Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

In a previous paper, we described the room temperature rapid, selective, reversible, and near quantitative Cu-activated nitroxide radical coupling (NRC) technique to prepare 3-arm polystyrene stars. In this work, we evaluated the Cu-activation mechanism, either conventional atom transfer or single electron transfer (SET), through kinetic simulations. Simulation data showed that one can describe the system by either activation mechanism. We also found through simulations that bimolecular radical termination, regardless of activation mechanism, was extremely low and could be considered negligible in an NRC reaction. Experiments were carried out to form 2- and 3-arm PSTY stars using two ligands, PMDETA and Me6TREN, in a range of solvent conditions by varying the ratio of DMSO to toluene, and over a wide temperature range. The rate of 2- or 3-arm star formation was governed by the choice of solvent and ligand. The combination of Me6TREN and toluene/DMSO showed a relatively temperature independent rate, and remarkably reached near quantitative yields for 2-arm star formation after only 1 min at 25 °C.

Counter-figures : An Essay on Antimetaphoric Resistance: Paul Celan's Poetry and Poetics at the Limits of Figurality

Titled "An Essay on Antimetaphoric Resistance", the dissertation investigates what is here being called "Counter-figures": a term which has in this context a certain variety of applications. Any other-than-image or other-than-figure, anything that cannot be exhausted by figuration (and that is, more or less, anything at all, except perhaps the reproducible images and figures themselves) can be considered "counter-figurative" with regard to the formation of images and figures, ideas and schemas, "any graven image, or any likeness of any thing". Singularity and radical alterity, as well as temporality and its peculiar mode of uniqueness are key issues here, and an ethical dimension is implied by, or intertwined with, the aesthetic. In terms borrowed from Paul Celan's "Meridian" speech, poetry may "allow the most idiosyncratic quality of the Other, its time, to participate in the dialogue". This connection between singularity, alterity and temporality is one of the reasons why Celan so strongly objects to the application of the traditional concept of metaphor to poetry. As Celan says, "carrying over [übertragen]" by metaphor may imply an unwillingness to "bear with [mittragen]" and to "endure [ertragen]" the poem. The thesis is divided into two main parts. The first consists of five distinct prolegomena which all address the mentioned variety of applications of the term "counter-figures", and especially the rejection or critique of either metaphor (by Aristotle, for instance) or the concept of metaphor (defined by Aristotle, and sometimes deemed "anti-poetic" by both theorists and poets). Even if we restrict ourselves to the traditional rhetorico-poetical terms, we may see how, for instance, metonymy can be a counter-figure for metaphor, allegory for symbol, and irony for any single trope or for any piece of discourse at all. The limits of figurality may indeed be located at these points of intersection between different types of tropes or figures, and even between figures or tropes and the "non-figurative trope" or "pseudo-figure" called catachresis. The second part, following on from the open-ended prolegomena, concentrates on Paul Celan's poetry and poetics. According to Celan, true poetry is "essentially anti-metaphoric". I argue that inasmuch as we are willing to pay attention to the "will" of the poetic images themselves (the tropes and metaphors in a poem) to be "carried ad absurdum", as Celan invites us to do, we may find alternative ways of reading poetry and approaching its "secret of the encounter", precisely when the traditional rhetorical instruments, and especially the notion of metaphor, become inapplicable or suspicious — and even where they still seem to impose themselves.

Impedance tube technology for flow acoustics

Acoustic impedance of a termination, or of a passive subsystem, needs to be measured not only for acoustic lining materials but also in the exhaust systems of flow machinery, where mean flow introduces peculiar problems. Out of the various methods of measurement of acoustic impedance, the discrete frequency, steady state, impedance tube method [1] is most reliable, though time consuming, and requires no special instrumentation.

ESR Studies of Phase Transitions in Double Propionates: Dicalcium Barium Propionate Ca2Ba(C2H5COO)6

Single crystal [(111) and (100) planes], and powder ESR of Mn2+ (substituting for Ca2+) in Ca2Ba(C2H5COO)6 in the temperature range 220°C to -160°C shows (i) a doubling of both the physically and chemically inequivalent sites, and a change in the magnitude (150 G at -6°C to 170 G at -8°C) as well as the orientation of the D tensor across the -6°C transition and (ii) an inflection point in the D vs T plot across the -75°C transition. The oxygen octahedra around the Ca2+ sites are inferred to undergo alternate rotations, showing the participation of the carboxyl oxygens in the -6°C transition. A relation of the type D=D0(1+αT+βT2) seems to fit the D variation satisfactorily.

Mediated music makers : Constructing author images in popular music

The subject of the thesis is the mediated construction of author images in popular music. In the study, the construction of images is treated as a process in which artists, the media and the members of the audience participate. The notions of presented, mediated and compiled author images are used in explaining the mediation process and the various authorial roles of the agents involved. In order to explore the issue more closely, I analyse the author images of a group of popular music artists representing the genres of rock, pop and electronic dance music. The analysed material consists mostly of written media texts through which the artists authorial roles and creative responsibilities are discussed. Theoretically speaking, the starting points for the examination lie in cultural studies and discourse analysis. Even though author images may be conceived as intertextual constructions, the artist is usually presented as a recognizable figure whose purpose is to give the music its public face. This study does not, then, deal with musical authors as such, but rather with their public images and mediated constructions. Because of the author-based functioning of popular music culture and the idea of the artist s individual creative power, the collective and social processes involved in the making of popular music are often superseded by the belief in a single, originating authorship. In addition to the collective practices of music making, the roles of the media and the marketing machinery complicate attempts to clarify the sharing of authorial contributions. As the case studies demonstrate, the differences between the examined author images are connected with a number of themes ranging from issues of auteurism and stardom to the use of masked imagery and the blending of authorial voices. Also the emergence of new music technologies has affected not only the ways in which music is made, but also how the artist s authorial status and artistic identity is understood. In the study at hand, the author images of auteurs, stars, DJs and sampling artists are discussed alongside such varied topics as collective authorship, evaluative hierarchies, visual promotion and generic conventions. Taken altogether, the examined case studies shed light on the functioning of popular music culture and the ways in which musical authorship is (re)defined.

Ruumiinkuvia! : Suomalainen performanssi- ja kehotaide 1980- ja1990-luvulla psykoanalyysin valossa

My PhD-thesis Body Images! Psychoanalytical Analysis of Finnish Performance and Body Art in the 1980s and 1990s considers Finnish performance and body art performed mainly by visual artists. In Part I, I chart the historical construction of performance art and its extension since the beginning of the 21st century. There are several wievs of the historical background of performance art. I introduce three different genealogies of performance art. One is Rose-Lee Goldberg s view. She connects performance art with the European avant-garde already at the beginning of the 20th century from futurists and dadaists to Russian avant-garde and the Bauhaus. I prefer to present performance art as contemporary art, which began to take shape in connection with visual arts in the 1950s and 1960s. The focus on the body is apparent in nearly all performance art. Nevertheless, throug the concept of body art I want to empasize the artist s body as the place of art. Body art (as part of performance art) functions as thematic and interpretive concept, which allows me to focus on performances where the questions of body image, narcissism, desire, language and pleasure are incorporated in particular intensive ways. In Part II, I explore the arrival of performance art in Finnish visual arts in the 1980s. I study the new generation s relation to earlier Finnish happenings (1960s) and performative actions in 1970 s. I briefly introduce performance groups of the 1980s art scene and consider their reception in media. The main focus is on the group Jack Helen Brut, in which I see many similarities to the so- called Theatre of Images. The goal of this part II is to provide historical context for the performance analysis that follows. In Part III, I develop the concept of body image which is my main theoretical term. The concept of body image is used according to Lacanian psychoanalytical theory, especially his considerations of mirror stages. My first mapping of body image, which I call imaginary body image, is based on Lacan s famous mirror stage article (1949). According to my reading, body image is narcistic and aggressive. The important concepts here are ego, imaginary, méconnaisance and alienation. In 1953 Lacan began to develop different version on mirror stage, in which he emphasized the primacy of symbolic dimension. It is not image, but language which constructs the foundations of body image. Central concepts in this chater are Other as language, ego-ideal, demand and desire. In the last chapter I connect the third version of the mirror stage to concepts of gaze, phantasy, real, jouissance and object a. In previous chapters I had considered body image in relation to ego. Now I explore it in relation to subject. In my reading the body image is fragile phenomen, which oscillates between yearning for coherence and phantasies of fragmented images. Part IV of the thesis begins with an introduction to the central concepts and debates in performace studies over the last few decades. Important concepts are presence, performativity and theatricality. The main substance of my thesis, however, is the performance analysis, which focuses on works by three Finnish artists and one Finnish group. The first analysis concerns the performance (1992) of Kimmo Schroderus. I discuss the relationship between narcissism and body art and the changes in demands projected on body images of men in recent decades in a Euro-American context. I also explore this performance in relation to the myth of Narcissus, which I reinterpret through Narcissus s aggression against his own body. The group Homo S is the main subject of the next analysis. I discuss the relationship between feminist art and performance art, especially in the United States in the 1960s and 1970s. Homo S is different from this early performance art because of its anarchism, humor and rejection of all ideals. Homo S characterizes its performance Body Body (1983) as liberating vulgar feminism . Sociality and performance of erotic relations between women are central in Body Body. Pia Lindman s performances are the subjects of my third analysis. I study three of her performances: Olen muoto (1993), 17 and in love (1994) and Arranged views (1995). I interpret these performances as efforts to disperse the imaginary and symbolic structures of the body image. She constructs the peculiar object a and phantasy space of her own. In the last analysis I move from questions of image and gaze to a study of language, sound and jouissance. I discuss at a general level the performance of orality and helplesness (Hilflosigkeit) in body art. The central elements in Pentti Otto Koskinen s performances are the ear, listening and receptive gestures and postions. Perseveraatio (1998) can be understood representing as submission to the super-ego s power, which compels one to enjoy. I examine particularly closely the performance Maissi on hyvää ei missään nimessä maissia (1995), which I interpret as the return of a baby s body image to the liminal site of choice: language or jouissance?

Passion vallassa : Hermostunut aika Minna Canthin teoksissa

Under the power of passion. The age of nervousness in Minna Canth s works This research contemplates the psychology of Minna Canth s characters through the historical image of man in late 19th century Europe. The central operative term of the study is passion , understood as a twofold philosophical concept that includes both desire and suffering. The method of this study is historical and contextual. The study interprets the passions and the psychology of Canth s characters as they were understood in their own time. The indicator of the relevant contexts is the realist and naturalist genre of Canth s works. New research on the genre of the time is also the basis of a new kind of psychological approach to Canth s works. The most important context of passion in Canth s works is the positivistic and pathological image of man at the end of the 19th century. Then, passion was widely discussed, and was perceived as a physiological phenomenon that influenced humans neurologically and caused different kinds of physiological symptoms and nervous disorders. But at the same time, passion was understood as a manifestation of human instincts and drives. The naturalistic literature of the day aimed at creating deterministic studies of human morality and psychology following Émile Zola s application of experimental science methods in his writing. The pathological image of man is most explicitly manifested in Canth s formerly unknown short story Lääkäri (Doctor, 1891), in which a doctor who is interested in psychology visits a jail to meet a peculiar criminal, a girl who feels no remorse for her multiple crimes. In other works of Canth the medically motivated viewpoint is more hidden in the deterministic narrative and depiction of the characters. The present study approaches the passion in Minna Canth s works through five thematic chapters, in witch characters are interpreted suffering from blind love, ennui, crippling romantic idealism, melancholy, guilt and nostalgia, and their stories can be prescribed as medical histories which depict the born of the passion and its development towards ruin. All protagonists are also manifestations of their own time. Canth criticises the modern life and its demands as well as social defects through the tragic stories of individuals. The study demonstrates that Canth did not, like previous research has suggested, wait until the 1890s before writing works of a psychological nature but had already written according to the psychological paradigm of her time in Työmiehen vaimo (1885). The social and psychological interests intertwine in Canth s works and are not exclusionary as has formerly been interpreted. Canth is also critical of the medical power implicit in the naturalist experimental method and this shows itself especially in her depiction of working class women.

Effect of Structural Modification on the Quantum-Size Effect in II-VI Semiconducting Nanocrystals

The electronic structure of group II-VI semiconductors in the stable wurtzite form is analyzed using state-of-the-art ab initio approaches to extract a simple and chemically transparent tight-binding model. This model can be used to understand the variation in the bandgap with size, for nanoclusters of these compounds. Results complement similar information already available for same systems in the zinc blende structure. A comparison with all available experimental data on quantum size effects in group II-VI semiconductor nanoclusters establishes a remarkable agreement between theory and experiment in both structure types, thereby verifying the predictive ability of our approach. The significant dependence of the quantum size effect on the structure type suggests that the experimental bandgap change at a given size compared to the bulk bandgap, may be used to indicate the structural form of the nanoclusters, particularly in the small size limit, where broadening of diffraction features often make it difficult to unambiguously determine the structure.

The apical control of lateral bud development in excised shoot tips of Cuscuta reflexa cultured in vitro

Excised shoot tips of Cuscuta reflexa Roxb. (dodder), a rootless and leafless angiospermic plant parasite, were cultured in vitro for the study of the control of lateral bud development by the apex. In a chemically defined medium lacking hormones, the basal bud alone developed into a shoot. The addition of coconut milk to the growth medium induced the activation of multiple lateral buds, but only a single bud developed further into a shoot. The decapitation of this shoot induced the development of another shoot and the process could be repeated. This showed the controlling effect of the apex in correlative control of bud development. Application of indole-3-acetic acid to the shoot tip explant delayed the development of the lateral bud. Gibberellic acid A3 induced a marked elongation growth of the explant and reinforced apical dominance. The direct application of cytokinin to an inhibited bud relieved it from apical dominance. A basipetally decreasing concentration gradient of auxin may prevail at the nodes. Bud outgrowth is probably stimulated by cytokinin produced locally in the bud.

Preparation of CaTiO3 fine powders by the hydrothermal method

Fine powders consisting of 0.1–0.5 μm size crystallites of CaTiO3 are prepared at 150–200°C by the hydrothermal method starting from hydrated titania gel and reactive calcium oxide suspended as an aqueous slurry in an autoclave. The resulting high-purity CaTiO3 is characterised by TEM, X-ray powder diffraction, chemical analyses and sintering characteristics. The hydrothermally prepared CaTiO3 powders are sinterable to high-density ceramics below 1400°C. The dc conductivity behaviour of the chemically reduced ceramics is presented.

Peer leader led revision skills workshop – who benefits?

In response to student requests, a peer leader led revision skills workshop was run just prior to a mid-semester exam in pharmacology. This skills workshop was well attended and received by equal percentages of both accelerated and traditional students (who were in their 4th semester at university). This suggests that both accelerated and traditional students can benefit from peer led revision skills workshops.

Which accelerated nursing students withdraw and fail in their first year of a Bachelor of Nursing (BN)?

Accelerated students in nursing have their first experience of university entering into second year subjects such as pharmacology. These accelerated students may have a Diploma of Nursing or equivalent experience or may be domestic or international graduates in any subject area. We have previously shown that the withdrawal rates are higher for accelerated than traditional students. We now show that of the accelerated students, it is only the diploma students that have difficulty transitioning to a BN.

Reduced attrition of accelerated nursing students from pharmacology – is it associated with graduation?

In order to reduce the attrition of accelerated nursing students in bioscience/pharmacology, we introduced an innovation to help these students. Although this innovation was associated with reduced attritions from the units in their first year at university, we now show that there was a reduced graduation rate of the accelerated students who survived pharmacology, compared to the traditional students.

Pyrrolizidine Alkaloids in Crotalaria Taxa from Northern Australia: Risk to Grazing Livestock.

Crotalaria species containing hepatotoxic pyrrolizidine alkaloids grow widely in pastures in northern Australia and have sporadically poisoned grazing livestock. The diverse Crotalaria taxa present in these pastures include varieties, subspecies, and chemotypes not previously chemically examined. This paper reports the pyrrolizidine alkaloid composition and content of 24 Crotalaria taxa from this region and assesses the risk of poisoning in livestock consuming them. Alkaloids present in C. goreensis, C. aridicola subsp. densifolia, and C. medicaginea var. neglecta lack the esterified 1,2-unsaturated functionality required for pyrrole adduct formation, and these taxa are not hepatotoxic. Taxa with high levels of hepatotoxic alkaloids, abundance, and biomass pose the greatest risk to livestock health, particularly C. novae-hollandiae subsp. novae-hollandiae, C. ramosissima, C. retusa var. retusa, and C. crispata. Other species containing moderate alkaloid levels, C. spectabilis and C. mitchellii, also pose significant risk when locally abundant.

Oikein, nurin - miten Suomessa kudin : Tutkimus neulonnan työotteista.

The aim of this work was to study what kind of working grips people use to knit in Finland and decide if one grip is superior to others. I investigated how knitters have adopted their grips and how they experience their knitting. I also explored whether it is possible to change one's grip. To provide a theoretical basis for the research I observed knitting in terms of culture, skill and ergonomics. The first part of the study material comprised video recordings of the grips of 95 knitters together with background information collected via a questionnaire during the education of craft teachers at the University of Helsinki in spring 2004, 2005 and 2006. Using the data obtained I focused on three knitters, whose grip of the knitting needles clearly differed from the ergonomically good grip. In addition to them I interviewed one student, who had changed over to more ergonomic way of knitting after participating in the first part of this study. In this respect my study is a several events' case study. In order to analyse my data I used both qualitative and quantitative content analysis methods to complement each other. Most of my research participants had learned to knit in first years of elementary school or comprehensive school. Almost everyone had adopted the basics of knitting by imitating, and many of them had corrected "incorrect" positions from verbal instructions. Through practice the imitated position had gradually become the style unique to each knitter. The findings showed that students' background in knitting is quite varied due to the diverse level of craft teaching. This is reflected in their knitting grips and their interest in knitting. Students do not think that there is one right working grip. The most important thing is that working seems as fluent and relaxed as possible, at which point knitting is easy and flows freely. They often consider their own style so pleasing and well-functioning that they do not think there could be any room for improvement. This study pointed out that, while it is possible to change a knitter's working grip, there is a bigger challenge in acknowledging weaknesses in one's know how. According to the results of my research, the most common working grip among Finnish knitters' corresponds with the grip that has been described as ergonomically good. Over one third of all participants knitted this way. Hands keep the knitting firmly but without tension. The forefinger that guides the yarn from the ball rests gently against the knitting needle, and the yarn goes in front of the first joint of the forefinger. The position of the hands and loops is the same as in the ergonomically good grip, i.e. the fingertips of both hands and the loops are near the tips of the knitting needles, so that the fingers only have to move small distances. When knitters purl and plain, they commonly pick up the yarn from the back of the knitting needle in the same way as when knitting. While researching the common features of working grips I have learned what abnormal grips are like. Although I recognized many different ways to knit, all the peculiar grips were modifications of the continental way of knitting. The results of this study give a clear picture of those points knitters should focus their attention on in order to gain a good hold of the needles.