Chemoenzymatic Synthesis of Chiral Organosulfur Compounds

This thesis is primarily concerned with the enzyme- catalysed synthesis of sulfoxides using reductase and dioxygenase enzymes. Chapter 1 provides an introduction to the topic of redox chemistry with particular emphasis on the application of reductase and dioxygenase enzymes in organosulfur chemistry. Earlier literature methods for the production of enantiopure sulfoxides are reviewed. A brief discussion of the methods used for the determination of enantiomeric excess and absolute configuration is provided. Chapter 2 contains results obtained using a range of whole-cell bacteria each using a dimethyl sulfoxide reductase enzyme. The synthesis of a series of racemic sulfoxides and the development of appropriate CSPHPLC analytical methods is discussed. Kinetic resolutions of a series of sulfoxides have been achieved. Chapter 3 contains a presentation of results using dioxygenase enzymes as biocatalysts for the asymmetric sulfoxidation of dialkyl sulfoxides including thioacetal sulfoxides. A new range of monosulfoxides, cis-dihydrodiols and cis- dihydrodiol sulfoxides have been isolated in enantiopure form. Chapter 4 is focussed on the application of chiral sulfoxides in synthesis. A new chemoenzymatic route to diol sulfoxide enantiomers and the derived enantiopure phenols and catechols is discussed. The application of chemically synthesised sulfoxide enantiomers in the production of hydroxy sulfoxides is reported. Chapter 5 provides a full experimental section where the synthesis of sulfides and racemic sulfoxides is included. The methods used in the isolation and characterisation of bioproducts from the biotransformation are discussed and full experimental details given.

Ivanov-mistik : Okkul'tnye motivy v poèzii i proze Vjačeslava Ivanova (1907-1919)

The subject of this work is the mysticism of Russian poet, critic and philosopher Vjacheslav Ivanov (1866-1949). The approach adopted involves the textual and discourse analysis and findings of the history of ideas. The subject has been considered important because of Ivanov's visions of his dead wife, writer Lydia Zinovieva-Annibal, which were combined with audible messages ("automatic writings"). Several automatic writings and descriptions of the visions from Ivanov's archive collections in St.Petersburg and Moscow are presented in this work. Right after the beginning of his hallucinations in the autumn of 1907, Ivanov was totally captivated by the theosophical ideas of Anna Mintslova, the background figure for this work. Anna Mintslova, a disciple of Rudolf Steiner's Esoteric School, offered Ivanov the theosophical concept of initiation to interpret paranormal phenomena in his intimate life. The work is divided into three main chapters, an introduction and aconclusion. The first chapter is called The Mystical Person: Anthropology of Ivanov and describes the role of the inner "Higher Self" in Ivanov's views on the nature of human consciousness. The political implications of the concepts, "mystical anarchism" and "sobornost" (religious unity) are also examined. The acquaintance and contacts with Anna Mintslova during 1906-1907 gave a framework to Ivanov's search for an organic society and personal religious experience. The second part, Mystics of Initiation and Visionary Aesthetics describes the influence of the initiation concept on Ivanov's aesthetic views (mainly "realistic symbolism"). On the other hand, some connections between the imagery of his visions and symbols in his verses of that period are established. Since Mintslova represented the ideas of Rudolf Steiner in Russia, several symbols shared by Steiner and Ivanov ("rose", "rose and cross") have been another subject of investigation. The preference for strict verse form in the lyrics of Ivanov's visionary period is interpreted as an attempt to place his own poetic creation within two traditions, a mystical and literary one. The third part of this work, Mystics of Hope and Terror, examines Ivanov's conception of Russia in connection with Mintslova's ideas of occult danger from the East. Ivanov's view of the "Russian idea" and his nationalistic idea during World War I are considered as a representation of the fear of the danger. Ivanov's interpretation of the October revolution is influenced by the theosophical concept of the "keeper of the threshold" which occurs in the context of the discourse of occult danger.

Other Side of This Life : Death, Value, and Social Being in Thomas Pynchon's Fiction

This dissertation analyzes the interrelationship between death, the conditions of (wo)man s social being, and the notion of value as it emerges in the fiction of the American novelist Thomas Pynchon (1937 ). Pynchon s present work includes six novels V. (1963), The Crying of Lot 49 (1966), Gravity s Rainbow (1973), Vineland (1990), Mason & Dixon (1997), Against the Day (2006) and several short stories. Death constitues a central thematic in Pynchon s work, and it emerges through recurrent questions of mortality, suicide, mass destruction, sacrifice, afterlife, entropy, the relationship between the animate and the inanimate, and the limits of representation. In Pynchon, death is never a mere biological given (or event); it is always determined within a certain historical, cultural, and ideological context. Throughout his work, Pynchon questions the strict ontological separation of life and death by showing the relationship between this separation and social power. Conceptual divisions also reflect the relationship between society and its others, and death becomes that through which lines of social demarcation are articulated. Determined as a conceptual and social "other side", death in Pynchon forms a challenge to modern culture, and makes an unexpected return: the dead return to haunt the living, the inanimate and the animate fuse, and technoscientific attempts at overcoming and controlling death result in its re-emergence in mass destruction and ecological damage. The questioning of the ontological line also affects the structuration of Pynchon's prose, where the recurrent narrated and narrative desire to reach the limits of representation is openly associated with death. Textualized, death appears in Pynchon's writing as a sudden rupture within the textual functioning, when the "other side", that is, the bare materiality of the signifier is foregrounded. In this study, Pynchon s cultural criticism and his poetics come together, and I analyze the subversive role of death in his fiction through Jean Baudrillard s genealogy of the modern notion of death from L échange symbolique et la mort (1976). Baudrillard sees an intrinsic bond between the social repression of death in modernity and the emergence of modern political economy, and in his analysis economy and language appear as parallel systems for generating value (exchange value/ sign-value). For Baudrillard, the modern notion of death as negativity in relation to the positivity of life, and the fact that death cannot be given a proper meaning, betray an antagonistic relation between death and the notion of value. As a mode of negativity (that is, non-value), death becomes a moment of rupture in relation to value-based thinking in short, rationalism. Through this rupture emerges a form of thinking Baudrillard labels the symbolic, characterized by ambivalence and the subversion of conceptual opposites.

Beatific Enjoyment in Scholastic Philosophy and Theology: 1240-1335

This dissertation examines the concept of beatific enjoyment (fruitio beatifica) in scholastic theology and philosophy in the thirteenth and early fourteenth century. The aim of the study is to explain what is enjoyment and to show why scholastic thinkers were interested in discussing it. The dissertation consists of five chapters. The first chapter deals with Aurelius Augustine's distinction between enjoyment and use and the place of enjoyment in the framework of Augustine's view of the passions and the human will. The first chapter also focuses upon the importance of Peter Lombard's Sentences for the transmission of Augustine's treatment of enjoyment in scholastic thought as well as upon Lombard's understanding of enjoyment. The second chapter treats thirteenth-century conceptions of the object and psychology of enjoyment. Material for this chapter is provided by the writings - mostly Sentences commentaries - of Alexander of Hales, Albert the Great, Bonaventure, Thomas Aquinas, Peter of Tarentaise, Robert Kilwardby, William de la Mare, Giles of Rome, and Richard of Middleton. The third chapter inspects early fourteenth-century views of the object and psychology of enjoyment. The fourth chapter focuses upon discussions of the enjoyment of the Holy Trinity. The fifth chapter discusses the contingency of beatific enjoyment. The main writers studied in the third, fourth and fifth chapters are John Duns Scotus, Peter Aureoli, Durandus of Saint Pourçain, William of Ockham, Walter Chatton, Robert Holcot, and Adam Wodeham. Historians of medieval intellectual history have emphasized the significance of the concept of beatific enjoyment for understanding the character and aims of scholastic theology and philosophy. The concept of beatific enjoyment was developed by Augustine on the basis of the insight that only God can satisfy our heart's desire. The possibility of satisfying this desire requires a right ordering of the human mind and a detachment of the will from the relative goals of earthly existence. Augustine placed this insight at the very foundation of the notion of Christian learning and education in his treatise On Christian Doctrine. Following Augustine, the twelfth-century scholastic theologian Peter Lombard made the concept of enjoyment the first topic in his plan of systematic theology. The official inclusion of Lombard's Sentences in the curriculum of theological studies in the early universities stimulated vigorous discussions of enjoyment. Enjoyment was understood as a volition and was analyzed in relation to cognition and other psychic features such as rest and pleasure. This study shows that early fourteenth-century authors deepened the analysis of enjoyment by concentrating upon the relationship between enjoyment and mental pleasure, the relationship between cognition and volition, and the relationship between the will and the beatific object (i.e., the Holy Trinity). The study also demonstrates the way in which the idea of enjoyment was affected by changes in the method of theological analysis - the application of Aristotelian logic in a Trinitarian context and the shift from virtue ethics to normative ethics.

Puukaupan säännöt : Yksityismetsänomistajien ja metsäteollisuuden puukauppa Itä-Suomessa 1919 - 1939

The Finnish forest industry bought more than half of the timber used in factories and sawmills in the 1930s from non-industrial private forests (NIPF). This research investigates the rules conformed to this timber trade. The main research questions are: what were the rules that influenced the timber trade; and by whom they were set up? Attention is also paid to the factors which advanced the forest owners’ negotiation possibilities. A variety of sources were used: legal and company statutes, timber trade contracts, archives of the forest companies and organisations. Moreover, the written reminiscences collected by the Finnish Literature Society in the early 1970s were used to analyse the views of individual sellers and buyers. An institutional economics approach was applied as the theoretical framework of this study. In the timber trade the seller (forest owner) and the buyer (the employee of the forest company) agreed to the rules of the timber trade. They agreed about the amount and the price of the timber on sale, but also rules concerning, e.g., timber marking and harvesting. The forest companies had a strong control over the written contracts. Neither the private forest owners nor the forest organisations had much influence over these contracts. However, they managed to influence the rules which could not be found in the contracts. These written and unwritten rules regulated, for instance, the timber marking and measurement. The forest organisations such as Central Forestry Board Tapio (Keskusmetsäseura Tapio) and associations of forest owners (metsänhoitoyhdistykset) helped private forest owners in gaining more control over the timber marking. In timber marking, the forest owner selected trees to be included in the timber trade and gained more information, which he could use in the negotiations. The other rule, which was changed despite forest companies’ resistance, was the timber measurement. The Central Union of Agricultural Producers (MTK) negotiated with the Central Association of Finnish Woodworking Industries (SPKL) about changing the rules of the measurement practices. Even though SPKL did not support any changes, the new timber measurement law was accepted in the year 1938. The new law also created a supervisory authority to solve possible disagreements. Despite this the forest companies were still in charge of the measurement process in most cases. The private forest owners attained changes in the rules of the timber trade mainly during the 1930s. Earlier the relative weakness of the private forest organisations had diminished their negotiation positions. This changed in the 1930s as the private forest owners and their organisations became more active. At the same time the forest industry experienced a shortage of timber, especially pulp wood, and this provided the private forest owners with more leverage. Full-text (in Finnish) available at http://helda.helsinki.fi/handle/10224/4081

Kansan raittiudeksi ja kotien onneksi : Naisten kieltolakimielipiteet ja toiminta kieltolain puolesta ja sitä vastaan 1919 - 1932

It is often maintained that the Prohibition Act (in force from 1 June 1919 to 5 April 1932) still influences both the Finnish alcohol policy and notions about alcohol. This study focuses on the development of women s opinions concerning Prohibition in Finland. What role did the formulation and expression of women s opinions and women's actions play in the final outcome of the Prohibition Act? What do the debate on Prohibition and women s activities for and against the legislation tell us about the status and possibilities of women to exert influence in the Finnish society of the Prohibition era? Women s opinions are particularly interesting since they deviated radically from what has generally been assumed. It was expected that the referendum of 1931 would result in a resounding vote of 100% in favour of Prohibition, but the outcome was a majority vote against it. Over 65% of the women who cast their vote in the referendum wanted a full repeal of Prohibition. The study approaches the history of Prohibition by combining methods and theories of the history of mentalities and social history with gender history. Women are examined as a heterogeneous group with dissimilar objectives and differing ways of acting and thinking. The research material consists of press materials, archival materials from organisations, personal materials and statistics from the Prohibition period. Both discourses and practices are examined; the object of the research is best described by Michel Foucault's concept of dispositif. When participating in the public debate on Prohibition, women based their right to express their opinions and take part in action on an ideological continuum spanning a hundred years, according to which home and family were central areas of women s interest. This idea was linked to questions of morality and social policy. On the other hand, women presented themselves as working taxpayers, voters and equal citizens. The most crucial issue in women's discussions was whether Prohibition improved or worsened the temperance of fathers, husbands and sons. The dichotomies town dweller - countryside dweller, Swedish-speaking Finnish-speaking, and middle class - working class were highly significant backgrounds both as factors dividing women and in public discussions regarding Prohibition. The 1931 referendum showed that the lines of demarcation drawn during the preceding debate did not materialise in political action in line with these dichotomies: the dispositif did not correspond to the discourse. Contrary to what was expressed in public, a great number of women among the labour and rural classes, among inland inhabitants and among Finnish-speakers were also against Prohibition. The media and organisations defended temperance and Prohibition almost until the end of the Prohibition era. This discourse was in conflict with the discourse of everyday conversations and practices in which alcohol was present.