Sairen, Sairen 2 and Sairen Nyûtoransurêshon, and English-language localized versions of the same games as published in Scandinavia and Australia/New Zealand. All games are developed by Sony Computer Entertainment Inc. and published exclusively for Playstation2 and Playstation3 consoles. The fictional world of the Sairen games draws much influence from Japanese history, as well as from popular and contemporary culture, and in doing so caters mainly to a Japanese audience. For localization, i.e. the adaptation of a product to make it accessible to users outside the original market it was intended for in the first place, this is a challenging issue. Video games are media of entertainment, and therefore localization practice must preserve the games’ effects on the players’ emotions. Further, video games are digital products that are comprised of a multitude of distinct elements, some of which are part of the game world, while others regulate the connection between the player as part of the real world and the game as digital medium. As a result, video game localization is also a practice that has to cope with the technical restrictions that are inherent to the medium. The main theory used throughout the thesis is Anthony Pym’s framework for localization studies that considers the user of the localized product as a defining part of the localization process. This concept presupposes that localization is an adaptation that is performed to make a product better suited for use during a specific reception situation. Pym also addresses the factor that certain products may resist distribution into certain reception situations because of their content, and that certain aspects of localization aim to reduce this resistance through significant alterations of the original product. While Pym developed his ideas with mainly regular software in mind, they can also be adapted well to study video games from a localization angle. Since modern video games are highly complex entities that often switch between interactive and non-interactive modes, Pym’s ideas are adapted throughout the thesis to suit the particular elements being studied. Instances analyzed in this thesis include menu screens, video clips, in-game action and websites. The main research questions focus on how the games’ rules influence localization, and how the games’ fictional domain influences localization. Because there are so many peculiarities inherent to the medium of the video game, other theories are introduced as well to complement the research at hand. These include Lawrence Venuti’s discussions of foreiginizing and domesticating translation methods for literary translation, and Jesper Juul’s definition of games. Additionally, knowledge gathered from interviews with video game localization professionals in Japan during September and October 2009 is also utilized for this study. Apart from answering the aforementioned research questions, one of this thesis’ aims is to enrich the still rather small field of game localization studies, and the study of Japanese video games in particular, one of Japan’s most successful cultural exports.

From Iron Horse to Rauta-airot - a Semiotic View on the Domestication of Metaphors in Literary Translation

The thesis concentrates on two questions: the translation of metaphors in literary texts, and the use of semiotic models and tools in translation studies. The aim of the thesis is to present a semiotic, text based model designed to ease the translation of metaphors and to analyze translated metaphors. In the translation of metaphors I will concentrate on the central problem of metaphor translations: in addition to its denotation and connotation, a single metaphor may contain numerous culture or genre specific meanings. How can a translator ensure the translation of all meanings relevant to the text as a whole? I will approach the question from two directions. Umberto Eco's holistic text analysis model provides an opportunity to concentrate on the problematic nature of metaphor translation from the level of a text as a specific entity, while George Lakoff's and Mark Johnson's metaphor research makes it possible to approach the question from the level of individual metaphors. On the semiotic side, the model utilizes Eero Tarasti's existential semiotics supported by Algirdas Greimas' actant model and Yuri Lotman's theory of cultural semiotics. In the model introduced in the thesis, individual texts are deconstructed through Eco's model into elements. The textual roles and features of these elements are distilled further through Tarasti's model into their coexistent meaning levels. The priorization and analysis of these meaning levels provide an opportunity to consider the contents and significance of specific metaphors in relation to the needs of the text as a whole. As example texts, I will use Motörhead's hard rock classic Iron Horse/Born to Lose and its translation into Rauta-airot by Viikate. I will use the introduced model to analyze the metaphors in the source and target texts, and to consider the transfer of culture specific elements between the languages and cultural borders. In addition, I will use the analysis process to examine the validity of the model introduced in the thesis.

Encounters with the Virtual : The Experience of Art In Gilles Deleuze's Philosophy

My thesis concerns the notion of existence as an encounter, as developed in the philosophy of Gilles Deleuze (1925 1995). What this denotes is a critical stance towards a major current in Western philosophical tradition which Deleuze nominates as representational thinking. Such thinking strives to provide a stable ground for identities by appealing to transcendent structures behind the apparent reality and explaining the manifest diversity of the given by such notions as essence, idea, God, or totality of the world. In contrast to this, Deleuze states that abstractions such as these do not explain anything, but rather that they need to be explained. Yet, Deleuze does not appeal merely to the given. He sees that one must posit a genetic element that accounts for experience, and this element must not be naïvely traced from the empirical. Deleuze nominates his philosophy as transcendental empiricism and he seeks to bring together the approaches of both empiricism and transcendental philosophy. In chapter one I look into the motivations of Deleuze s transcendental empiricism and analyse it as an encounter between Deleuze s readings of David Hume and Immanuel Kant. This encounter regards, first of all, the question of subjectivity and results in a conception of identity as non-essential process. A pre-given concept of identity does not explain the nature of things, but the concept itself must be explained. From this point of view, the process of individualisation must become the central concern. In chapter two I discuss Deleuze s concept of the affect as the basis of identity and his affiliation with the theories of Gilbert Simondon and Jakob von Uexküll. From this basis develops a morphogenetic theory of individuation-as-process. In analysing such a process of individuation, the modal category of the virtual becomes of great value, being an open, indeterminate charge of potentiality. As the virtual concerns becoming or the continuous process of actualisation, then time, rather than space, will be the privileged field of consideration. Chapter three is devoted to the discussion of the temporal aspect of the virtual and difference-without-identity. The essentially temporal process of subjectification results in a conception of the subject as composition: an assemblage of heterogeneous elements. Therefore art and aesthetic experience is valued by Deleuze because they disclose the construct-like nature of subjectivity in the sensations they produce. Through the domain of the aesthetic the subject is immersed in the network of affectivity that is the material diversity of the world. Chapter four addresses a phenomenon displaying this diversified indentity: the simulacrum an identity that is not grounded in an essence. Developed on the basis of the simulacrum, a theory of identity as assemblage emerges in chapter five. As the problematic of simulacra concerns perhaps foremost the artistic presentation, I shall look into the identity of a work of art as assemblage. To take an example of a concrete artistic practice and to remain within the problematic of the simulacrum, I shall finally address the question of reproduction particularly in the case recorded music and its identity regarding the work of art. In conclusion, I propose that by overturning its initial representational schema, phonographic music addresses its own medium and turns it into an inscription of difference, exposing the listener to an encounter with the virtual.

Characterisation and early detection of an offtype from micropropagated Lady Finger bananas

An offtype has been identified from micropropagated Lady Finger bananas (Musa spp., AAB group, Pome subgroup) that is characterised by its slow growth and poor bunch size. Bunch weights were approximately 25% those of normal Lady Finger plants and all of the fruit produced was unmarketable. This particular offtype is the most commonly encountered from micropropagated Lady Finger plants and, in 2 instances, blocks of 3000 and 1500 plants were entirely comprised of this single offtype. Detection of offtype plants was possible during establishment and growth of plants in the glasshouse by the presence of chlorotic streaks in the leaves. In more severe cases the streaks coalesced into chlorotic patches that developed thin, necrotic areas that eventually produced holes or splits in the leaves. Symptom expression was not ameliorated by the addition of fertiliser and even though symptoms were similar to severe Ca and B deficiency, both normal and offtype plants had similar levels of these elements in the leaves. The offtype plants were also slow growing in the glasshouse and produced significantly (P<0.05) smaller pseudostems and leaves than normal plants. Offtype plants could be readily detected after 4 weeks deflasking using the presence of chlorotic streaks in the leaves as the main selection criterion. Maximum discrimination was possible between weeks 5–7 and at the 6-leaf stage when all of the offtypes could be detected.

Double-Edged Imitation : Theories and Practices of Pastiche in Literature

This study concentrates on the contested concept of pastiche in literary studies. It offers the first detailed examination of the history of the concept from its origins in the seventeenth century to the present, showing how pastiche emerged as a critical concept in interaction with the emerging conception of authorial originality and the copyright laws protecting it. One of the key results of this investigation is the contextualisation of the postmodern debate on pastiche. Even though postmodern critics often emphasise the radical novelty of pastiche, they in fact resuscitate older positions and arguments without necessarily reflecting on their historical conditions. This historical background is then used to analyse the distinction between the primarily French conception of pastiche as the imitation of style and the postmodern notion of it as the compilation of different elements. The latter s vagueness and inclusiveness detracts from its value as a critical concept. The study thus concentrates on the notion of stylistic pastiche, challenging the widespread prejudice that it is merely an indication of lack of talent. Because it is multiply based on repetition, pastiche is in fact a highly ambiguous or double-edged practice that calls into question the distinction between repetition and original, thereby undermining the received notion of individual unique authorship as a fundamental aesthetic value. Pastiche does not, however, constitute a radical upheaval of the basic assumptions on which the present institution of literature relies, since, in order to mark its difference, pastiche always refers to a source outside itself against which its difference is measured. Finally, the theoretical analysis of pastiche is applied to literary works. The pastiches written by Marcel Proust demonstrate how it can become an integral part of a writer s poetics: imitation of style is shown to provide Proust with a way of exploring the role of style as a connecting point between inner vision and reality. The pastiches of the Sherlock Holmes stories by Michael Dibdin, Nicholas Meyer and the duo Adrian Conan Doyle and John Dickson Carr illustrate the functions of pastiche within a genre detective fiction that is itself fundamentally repetitive. A.S. Byatt s Possession and D.M. Thomas s Charlotte use Victorian pastiches to investigate the conditions of literary creation in the age of postmodern suspicion of creativity and individuality. The study thus argues that the concept of pastiche has valuable insights to offer to literary criticism and theory, and that literary pastiches, though often dismissed in reviews and criticism, are a particularly interesting object of study precisely because of their characteristic ambiguity.

Subsoil constraints to grain production in the cropping soils of the north-eastern region of Australia: an overview

In dryland agricultural systems of the subtropical, semi-arid region of north-eastern Australia, water is the most limiting resource. Crop productivity depends on the efficient use of rainfall and available water stored in the soil during fallow. Agronomic management practices including a period of fallow, stubble retention, and reduced tillage enhance reserves of soil water. However, access to stored water in these soils may be restricted by the presence of growth-limiting conditions in the rooting zone of the crop. These have been termed as subsoil constraints. Subsoil constraints may include compacted or gravel layers (physical), sodicity, salinity, acidity, nutrient deficiencies, presence of toxic elements (chemical) and low microbial activity (biological). Several of these constraints may occur together in some soils. Farmers have often not been able to obtain the potential yield determined by their prevailing climatic conditions in the marginal rainfall areas of the northern grains region. In the past, the adoption of soil management practices had been largely restricted to the top 100 mm soil layer. Exploitation of the subsoil as a source of water and nutrients has largely been overlooked. The key towards realising potential yields would be to gain better understanding of subsoils and their limitations, then develop options to manage them practically and economically. Due to the complex nature of the causal factors of these constraints, efforts are required for a combination of management approaches rather than individual options, with the aim to combat these constraints for sustainable crop production, managing natural resources and avoiding environmental damage.

Consonance in urban form: The architectural dimension of urban morphology

Consonance in urban form is contingent on the continuity of the fine grain architectural features that are imbued in the commodity of the evolved historic urban fabric. A city's past can be viewed therefore as a repository of urban form characteristics from which concise architectural responses can result in a congruent urban landscape. This thesis proposes new methods to evaluate the interplay of architectural elements that can be traced throughout the lifespan of the particular evolving urban areas under scrutiny, and postulates a theory of how the mapping of historical urban form can correlate with deriving parameters for new buildings.

MAS NMR as a probe for investigating the distribution of Si---O---Si angles in lithium silicate glasses

Magic-angle-spinning NMR has been used to study Si---O---Si bond-angle distributions associated with various structural elements, Qn, present in lithium silicate glasses of different compositions. It is shown that glasses contain a plurality of structural elements with a broad distribution of Si---O---Si bond angles, and that the width of the distribution is characteristic of a particular Qn species

NQR Studies of the chloro(amino)cyclotriphosphazenes, N3P3(NHCH2·CH2NH)Cl4, N3P3(NHBut)4Cl4 and N3P3(NHBut)4Cl2

The frequencies and variable-temperature behaviour of 35Cl nuclear quadrupole resonance in three aminocyclophosphazene derivatives are reported. The observed frequencies and multiplicity are correlated with the disposition of the substituents and the crystal structure. The temperature-dependence data are discussed in the framework of Bayer-Kushida-Brown equations and low-lying torsional (librational) frequencies and their average temperature coefficients are estimated. Brown's parabolic equation provides a good fit to the experimental data. Variable-temperature proton FT-NMR measurements (at 270 MHz) have also been carried out. The results are consistent with the NQR data and indicate the presence of two-site chemical exchange of the -NH protons and hydrogen bonding.

UV-induced NOy emissions in gas-exchange chambers enclosing Scots pine shoots: an analysis on their origin and significance

It is essential to have a thorough understanding of the sources and sinks of oxidized nitrogen (NOy) in the atmosphere, since it has a strong influence on the tropospheric chemistry and the eutrophication of ecosystems. One unknown component in the balance of gaseous oxidized nitrogen is vegetation. Plants absorb nitrogenous species from the air via the stomata, but it is not clear whether plants can also emit them at low ambient concentrations. The possible emissions are small and difficult to measure. The aim of this thesis was to analyse an observation made in southern Finland at the SMEAR II station: solar ultraviolet radiation (UV) induced NOy emissions in chambers measuring the gas exchange of Scots pine (Pinus sylvestris L.) shoots. Both measuring and modelling approaches were used in the study. The measurements were performed under noncontrolled field conditions at low ambient NOy concentrations. The chamber blank i.e. artefact NOy emissions from the chamber walls, was dependent on the UV irradiance and increased with time after renewing the Teflon film on chamber surfaces. The contribution of each pine shoot to the total NOy emissions in the chambers was determined by testing whether the emissions decrease when the shoots are removed from their chambers. Emissions did decrease, but only when the chamber interior was exposed to UV radiation. It was concluded that also the pine shoots emit NOy. The possible effects of transpiration on the chamber blank are discussed in the summary part of the thesis, based on previously unpublished data. The possible processes underlying the UV-induced NOy emissions were reviewed. Surface reactions were more likely than metabolic processes. Photolysis of nitrate deposited on the needles may have generated the NOy emissions; the measurements supported this hypothesis. In that case, the emissions apparently would consist mainly of nitrogen dioxide (NO2), nitric oxide (NO) and nitrous acid (HONO). Within studies on NOy exchange of plants, the gases most frequently studied are NO2 and NO (=NOx). In the present work, the implications of the emissions for the NOx exchange of pine were analysed with a model including both NOy emissions and NOy absorption. The model suggested that if the emissions exist, pines can act as an NOx source rather than a sink, even under relatively high ambient concentrations.

The Significance of Wild Plants in the Evolutionary Ecology of Three Major Viruses Infecting Cultivated Sweetpotato in Uganda

The studies presented in this thesis contribute to the understanding of evolutionary ecology of three major viruses threatening cultivated sweetpotato (Ipomoea batatas Lam) in East Africa: Sweet potato feathery mottle virus (SPFMV; genus Potyvirus; Potyviridae), Sweet potato chlorotic stunt virus (SPCSV; genus Crinivirus; Closteroviridae) and Sweet potato mild mottle virus (SPMMV; genus Ipomovirus; Potyviridae). The viruses were serologically detected and the positive results confirmed by RT-PCR and sequencing. SPFMV was detected in 24 wild plant species of family Convolvulacea (genera Ipomoea, Lepistemon and Hewittia), of which 19 species were new natural hosts for SPFMV. SPMMV and SPCSV were detected in wild plants belonging to 21 and 12 species (genera Ipomoea, Lepistemon and Hewittia), respectively, all of which were previously unknown to be natural hosts of these viruses. SPFMV was the most abundant virus being detected in 17% of the plants, while SPMMV and SPCSV were detected in 9.8% and 5.4% of the assessed plants, respectively. Wild plants in Uganda were infected with the East African (EA), common (C), and the ordinary (O) strains, or co-infected with the EA and the C strain of SPFMV. The viruses and virus-like diseases were more frequent in the eastern agro-ecological zone than the western and central zones, which contrasted with known incidences of these viruses in sweetpotato crops, except for northern zone where incidences were lowest in wild plants as in sweetpotato. The NIb/CP junction in SPMMV was determined experimentally which facilitated CP-based phylogenetic and evolutionary analyses of SPMMV. Isolates of all the three viruses from wild plants were genetically similar to those found in cultivated sweetpotatoes in East Africa. There was no evidence of host-driven population genetic structures suggesting frequent transmission of these viruses between their wild and cultivated hosts. The p22 RNA silencing suppressor-encoding sequence was absent in a few SPCSV isolates, but regardless of this, SPCSV isolates incited sweet potato virus disease (SPVD) in sweetpotato plants co-infected with SPFMV, indicating that p22 is redundant for synergism between SCSV and SPFMV. Molecular evolutionary analysis revealed that isolates of strain EA of SPFMV that is largely restricted geographically in East Africa experience frequent recombination in comparison to isolates of strain C that is globally distributed. Moreover, non-homologous recombination events between strains EA and C were rare, despite frequent co-infections of these strains in wild plants, suggesting purifying selection against non-homologous recombinants between these strains or that such recombinants are mostly not infectious. Recombination was detected also in the 5 - and 3 -proximal regions of the SPMMV genome providing the first evidence of recombination in genus Ipomovirus, but no recombination events were detected in the characterized genomic regions of SPCSV. Strong purifying selection was implicated on evolution of majority of amino acids of the proteins encoded by the analyzed genomic regions of SPFMV, SPMMV and SPCSV. However, positive selection was predicted on 17 amino acids distributed over the whole the coat protein (CP) in the globally distributed strain C, as compared to only 4 amino acids in the multifunctional CP N-terminus (CP-NT) of strain EA largely restricted geographically to East Africa. A few amino acid sites in the N-terminus of SPMMV P1, the p7 protein and RNA silencing suppressor proteins p22 and RNase3 of SPCSV were also submitted to positive selection. Positively selected amino acids may constitute ligand-binding domains that determine interactions with plant host and/or insect vector factors. The P1 proteinase of SPMMV (genus Ipomovirus) seems to respond to needs of adaptation, which was not observed with the helper component proteinase (HC-Pro) of SPMMV, although the HC-Pro is responsible for many important molecular interactions in genus Potyvirus. Because the centre of origin of cultivated sweetpotato is in the Americas from where the crop was dispersed to other continents in recent history (except for the Australasia and South Pacific region), it would be expected that identical viruses and their strains occur worldwide, presuming virus dispersal with the host. Apparently, this seems not to be the case with SPMMV, the strain EA of SPFMV and the strain EA of SPCSV that are largely geographically confined in East Africa where they are predominant and occur both in natural and agro-ecosystems. The geographical distribution of plant viruses is constrained more by virus-vector relations than by virus-host interactions, which in accordance of the wide range of natural host species and the geographical confinement to East Africa suggest that these viruses existed in East African wild plants before the introduction of sweetpotato. Subsequently, these studies provide compelling evidence that East Africa constitutes a cradle of SPFMV strain EA, SPCSV strain EA, and SPMMV. Therefore, sweet potato virus disease (SPVD) in East Africa may be one of the examples of damaging virus diseases resulting from exchange of viruses between introduced crops and indigenous wild plant species. Keywords: Convolvulaceae, East Africa, epidemiology, evolution, genetic variability, Ipomoea, recombination, SPCSV, SPFMV, SPMMV, selection pressure, sweetpotato, wild plant species Author s Address: Arthur K. Tugume, Department of Agricultural Sciences, Faculty of Agriculture and Forestry, University of Helsinki, Latokartanonkaari 7, P.O Box 27, FIN-00014, Helsinki, Finland. Email: tugume.arthur@helsinki.fi Author s Present Address: Arthur K. Tugume, Department of Botany, Faculty of Science, Makerere University, P.O. Box 7062, Kampala, Uganda. Email: aktugume@botany.mak.ac.ug, tugumeka@yahoo.com