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.

Poptähden muotokuva. Myytit, arkkityypit ja Michael Jacksonin video Smooth Criminal (1988)

Tämä tutkielma käsittelee poptähti Michael Jacksonin tähtikuvaa populaarina myyttinä arkkityyppien näkökulmasta. Tutkimus käsittelee myös tähteyden historiaa ja siirtymää klassisesta Hollywood -tähteydestä postmoderniin tähteyteen. Tutkimus pyrkii selvittämään Jacksonin positiota kulttuurisella tähtikentällä ja sitä, mitä uutta rajatilasankarin, initiaation ja tricksterin arkkityypit voivat kertoa tunnetusta poptähdestä. Tutkimusaineistoksi on valittu Jacksonin Moonwalker –elokuva (1988) ja sen sisällä oleva Smooth Criminal -osio, joka sisältää juonellisen tarinan ja musiikkivideokohtauksen. Smooth Criminal -musiikkikohtaus viittaa kulta-ajan Hollywood -tähden Fred Astairen Band Wagon –musikaalin (1953) Girl Hunt Ballet -musikaalinumeroon. Tutkimuksen kulttuurihistoriallisessa osiossa tuodaan vertailuun Astairen ja Jacksonin erilaiset tähteydet, videoiden narratiivit ja sankaruudet, joita tähdet ilmentävät narratiiveissa. Arkkityyppeihin keskittyvässä osiossa sama Smooth Criminal -narratiivi luetaan uudestaan näiden kolmen arkkityypin kautta, jolloin Jacksonin tähtikuvasta avautuu uusia aspekteja. Tutkimuksen teoreettisen rungon muodostavat sveitsiläisen analyyttisen psykologian perustajan Carl Gustav Jungin teoria arkkityypeistä ja tätä teoriaa soveltava postjungilainen tutkimus. Tutkimuksen kulttuurihistoriallinen puoli pohjaa perinteiseen tähtitutkimukseen ja erityisesti Richard Dyerin sekä Edgar Morinin teoksiin. Käytän postjungilaista elokuva- ja tähtitutkimusta tutkimuksessani, joista tärkeimpiä ovat John Izodin ja Luke Hockleyn teokset. Tutkimuksen perusteella voidaan todeta, että tähteys on kulttuurisidonnaista ja ilmentää omaa aikaansa. Astairen tähteys ja narratiivin sankaruus koostuu muutamista pelkistetyistä aspekteista. Jackson on tähtenä eräänlainen hybridisankari, jossa yhdistyvät monet vastakkaiset merkitykset. Rajatilasankarin, initiaation ja tricksterin arkkityypit ovat kaikki löydettävissä tutkinnan kohteena olevasta narratiivista. Arkkityyppien kautta voi nähdä, että Jacksonin ilmensi tähteydessään myös näitä kaikille ihmisille yhteisiä psyykkisiä sisältöjä, mikä voi osaltaan selittää hänen globaalia suosiotaan.

Median rituaalit ja moderni pyhyys : kuoliko Michael Jackson pyhän uhrikuoleman?

Kirjallisuusarvostelu

Measuring the performance of corporate events : an empirical study of measuring practices in Finnish companies

Corporate events as an effective part of marketing communications strategy seem to be underestimated in Finnish companies. In the rest of the Europe and the USA, investments in events are increasing, and their share of the marketing budget is significant. The growth of the industry may be explained by the numerous advantages and opportunities that events provide for attendees, such as face-to-face marketing, enhancing corporate image, building relationships, increasing sales, and gathering information. In order to maximize these benefits and return on investment, specific measurement strategies are required, yet there seems to exist a lack of understanding of how event performance should be perceived or evaluated. To address this research gap, this research attempts to describe the perceptions of and strategies for evaluating corporate event performance in the Finnish events industry. First, corporate events are discussed in terms of definitions and characteristics, typologies, and their role in marketing communications. Second, different theories on evaluating corporate event performance are presented and analyzed. Third, a conceptual model is presented based on the literature review, which serves as a basis for the empirical research conducted as an online questionnaire. The empirical findings are to a great extent in line with the existing literature, suggesting that there remains a lack of understanding corporate event performance evaluation, and challenges arise in determining appropriate measurement procedures for it. Setting clear objectives for events is a significant aspect of the evaluation process, since the outcomes of events are usually evaluated against the preset objectives. The respondent companies utilize many of the individual techniques that were recognized in theory, such as calculating the number of sales leads and delegates. However, some of the measurement tools may require further investments and resources, thus restricting their application especially in smaller companies. In addition, there seems to be a lack of knowledge of the most appropriate methods in different contexts, which take into account the characteristics of the organizing party as well as the size and nature of the event. The lack of inhouse expertise enhances the need for third-party service-providers in solving problems of corporate event measurement.

Cysteine addition on short-term cooled boar semen preservation and its relationship with swine field fertility

Artificial insemination is routinely used in the swine industry to reduce the costs of production through to increase the efficiency of the refrigerated boar semen process. The objective of this study was to evaluate the effect of different levels of cysteine (CYS) added to the Beltsville Thawing Solution (BTS) extender semen during cooling for up to 72 hours. Ejaculated from three boars were collected with the gloved-hand technique and semen aliquots were diluted in BTS as follow: BTS only (BTS), BTS + 0.1mM cysteine (CYS0.1), BTS + 0.5mM cysteine (CYS0.5), BTS + 1.0mM cysteine (CYS1.0), BTS + 2.5mM cysteine (CYS2.5), BTS + 5.0mM cysteine (CYS5.0), BTS + 10.0mM cysteine (CYS10.0), and BTS + 20.0mM cysteine (CYS20.0). Evaluation of sperm integrity were analyzed using 0.5mg/ml propidium iodide (plasma membrane), 100µg/ml isothiocynate-conjugated Pisum sativun agglutinin (acrosomal membrane) and 153µM 5,5',6,6'-tetrachloro-1,1',3,3'-tetraethylbenzimidazolyl carbocyanine iodide (mitochondria potential) after semen dilution at specific times (0, 24, 48 and 72 hours). Additionally, we also evaluated the effects of 5.0 mM CYS addition in the BTS extender on the maintenance of sperm quality and their influence on fertility in the swine production. After artificial insemination, animals were evaluated based on the estrous return and the number of piglet's born. Cysteine at concentrations of 10.0 and 20.0mM resulted in more pronounced reductions even at the time zero. Semen viability decreased to levels below 10% at these high levels of CYS in the first 24 hour of storage at 17ºC. At the end of the storage time, less than 65% of sperm cells had intact plasma membrane in all groups. The sperm viability decreased significantly when the semen was added at high concentrations of CYS (time "0"; CYS10.0 and CYS20.0; p<0.05), when compared to the other CYS concentrations. The BTS (10.20±0.39) treated group showed a lower rate of estrus return when compared to other (BTSCYS; 86.05±039), and it showed also the highest total number of piglets borne per treatment (12.71±3.38 vs. 9.00±3.38, respectively). In conclusion, the addition of CYS in the BTS semen extender did not maintain spermatic viability of boar cooled spermatozoa and it results in a higher percentage of return to estrus and lower number of piglets borne.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Choræus, Michael

f. 15.3.1774 i Vörå d. 3.6.1806 i Stockholm, Sverige Michael Choræus har gått till historien som sen upplysningstida finländsk diktare. Han publicerade sina litterära verk kring år 1800, vid sidan om sin akademiska och teologiska bana. I fråga om stil och tematik var han influerad av den samtida och likaså svenskspråkiga diktarkollegan Frans Michael Franzén. I sin samtid väckte Choræus uppseende med sin kvickhet och sitt intellekt, samt har setts som den mest begåvade finländska lyrikern i sin tid. I hans produktion ingår flytande verskonst som inte sällan tonsatts, däribland också psalmbearbetningar, samt även t.ex. tillfällesdikt och satir. Som exempel på hans dikter kan nämnas En tanke på min egen graf, Ehrensvärd. Skaldesång och Lilla Calle (utgivna i t.ex. tidningar under diktarens livstid och senare i Choræus samlade skaldestycken 1815). Biografiskt lexikon för Finland: http://www.blf.fi/artikel.php?id=2355

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

Evaluation of the addition of ascorbic acid to the ration of cultivated Piaractus mesopotamicus (Characidae) on the infrapopulation of Anacanthorus penilabiatus (Monogenea)

Sixty Piaractus mesopotamicus Holmberg, 1887 (pacu) fry fed a diet containing 0, 50, 100 and 200 mg ascorbic acid/kg dry feed were studied to evaluate the effect on parasitic infestation by the monogenean Anacanthorus penilabiatus Boeger, Husak and Martins, 1995 (Monogenea: Dactylogyridae) for a period of 24 weeks. The temperature of the aquaria was measured daily and remained between 28 and 31oC. At the beginning of the experiment, fish showed 6.15 ± 0.33 cm standard length and 8.64 ± 1.62 g average body weight. A sample of fish was examined and showed 43 ± 17 monogeneans per fish. At the end of the experiment, the gills of control and vitamin C-treated fish were collected for parasite counts. Control fish had 42.5 parasites per fish, a significantly higher number (P<0.05) when compared with fish fed vitamin C, that showed 16.5 parasites per fish. Ascorbic acid fortification in the food promoted an increase in fish resistance to parasites. It is suggested that an optimum level of 139 mg/kg vitamin C supplementation either elicited better nutritional conditions by stimulating the appetite of the fish or improved the immune response.