α-Pinene oxide and verbenol oxide isomerizations over heterogeneous catalysts

Terpenes are a valuable natural resource for the production of fine chemicals. Turpentine, obtained from biomass and also as a side product of softwood industry, is rich in monoterpenes such as α-pinene and β-pinene, which are widely used as raw materials in the synthesis of flavors, fragrances and pharmaceutical compounds. The rearrangement of their epoxides has been thoroughly studied in recent years, as a method to obtain compounds which are further used in the fine chemical industry. The industrially most desired products of α-pinene oxide isomerization are campholenic aldehyde and trans-carveol. Campholenic aldehyde is an intermediate for the manufacture of sandalwood-like fragrances such as santalol. Trans-carveol is an expensive constituent of the Valencia orange essence oil used in perfume bases and food flavor composition. Furthermore it has been found to exhibit chemoprevention of mammary carcinogenesis. A wide range of iron and ceria supported catalysts were prepared, characterized and tested for α-pinene oxide isomerization in order to selective synthesis of above mentioned products. The highest catalytic activity in the preparation of campholenic aldehyde over iron modified catalysts using toluene as a solvent at 70 °C (total conversion of α-pinene oxide with a selectivity of 66 % to the desired aldehyde) was achieved in the presence of Fe-MCM-41. Furthermore, Fe-MCM-41 catalyst was successfully regenerated without deterioration of catalytic activity and selectivity. The most active catalysts in the synthesis of trans-carveol from α-pinene oxide over iron and ceria modified catalysts in N,N-dimethylacetamide as a solvent at 140 °C (total conversion of α-pinene oxide with selectivity 43 % to trans-carveol) were Fe-Beta-300 and Ce-Si-MCM-41. These catalysts were further tested for an analogous reaction, namely verbenol oxide isomerization. Verbenone is another natural organic compound which can be found in a variety of plants or synthesized by allylic oxidation of α-pinene. An interesting product which is synthesized from verbenone is (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol. It has been discovered that this diol possesses potent anti-Parkinson activity. The most effective way leading to desired diol starts from verbenone and includes three stages: epoxidation of verbenone to verbenone oxide, reduction of verbenone oxide and subsequent isomerization of obtained verbenol oxide, which is analogous to isomerization of α-pinene oxide. In the research focused on the last step of these synthesis, high selectivity (82 %) to desired diol was achieved in the isomerization of verbenol oxide at a conversion level of 96 % in N,N-dimethylacetamide at 140 °C using iron modified zeolite, Fe-Beta-300. This reaction displayed surprisingly high selectivity, which has not been achieved yet. The possibility of the reuse of heterogeneous catalysts without activity loss was demonstrated.

Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.

Fiber-reinforced composite fixed dental prostheses: Studies of the materials used as pontics

Fiber-reinforced composite fixed dental prostheses – Studies of the materials used as pontics University of Turku, Faculty of Medicine, Institute of Dentistry, Department of Biomaterials Science, Finnish Doctoral Program in Oral Sciences – FINDOS, Annales Universitatis Turkuensis, Turku, Finland 2015 Fiber-reinforced composites (FRC), a non-metallic biomaterial, represent a suitable alternative in prosthetic dentistry when used as a component of fixed dental prostheses (FDPs). Some drawbacks have been identified in the clinical performance of FRC restorations, such as delamination of the veneering material and fracture of the pontic. Therefore, the current series of studies were performed to investigate the possibilities of enhancing the mechanical and physical properties of FRC FDPs by improving the materials used as pontics, to then heighten their longevity. Four experiments showed the importance of the pontic design and surface treatment in the performance of FRC FDPs. In the first, the load-bearing capacities of inlay-retained FRC FDPs with pontics of various materials and thicknesses were evaluated. Three different pontic materials were assessed with different FRC framework vertical positioning. Thicker pontics showed increased load-bearing capacities, especially ceramic pontics. A second study was completed investigating the influence of the chemical conditioning of the ridge-lap surface of acrylic resin denture teeth on their bonding to a composite resin. Increased shear bond strength demonstrated the positive influence of the pretreatment of the acrylic surfaces, indicating dissolution of the denture surfaces, and suggesting potential penetration of the monomer systems into the surface of denture teeth. A third study analyzed the penetration depth of different monomer systems on the acrylic resin denture teeth surfaces. The possibility of establishing a durable bond between acrylic pontics and FRC frameworks was demonstrated by the ability of monomers to penetrate the surface of acrylic resin denture teeth, measured by a confocal scanning type microscope. A fourth study was designed to evaluate the load-bearing capacities of FRC FDPs using the findings of the previous three studies. In this case, the performance of pre-shaped acrylic resin denture teeth used as pontics with different composite resins as filling materials was evaluated. The filling material influenced the load-bearing capacities, providing more durable FRC FDPs. It can be concluded that the mechanical and physical properties of FRC FDPs can be improved as has been shown in the development of this thesis. The improvements reported then might provide long lasting prosthetic solutions of this kind, positioning them as potentially permanent rehabilitation treatments. Key words: fiber-reinforced composite, fixed dental prostheses, inlay-retained bridges, adhesion, acrylic resin denture teeth, dental material.

This Is a Gorgeous-looking Movie”: Multimodal Interplay between Commentary and Subject Materials in Movie Review Entertainment

The present thesis is a study of movie review entertainment (MRE) which is a contemporary Internet-based genre of texts. MRE are movie reviews in video form which are published online, usually as episodes of an MRE web show. Characteristic to MRE is combining humor and honest opinions in varying degrees as well as the use of subject materials, i.e. clips of the movies, as a part of the review. The study approached MRE from a linguistic perspective aiming to discover 1) whether MRE is primarily text- or image-based and what the primary functions of the modes are, 2) how a reviewer linguistically combines subject footage to her/his commentary?, 3) whether there is any internal variation in MRE regarding the aforementioned questions, and 4) how suitable the selected models and theories are in the analysis of this type of contemporary multimodal data. To answer the aforementioned questions, the multimodal system of image—text relations by Martinec and Salway (2005) in combination with categories of cohesion by Halliday and Hasan (1976) were applied to four full MRE videos which were transcribed in their entirety for the study. The primary data represent varying types of MRE: a current movie review, an analytic essay, a riff review, and a humorous essay. The results demonstrated that image vs. text prioritization can vary between reviews and also within a review. The current movie review and the two essays were primarily commentary-focused whereas the riff review was significantly more dependent on the use of imagery as the clips are a major source of humor which is a prominent value in that type of a review. In addition to humor, clips are used to exemplify the commentary. A reviewer also relates new information to the imagery as well as uses two modes to present the information in a review. Linguistically, the most frequent case was that the reviewer names participants and processes lexically in the commentary. Grammatical relations (reference items such as pronouns and adverbs and conjunctive items in the riff review) were also encountered. There was internal variation to a considerable degree. The methods chosen were deemed appropriate to answer the research questions. Further study could go beyond linguistics to include, for instance, genre and media studies.

Production of fungal volatile organic compounds in bedding materials

Selostus: Haihtuvien orgaanisten yhdisteiden muodostuminen kuivikkeissa

Reactivity of silicate liming materials from Northern Europe assessed by Soil Incubation and two pH Stat methods

Selostus: Pohjois-Euroopan silikaattisten kalkitusaineiden reaktiivisuus astiakoemenetelmällä ja kahdella pH-staattisella menetelmällä arvioituna

Pakkausrakenteenmateriaalinvalinta ja rakennesuunnittelu

Epäherkkien räjähteiden teknologian käyttö mahdollistaa räjähdeturvallisuuden ja sa-malla sotilaallisen suorituskyvyn parantumisen. Suomen Puolustusvoimat päätti IM-teknologian käyttöönotosta vuonna 2004, mikä on edellyttänyt räjähdevalmistajilta tuotteidensa kehitystoimenpiteitä. Yksi osa-alue erään räjähdevalmistajan ajopanostuotteen kehitystyöstä on Exel Oyj:n valmistama panospakkaus, joka pyritään kehittämään uudistuneiden vaatimusten mukaiseksi. Tässä diplomityössä selvitettiin IM-tuotteen vaatimukset ja laadittiin panospakkauksen vaatimusprofiili, jonka perusteella tehtiinkirjallisen selvitys ballistisista materiaaleista. Panospakkauksen rakenneratkaisut perustuivat materiaalinvalintaan, joka toteutettiin ominaisarvovertailulla.Rakenneratkaisuja testattiin sekä ballistisesti että mekaanisilla testausmenetelmillä. Lisäksi testausmenetelmien välille tehtiin korrelaatiovertailuja, joidentulokset ovat lupaavia. Projektin lopputuloksena saatiin kehitettyä Exel Oyj:lle panospakkausratkaisu, jolla voidaan edistää suojattavan tuotteen IM-vaatimusten täyttymistä. Rakenteelle toteutetun lujuusanalyysin perusteella pakkausrakennetta voidaan pitää käyttökohteeseen soveltuvana.

Sidosryhmien odotukset voittoa tavoittelemattomalle kehitysyhtiölle. Case: Lappeenranta Innovation Oy

Tässä tutkimuksessa tarkastellaan, mitä sidosryhmät odottivat voittoa tavoittelemattomalta case-yritykseltä Lappeenranta Innovation Oy:ltä sen perustamisen yhteydessä ja reilun vuoden toiminnan jälkeen. Tutkimuksessa selvitetään myös niitä kehittämisehdotuksia, joita sidosryhmillä on yritykselle. Tutkimus on laadullinen tapaustutkimus jasen aineisto koostuu dokumenteista, mediateksteistä ja haastatteluista. Menetelminä on käytetty teemoittelua ja diskurssianalyysiä. Tutkimuksen tuloksena löytyi kuusi alkuvaiheen odotuskokonaisuutta: 1) yrittäjien auttaminen; 2) tutkimuksen ja liiketoiminnan yhdistäminen; 3) rahoituksen hakeminen; 4) public-private -yhteistyön kehittäminen; 5) Venäjä-yhteistyön kehittäminen ja6) verkostojen luominen. Reilun vuoden toiminnan jälkeen odotukset ovat muuttuneet jonkin verran: public-private-yhteistyön odotuksen merkitys on kasvanut ja uutena odotuksena on tullut IP-oikeuksien suojaaminen. Kehittämisehdotuksia tutkimuksessa löytyi 10 eri toiminta-alueelta: yritys-kehitys; rahoitus; Venäjä-yhteistyö; verkostot; maakunnallisuus; toiminnan laajuus; yhteistyö sidosryhmien kanssa; tiedottaminen, asioista kertominen, selkeys; fokusointi ja priorisointi; sisäisen toiminnan kehittäminen ja hallituksen rakenne.

Theoretical Analysis and Simulations of Vertically Vibrated Granular Materials

The dynamical properties ofshaken granular materials are important in many industrial applications where the shaking is used to mix, segregate and transport them. In this work asystematic, large scale simulation study has been performed to investigate the rheology of dense granular media, in the presence of gas, in a three dimensional vertical cylinder filled with glass balls. The base wall of the cylinder is subjected to sinusoidal oscillation in the vertical direction. The viscoelastic behavior of glass balls during a collision, have been studied experimentally using a modified Newton's Cradle device. By analyzing the results of the measurements, using numerical model based on finite element method, the viscous damping coefficient was determinedfor the glass balls. To obtain detailed information about the interparticle interactions in a shaker, a simplified model for collision between particles of a granular material was proposed. In order to simulate the flow of surrounding gas, a formulation of the equations for fluid flow in a porous medium including particle forces was proposed. These equations are solved with Large Eddy Simulation (LES) technique using a subgrid-model originally proposed for compressible turbulent flows. For a pentagonal prism-shaped container under vertical vibrations, the results show that oscillon type structures were formed. Oscillons are highly localized particle-like excitations of the granular layer. This self-sustaining state was named by analogy with its closest large-scale analogy, the soliton, which was first documented by J.S. Russell in 1834. The results which has been reportedbyBordbar and Zamankhan(2005b)also show that slightly revised fluctuation-dissipation theorem might apply to shaken sand, which appears to be asystem far from equilibrium and could exhibit strong spatial and temporal variations in quantities such as density and local particle velocity. In this light, hydrodynamic type continuum equations were presented for describing the deformation and flow of dense gas-particle mixtures. The constitutive equation used for the stress tensor provides an effective viscosity with a liquid-like character at low shear rates and a gaseous-like behavior at high shear rates. The numerical solutions were obtained for the aforementioned hydrodynamic equations for predicting the flow dynamics ofdense mixture of gas and particles in vertical cylindrical containers. For a heptagonal prism shaped container under vertical vibrations, the model results were found to predict bubbling behavior analogous to those observed experimentally. This bubbling behavior may be explained by the unusual gas pressure distribution found in the bed. In addition, oscillon type structures were found to be formed using a vertically vibrated, pentagonal prism shaped container in agreement with computer simulation results. These observations suggest that the pressure distribution plays a key rolein deformation and flow of dense mixtures of gas and particles under vertical vibrations. The present models provide greater insight toward the explanation of poorly understood hydrodynamic phenomena in the field of granular flows and dense gas-particle mixtures. The models can be generalized to investigate the granular material-container wall interactions which would be an issue of high interests in the industrial applications. By following this approach ideal processing conditions and powder transport can be created in industrial systems.