During attempted enzyme-catalysed resolution of sterically hindered secondary alcohols, hemiacetals and their esters were unexpectedly detected. Hemiacetal esters are reactive compounds that decompose to alcohol, aldehyde and acid under ordinary work-up conditions i.e. in contact with water, acid, or silica gel. Thus, the presence of these side products might decrease the enantiomeric excess of the residual alcohol after workup of a lipase-catalysed resolution. The formation of these hemiacetal esters were further studied using both terpenoid and non-terpenoid substrate alcohols, various acyl donors, and lipases. The prerequisite for their formation is the presence of a sterically hindered substrate alcohol, an aldehyde or an aldehyde releasing acyl donor, and a lipase (PCL-L6, PCL-PS and CAL-B). Enantioselective synthesis of (S)- and (R)-cryptone was performed via a ring closing metathesis (RCM) of (S)- and (R)-6-isopropyl-1,7-octadien-3-one. The stereochemistry was induced by using pseudoephedrine as chiral auxiliary in an alkylation reaction which provided a chiral octadienone. Problems with removal of the RCM-catalyst resulted in low yields and low enantiomeric purity. In an alternative approach, racemic cryptone was subjected to conjugate addition with thiophenol followed by reduction to the corresponding alcohol. Lipase-catalysed resolution of this alcohol yielded, after oxidation and elimination, (R)- and (S)- cryptone with 76% and 98% ee, respectively. Marine fouling of immersed objects is a serious problem. Many coatings contain effective antifouling compounds having the drawback of being toxic to the marine environment. The marine natural product 10-isocyano-4-cadinene is a potentially non-toxic antifouling agent against the barnacle Balanus amphitrite and therefore an interesting target for organic synthesis. Cryptone was used as a starting material in attempted syntheses of this compound and other similar model compounds. / QC 20100901

I den här avhandlingen har vi studerat hur man kan göra nya tensider. En tensid är en speciell molekyl som har förmågan att lösa sig i både vatten och olja. Man kan göra följande experiment hemma: Fyll en glasburk till hälften med vatten och tillsätt en droppe matolja. Oljan bildar en droppe ovanpå vattnet, därför att vatten och olja inte är blandbara. Vatten är polärt och olja är opolärt. Om man rör om med en sked kommer oljedroppen förvisso att dela upp sig i mindre droppar, men så snart man slutar att röra kommer dessa att lägga sig på vattenytan igen. Sätt nu en droppe diskmedel till blandningen och rör om. Nu sprider sig oljedropparna mycket bättre i vattnet, och de lägger sig heller inte på vattenytan lika fort när man slutar att röra. Det här beror på att diskmedel innehåller en tensid, som har en polär och en opolär del. Den polära delen passar ihop med det polära vattnet, medan den opolära delen passar ihop med den opolära oljan. På så vis kan tensiden hjälpa till att lösa upp opolära ämnen i polära vätskor. Den aktiva delen av ett läkemedel består ofta av opolära ämnen, vilka inte löser sig i polära vätskor såsom vatten. Eftersom kroppen består till stor del av vatten måste man ändå försöka få läkemedlet vattenlösligt, för att möjliggöra transport via blodet till problemområdet. Det kan man uppnå genom att tillsätta tensider. Om läkemedel-tensidblandningen ska ges till djur eller människor får inte tensiden orsaka någon skada i kroppen. Vi har försökt framställa tensider som ska kunna användas för att just lösa läkemedel i vatten. För att kunna framställa nya tensider måste man ha kunskap i organisk syntes. Det betyder att man måste veta hur man från små intermediat (”byggstenar”) successivt kan bygga upp nya molekyler som har de önskvärda egenskaperna. Genom olika typer av organisk syntes har vi byggt upp tre nya tensidtyper, vars egenskaper vi studerat med olika mätningar. Ingen av dessa tensider lämpade sig som tillsats till läkemedel, men vårt arbete har givit mycket ny kunskap om hur framtida tensidmolkyler kan tillverkas och vilka egenskaper de får. / This thesis deals with the synthesis and characterization of new polyhydroxy surfactants. The first part describes the synthesis of three new surfactant classes, and the second part concerns the surface chemical characterization of the synthesized surfactants. A stereodivergent route for preparation of hydrophilic head groups was developed, that featured consecutive stereoselective dihydroxylations of a diene. This method provided in total four different polyhydroxylated head groups. These surfactant head groups were natural and unnatural sugar analogues, and were used for the coupling with two different hydrophobic tail groups. Another approach took advantage of a metathesis reaction and provided a polyhydroxylated compound that was coupled to 12-hydroxy stearic acid The third class of surfactants contained an amide linkage between the hydrophilic and the hydrophobic parts. The hydrophilic part consisted of two glucose units, and 12-hydroxy stearic acid was used as the hydrophobic part. The hydroxy moiety in the tail group was further functionalized as aliphatic esters, which provided in total four different surfactants. A selection of the surfactants was used to investigate the chiral discrimination in Langmuir monolayers at an air-water interface. The isotherms showed a remarkable difference in compressibility between diastereomeric surfactants and also a pronounced chiral discrimination between racemic and enantiomerically pure surfactants, favoring heterochiral discrimination. The monolayers were also investigated with Brewster angle microscopy (BAM) and grazing incidence X-ray diffraction (GIXD). It was not possible to observe any chirality dependent features from the BAM images, but the GIXD measurement supported the conclusion that heterochiral discrimination governed the intermolecular forces within the racemic monolayer. The third class of surfactants, containing an amide linkage between the glucose units and 12-hydroxy stearic acid was evaluated with respect to the CMC and the haemolytic activity. These surfactants were all haemolytic close to their respective CMC. / QC 20101015

Immobilization of different bio- and organic molecules on solid supports is fundamental within many areas of science. Sometimes, it is desirable to obtain a directed orientation of the molecule in the immobilized state. In this thesis, the copper (I) catalyzed Huisgen 1,3-dipolar cycloaddition, referred to as a “click chemistry” reaction, was explored as a means to perform directed immobilization of small molecule ligands on gold surfaces. The aim was to synthesize alkyne- and azide-terminated alkanethiols that would form well-organized self assembled monolayers (SAMs) on gold from the commercially available substances orthoethylene glycol and bromo alkanoic acid. N-(23-azido-3,6,9,12,15,18,21-heptaoxatricosyl)-n-mercaptododekanamide/hexadecaneamide (n = 12, 16) were successfully synthesized and allowed to form SAMs of different compositions to study how the differences in density of the functional groups on the surface would influence the structure of the monolayer and the click chemistry reaction. The surfaces were characterized by different optical methods: ellipsometry, contact angle goniometry and infrared reflection-absorption spectroscopy (IRAS). The click reaction was found to proceed at very high yields on all investigated surfaces. Finally, the biomolecular interaction between a ligand immobilized by click chemistry on the gold surfaces and a model protein (bovine carbonic anhydrase) was demonstrated by surface plasmon resonance using a Biacore system.

För att överleva i dagens näringslivsklimat krävs en väl anpassad strategi för att hantera alla svårigheter och möjligheter som ett företag ställs inför. Denna uppsats syftar till att undersöka den svenska energikoncernen Vattenfalls tillväxtstrategi. Konkret undersöks på vilka sätt företaget avser växa organiskt och genom förvärv, vilka marknader som skall exploateras och vilken typ av produktutveckling som sker. Vidare undersöks svenska statens ägarroll i Vattenfall. För att besvara uppsatsens syfte har vi använt såväl primär- som sekundärdata i form av intervjuer med representanter för både Vattenfall och Svenska staten samt dokumentation i form av rapporter, analyser och direktiv. Denna data har sedan tolkats med hjälp av tillväxtteori avseende både organisk och förvärvsinriktad tillväxt samt agentteori. Från vår data har vi kunnat dra slutsatser kring Vattenfalls strategi där företaget i nuläget står inför en större förändring från att vara inriktade på förvärvsbaserad tillväxt till en kombination där både förvärv och organisk tillväxt ingår. Denna strategi syftar till att fördubbla företagets energiproduktion fram till år 2030 och göra företaget klimatneutralt till år 2050. I ett längre perspektiv vill företaget utmärka sig som en av Europas ledande energiföretag.

The aim of this study is to examine the market reaction when information about a company’s foreign direct investment is announced and how that affects the shareholder’s value. Also of interest is whether the market reacts differently depending on which country the investment is established in and which mode of entry is used. This will be achieved by using an event study approach. The selection that was used consisted of 206 companies registered on the Nasdaq OMX Nordic homepage, which had during a time period stretching from 1999 to 2009 established a foreign direct investment in the regions BRIC, Europe or the USA using the mode of organic growth, joint venture or acquisition. The units were submitted to a hypothesis test, this was done to determine if an abnormal return was attained during the event window. The event window consisted of eleven days, five days before the announcement and five days after, which includes the announcement day. The tests were performed on the units as a whole and divided into categories depending on mode of entry, region and country. The event study was accompanied by a questionnaire. The result of the study show no statistically significant abnormal return related to the announcement of a foreign direct investment. There were however some indications of a deviation when the units were divided into region, most noticeably between the regions BRIC, which showed a steady negative development, and Europe, which showed a steady positive development. These results were however not significant.

This thesis consists of seven research publications concerning (i) pKa studies of nucleobases in model nucleotides to understand why RNA duplexes are more stable than DNA duplexes (Paper I), (ii) the role of Me(T)-π interactions in the relative stability of DNA-RNA heteroduplexes (Paper II), (iii) pKa measurements in nucleotides with different 2′-substituents (paper III), (iv) a conformation study of constrained sugars and a pKa study of 1-thyminyl to reveal effect of sugar constraints on the pKa of the nucleobase (paper IV), (v) NMR and MD studies of 1′, 2′-oxetane constrained thymidine incorporated Dickerson Drew dodecamer (paper V), (vi) the sequence dependent pKa perturbation of 9-guaninyl moeity in single stranded (ss) DNA and RNA (paper VI), (vii) the non identical chemical nature of internucleotidic phosphates in (ss) RNA using 31P NMR (paper VI), and an alkaline hydrolysis study of phosphodiesters in ssRNAs (paper VII). The architecture of DNA and RNA molecules is determined by (a) hydrogen bonding (b) base stacking (c) a variety of additional non-covalent interactions. In paper (I) we showed that A-U and G-C base pairings in RNA are more stable than A-T and G-C base pairings in DNA by 4.3 and 1 kJ mol-1 respectively. Me(T)-π interaction plays a dominant role in the relative stability of DNA-RNA duplexes (paper II). In paper III and IV, we have shown that 1′ , 2′- oxetane and azetidine rings have strong inductive effect on pyrimidine bases, and that the H2′-sugar proton can be the marker to understand the pseudoaromaticity of pyrimidine bases, as well as increasing constraints in sugar reducing the basicity of nucleobases. A 1′, 2′-oxetane locked thymidine (T) moiety deforms the local structure of Dickerson-Drew dodecamer, d(CGCGAATTCGCG)2- investigated by High resolution NMR and MD study, as is discussed in the paper V. In papers VI and VII, we showed sequence context dependent pKa (N1) of 9-guaninyl perturbation in (ss) DNAs and RNAs and the non identical chemical nature of inter-nucleotidic phosphate groups in single stranded RNAs.

Den här högskoleavhandlingen beskriver framtagningen av en modell för en kombinerad styr- och mätutrustning. Syftet med utrustningen är att använda denna för att underlätta vidare utveckling av organisk elektronik vilket är ett av Acreo AB:s forskningsområden. Istället för att till varje ny komponent eller system utveckla ett nytt testsystem kan denna modell användas på ett generellt sätt, vilket sparar värdefull utvecklingstid. I avhandlingen presenteras först de krav som utrustningen ska uppfylla följt av några förslag på lösningar. Därefter väljs ett av förslagen och en grundläggande implementering genomförs med hänsyn mot kraven. Slutligen innehåller rapporten förslag på hur vidare arbete med modellen kan ske. / This bachelor thesis describes the developing of a model for combined steering and measuring equipment. The purpose is to ease further developing of organic electronics, which is one of Acreo AB’s research areas. A test system is needed for every new component or system developed. Instead of constructing a new test environment for every case this equipment will be a general solution that will save valuable developing time. This thesis will first present the requirements followed by some proposal solutions. Thereafter one proposal will be chosen and an essential implementation will be done with consideration of the requirements. Finally the thesis contains suggestions on how to further develop the model.

There is a strong driving force to increase the competitiveness of the pulping industry by finding new business opportunities. In this context full utilisation of the wood raw material used in conventional pulping mills is of vital importance. One focus area is to increase the utilisation areas of lignin. LignoBoost is a new method to obtain kraft lignin of high purity. The aim of the project was to investigate and increase the ability of LignoBoost kraft lignins to bind metals in aqueous solutions. The metal binding property of kraft lignins was evaluated using copper (II) ions. The metal binding capacities were 1.76 mg Cu2+/g LignoBoost softwood kraft lignin, 0.96 mg Cu2+/g LignoBoost hardwood kraft lignin and 1.12 mg Cu2+/g condensed softwood kraft lignin. The metal binding capacities of the softwood and hardwood kraft lignins from LignoBoost were lower than expected, when compared to the metal binding capacities of other lignins found in literature. The highest copper binding capacity of a kraft lignin found in literature was almost 50 times greater than that of the LignoBoost softwood kraft lignin.   The Mannich reaction was used to increase the nitrogen content in softwood lignin, and thereby increase its electron-donating capacity. An increase in electron-donating capacity should promote its metal binding capacity.   The Mannich reaction occurs in the vacant ortho position of the phenolic groups of lignin, introducing an aminomethyl group at that position. The only vacant ortho position in the phenol unit for reaction is in the guaicyl unit. Softwood lignin underwent a Mannich reaction, since softwood contains a greater number of guaiacyl units than hardwoods.   A screening of the products from this Mannich reaction on LignoBoost softwood kraft lignin was performed to optimise the reaction conditions. The reaction time, temperature, amount of formaldehyde and dimethylamine were varied. The Mannich products were evaluated by elemental analysis. The conditions giving the highest nitrogen content in the product were used further in a Mannich reaction of condensed softwood kraft lignin. The condensed softwood kraft lignin (7 g) was treated with dimethylamine (0.35 mol) and formaldehyde (0.35 mol) at 80°C for 24 hours.   The metal binding experiment could not be carried out with Mannich-modified condensed softwood kraft lignin since the lignin dissolved in the copper solution.   When introducing nitrogen functionalities into lignin the electron-donating capacity should increase. An increase in donor groups should promote the metal binding capacity of the lignin. A problem that occurred when introducing aminomethyl groups was an increase in solubility of the lignin. Water solubility of the lignin derivative is undesirable in the envisaged utilization area, metal binding in, for example mine deposits, from where contaminated water may be a concentrated source of heavy metals.

<p>The Lattrell-Dax method of nitrite-mediated substitution of carbohydrate triflates is an efficient method to generate structures of inverse configuration. In this study it has been demonstrated that a neighboring equatorial ester group plays a highly important role in this carbohydrate epimerization reaction, inducing the formation of inversion compounds in good yields. Based on this effect, efficient synthetic routes to a range of carbohydrate structures, notably β-D-mannosides and β-D-talosides, were designed. By use of the ester activation effect for neighboring groups, a double parallel as well as a double serial inversion strategy was developed.</p>

<p>I den här avhandlingen har vi studerat hur man kan göra nya tensider. En tensid är en speciell molekyl som har förmågan att lösa sig i både vatten och olja.</p><p>Man kan göra följande experiment hemma: Fyll en glasburk till hälften med vatten och tillsätt en droppe matolja. Oljan bildar en droppe ovanpå vattnet, därför att vatten och olja inte är blandbara. Vatten är polärt och olja är opolärt. Om man rör om med en sked kommer oljedroppen förvisso att dela upp sig i mindre droppar, men så snart man slutar att röra kommer dessa att lägga sig på vattenytan igen. Sätt nu en droppe diskmedel till blandningen och rör om. Nu sprider sig oljedropparna mycket bättre i vattnet, och de lägger sig heller inte på vattenytan lika fort när man slutar att röra. Det här beror på att diskmedel innehåller en tensid, som har en polär och en opolär del. Den polära delen passar ihop med det polära vattnet, medan den opolära delen passar ihop med den opolära oljan. På så vis kan tensiden hjälpa till att lösa upp opolära ämnen i polära vätskor.</p><p>Den aktiva delen av ett läkemedel består ofta av opolära ämnen, vilka inte löser sig i polära vätskor såsom vatten. Eftersom kroppen består till stor del av vatten måste man ändå försöka få läkemedlet vattenlösligt, för att möjliggöra transport via blodet till problemområdet. Det kan man uppnå genom att tillsätta tensider. Om läkemedel-tensidblandningen ska ges till djur eller människor får inte tensiden orsaka någon skada i kroppen.</p><p>Vi har försökt framställa tensider som ska kunna användas för att just lösa läkemedel i vatten. För att kunna framställa nya tensider måste man ha kunskap i organisk syntes. Det betyder att man måste veta hur man från små intermediat (”byggstenar”) successivt kan bygga upp nya molekyler som har de önskvärda egenskaperna. Genom olika typer av organisk syntes har vi byggt upp tre nya tensidtyper, vars egenskaper vi studerat med olika mätningar. Ingen av dessa tensider lämpade sig som tillsats till läkemedel, men vårt arbete har givit mycket ny kunskap om hur framtida tensidmolkyler kan tillverkas och vilka egenskaper de får.</p> / <p>This thesis deals with the synthesis and characterization of new polyhydroxy surfactants. The first part describes the synthesis of three new surfactant classes, and the second part concerns the surface chemical characterization of the synthesized surfactants.</p><p>A stereodivergent route for preparation of hydrophilic head groups was developed, that featured consecutive stereoselective dihydroxylations of a diene. This method provided in total four different polyhydroxylated head groups. These surfactant head groups were natural and unnatural sugar analogues, and were used for the coupling with two different hydrophobic tail groups.</p><p>Another approach took advantage of a metathesis reaction and provided a polyhydroxylated compound that was coupled to 12-hydroxy stearic acid</p><p>The third class of surfactants contained an amide linkage between the hydrophilic and the hydrophobic parts. The hydrophilic part consisted of two glucose units, and 12-hydroxy stearic acid was used as the hydrophobic part. The hydroxy moiety in the tail group was further functionalized as aliphatic esters, which provided in total four different surfactants.</p><p>A selection of the surfactants was used to investigate the chiral discrimination in Langmuir monolayers at an air-water interface. The isotherms showed a remarkable difference in compressibility between diastereomeric surfactants and also a pronounced chiral discrimination between racemic and enantiomerically pure surfactants, favoring heterochiral discrimination. The monolayers were also investigated with Brewster angle microscopy (BAM) and grazing incidence X-ray diffraction (GIXD). It was not possible to observe any chirality dependent features from the BAM images, but the GIXD measurement supported the conclusion that heterochiral discrimination governed the intermolecular forces within the racemic monolayer.</p><p>The third class of surfactants, containing an amide linkage between the glucose units and 12-hydroxy stearic acid was evaluated with respect to the CMC and the haemolytic activity. These surfactants were all haemolytic close to their respective CMC.</p>