Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Travelling in a Palimpsest : Finnish nineteenth-century painters' encounters with Spanish art and culture

Utgångspunkten för avhandlingen är finländska konstnärsresor till Spanien under 1800-talet, och kontakterna med spansk konst och kultur. Endast ett fåtal finländare reste till Spanien, och inledningsvis utrycktes intresset för spansk konst i form av kopior efter gamla mästare, utförda både efter original utanför Spanien, och reproduktioner. Denna föga imponerande start efterföljdes av ett litet antal målare som verkligen reste till Spanien under 1800-talets senare hälft: Adolf von Becker (1831–1909), Albert Edelfelt (1854–1905) och Venny Soldan (1863–1945). Jag undersöker hur deras syn på landet manifesterades i deras resebilder i förhållande till den växande turistindustrin. Syftet med avhandlingen är att visa hur den resande målaren, likt en turist, föreställde sig, upplevde och tolkade den främmande kulturen, och hur detta avbildades och uttrycktes i deras resebilder. Vid sidan av ikonografisk analys och stilkritik utnyttjas forskningsmetoder från turismteorin. Resultatet av undersökningen visar att de flesta konstnärerna dyrkade konsten på Prado-museet, beundrade flamenco, Andalusiens vackra kvinnor, tjurfäktningar och zigenarna. De längtade efter en förgången och exotisk tid, samtidigt som de följde de vältrampade turiststigarna och hänfördes av de sedvanliga sevärdheterna; de reste i ett delvis mytiskt och delvis verkligt land. Likt turister (i allmänhet), såg de det de ville se, och sökte sig till på förhand inpräntade mentala (före)bilder. Resebilderna kan med fog tolkas som medvetet konstruerade minnen från resan, souvenirs d’Espagne. Samtidigt förstärkte och upprätthöll valen av motiv uppfattningen att Spaniens äldre konst och samtida kultur var mer ”äkta” (autentiska) än den kultur man själv tillhörde. Spanien uppfattades som en kvarleva från en förgången tid som hölls levande i nuet

Den etiske akten : den caritative etikken når pasientens fordringer er av eksistensiell art

The purpose of this thesis is to develop a theory model about some core concepts and phenomena within caritative ethics when patients' demands are existential. There are two research questions, (A) Which realities represent concepts such courage, responsibility, and sacrifice within the caritative ethics. (B) Which phenomena of ethical significance are made current and applicable when patients¿ demands are existential. This study takes as its point of departurecertain chosen theoretical perspectives that discuss some perspectives of the concepts of courage, responsibility, and sacrifice in terms of their significanceto the research questions A. This represents the study¿s theoretical data. The empirical data provide answers to the research question B. In the end, the thesis discusses synthesis of these two accesses of knowledge in order to formulate theses and create a theory model. Løgstrup's contribution and description of the ethical claim helps in understanding and interpreting the links between the substance of the caritative ethic and the concrete reality in the encounter with existential issues. This thesis is a study within the field of Caring Science. The nursing profession provides empirical data and reflects the study topic, by addressing issues of relevance to the application of the knowledge of Caring Sciencein light of the nursing profession's various daily challenges. This study proceeds from the basic assumption: "Caring relationships form the meaningful contextfor caring and derive from the ethos of love, responsibility, and sacrifice, i.e. a caritative ethics" (Eriksson 2001). This study attempts to explore and prove this statement in the light of theoretical and empirical data, in the light ofthe caring scientific perspective which is here linked particularly to the viewof man as a unity of body, mind, and soul, and to the ontological health model. Hermeneutics is the overall perspective for the interpretations proposed in this thesis. Through conversation and hermeneutic observations, I try to understandthe challenges of nursing performance in the encounter with existential issues. This constitutes the empirical data that was gathered on a ward treating cancerpatients. The discussion proceeds sequence by sequence, first by discussing theconditions of the caritative ethics when meeting the existential claims in the light of the concepts of courage, sacrifice, and responsibility. Then a thesis is formulated concerning the caritative ethics in the light of Caring Science. This is the foundation of the creation of the theory model. The resulting theses concern the chosen concepts and phenomena which promote caritative ethics when patients' claims are existential: Freedom is the hallmark of caritative ethics. Freedom is the basic category of caring. When attending to the patient's existential claims, it is of vital importance to secure human relationships as caring interpersonal communions, created by responsible persons who have shown courage and sacrifice. Courage and sacrifice constitute the ethos of caring communities (communions). Courage and sacrifice are then a part of the collective ethos of caring communities, because the patient is confirmed as the unity of body, mind, and soul.

Reise-Beschreibung von Lappland und Bothnien : worinnen nicht nur von der Landes-Art, Winter und Sommer, Nord-Licht oder Nord-Schein, Mineralien, Gewächsen, Thieren, wie auch der Einwohner Beschaffenheit, Religion, Gouvernement, Kauffmannschafft, Wohnungen, Jagden, und andern denckwürdigen Dingen, aus selbsteigenen Augenschein und Erfahrung durch einige Figuren gezeiget; sondern auch die dahin und wieder von dar zurück genommene Reise ordentlich dargeleget wird : von Johann Gerhard Schellern, h.t. Pastore zu Hermstedt und Stober.

Digital reproduction, The National Library of Finland, Centre for Preservation and Digitisation, Mikkeli

Herrn Johann Gerhard Schellers, ehemaligen Pastoris zu Hermstedt und Stobra Reise-Beschreibung nach Lappland und Bothnien : worinnen sowohl die dasige Landes-Art in deutlichen Abtheilungen und nöthigen Figuren aus eigenem Augenschein, gezeiget, als auch die Gelegenheit zur Reise und Rückreise kürtzlich angeführet wird : abermahls dem Druck übergeben von Gottlieb David Friedrich Scheller Rev. Min. Candid.

Digital reproduction, The National Library of Finland, Centre for Preservation and Digitisation, Mikkeli

Contemporary art galleries innovation management

This paper focuses on capabilities implemented by micro firms in actual art sector. After last two decades, since establishment of new art selling ventures has started, current art market of Russia is still in its emerging phase. Art galleries, who preserve to be the main place where the art is purchased, today have to survive in the hostile business environment. Whereas the rivalry does not affect gallery performance significantly, the major challenges for these micro firms are customer unawareness and shortages of financing. The business environment requires capabilities inherited by galleries to sustain the performance. Such capabilities may lead to innovation adoption. This paper represents the first explorative study on contemporary art market of Saint-Petersburg. In order to gain an understanding of the topic, qualitative method was chosen and in-depth interviews were done with 7 different micro firms using key informant method.

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures Biocatalysis opens the door to green and sustainable processes in synthetic chemistry allowing the preparation of single enantiomers, since the enzymes are chiral and accordingly able to catalyze chemical reactions under mild conditions. Immobilization of enzymes enhances process robustness, often stabilizes and activates the enzyme, and enables reuse of the same enzyme preparation in multiple cycles. Although hundreds of variations of immobilization methods exist, there is no universal method to yield the highly active, selective and stable enzyme catalysts. Therefore, new methods need to be developed to obtain suitable catalysts for different substrates and reaction environments. Lipases are the most widely used enzymes in synthetic organic chemistry. The literature part together with the experimental part of this thesis discusses of the effects of immobilization methods mostly used to enhance lipase activity, stability and enantioselectivity. Moreover, the use of lipases in the kinetic resolution of secondary alcohols in organic solvents and in ionic liquids is discussed. The experimental work consists of the studies of immobilization of Burkholderia cepacia lipase (lipase PS) using three different methods: encapsulation in sol-gels, cross-linked enzyme aggregates (CLEAs) and supported ionic liquids enzyme catalysts (SILEs). In addition, adsorption of lipase PS on celite was studied to compare the results obtained with sol-gels, CLEAs and SILEs. The effects of immobilization on enzyme activity, enantioselectivity and hydrolysis side reactions were studied in kinetic resolution of three secondary alcohols in organic solvents, in ionic liquids (ILs), and in their mixtures. Lipase PS sol-gels were shown to be active and stable catalysts in organic solvents and solvent:IL mixtures. CLEAs and SILEs were highly active and enantioselective in organic solvents. Sol-gels and SILEs were reusable in several cycles. Hydrolysis side reaction was suppressed in the presence of sol-gels and CLEAs.

Development of racemization catalysts for dynamic kinetic resolution

Preparation of optically active compounds is of high importance in modern medicinal chemistry. Despite recent advances in the field of asymmetric synthesis, resolution of racemates still remains the most utilized way for preparation of single enantiomers in industrial scale due to its cost-efficiency and simplicity. Enzymatic kinetic resolution (KR) of racemates is a classical method for separation of enantiomers. One of its drawbacks is the limitation of target enantiomer yield to 50%. Dynamic Kinetic Resolution (DKR) allows to reach yields up to 100% by in situ racemization of the less reactive enantiomer. In the first part of this thesis, a number of half-sandwich ruthenium complexes were prepared and evaluated as catalysts for racemization of optically active secondary alcohols. A leading catalyst, Bn5CpRu(CO)2Cl, was identified. The catalyst discovered was extensively characterized by its application for DKR of a broad range of secondary alcohols in a wide range of reaction loadings (1 mmol – 1 mol). Cost-efficient chromatography-free procedure for preparation of this catalyst was developed. Further, detailed kinetic and mechanistic studies of the racemization reactions were performed. Comparison of racemization rates in the presence of Bn5CpRu(CO)2Cl and Ph5CpRu(CO)2Cl catalysts reveals that the performance of the catalytic system can be adjusted by matching of the electronic properties of the catalysts and the substrates. Moreover, dependence of the rate-limiting step from the electronic properties of the reagents was observed. Important conclusions about reaction mechanism were made. Finally, an alternative approach to DKR of amines based on space separated vessels was addressed. This procedure allows the combination of thermolabile enzyme with racemization catalysts active only at high temperatures.

Defining the art of grammar: Ancient perceptions of γραμματική and grammatical

The subject of this dissertation, which belongs to the field of Classical Philology, are the definitions of the art of grammar found in Greek and Latin sources from the Classical era to the second century CE. Definitions survive from grammarians, philosophers, and general scholars. I have examined these definitions from two main points of view: how they are formed, and how they reflect the development of the art itself. Defining formed part of dialectic, in practice also of rhetoric, and was perceived as important from the Classical era onwards. Definitions of grammar seem to have become established as part of preliminary discussions, located at the beginning of grammatical manuals (tékhnai, artes). These discussions included certain principal notions of the art; in addition to the definition, a list of the parts of the art was also typically included. These lists were formed by two different methods: division (diaíresis, divisio) and partition (merismós, partitio). Many of the grammarians may actually have been unfamiliar with these methods, unlike the two most important scholars of the Late Republic, Varro and Cicero. Significant attention was devoted to the question whether the art of grammar is based on lógos or empeiría. This epistemological question had its roots in medical theories, which were prominent in Alexandria. In the history of the concept of grammatiké or grammatica, three stages become evident. In the Classical era, the Greek term is used to refer to a very concrete art of letters (grámmata); from the Hellenistic era onwards it refers to the art developed by the Alexandrian scholars, a matter of textual and literary criticism. Towards the end of the Hellenistic era, the grammarian also becomes involved with the question of correct language, which gradually begins to appear in the definitions as well.

RADAR Roadmap: The application of EPrints for the continued development of RADAR at The Glasgow School of Art

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Toward a-state-of-the-art IR copyright management system: a needs assessment

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Fedora 4 as a Shared Linked Data repository for the Art Institute of Chicago Collections

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Waste Management in Commercial Activity: State-of-the-Art and the Potential Innovation in the Urban Areas of Hanoi, Vietnam

As the rapid development of the society as well as the lifestyle, the generation of commercial waste is getting more complicated to control. The situation of packaging waste and food waste – the main fractions of commercial waste in different countries in Europe and Asia is analyzed in order to evaluate and suggest necessary improvements for the existing waste management system in the city of Hanoi, Vietnam. From all waste generation sources of the city, a total amount of approximately 4000 tons of mixed waste is transported to the composting facility and the disposal site, which emits a huge amount of 1,6Mt of GHG emission to the environment. Recycling activity is taking place spontaneously by the informal pickers, leads to the difficulty in managing the whole system and uncertainty of the overall data. With a relative calculation, resulting in only approximately 0,17Mt CO2 equivalent emission, incinerator is suggested to be the solution of the problem with overloaded landfill and raising energy demand within the inhabitants.