<p>På SSAB i Borlänge har man upptäckt att avgaser från färgen förorenar ugnarna vid härdning. Avgaserna består av lösningsmedel och andra flyktiga föreningar som sedan förkolnas och faller ner på lackerade plåtband. För att komma runt det här problemet har SSAB tillsammans med Akzo Nobel Industrial Finishes AB, i Gamleby, tillverkat en färg som inte ska ge ifrån sig något lösningsmedel och på så sätt minska bildandet av föroreningar i ugnarna. Färgen heter NOVA GreenCoat och innehåller rapsmetylester, RME, som är ett reaktivt lösningsmedel och ska binda till bindemedlet i färgen och på så sätt hindras från att avgå vid härdning.</p><p>Syftet har varit att undersöka om en viss metod fungerar bra för att samla upp avgaser vid härdning. Avgaserna analyserades med GC-MS och härdningen studerades med FTIR. Arbetet har utförts både i Borlänge och i Gamleby.</p><p>Metoden för uppsamling av avgaserna visade sig fungera, dock inte särskilt effektivt. Den skulle därför behöva optimeras.</p><p>Härdningen kunde till viss del följas med hjälp av FTIR. Förändring i IR-spektrumet syntes för hydroxyltoppen vid cirka 3500 cm^-1. En skillnad kunde ses för en topp vid 2858 cm^-1 som uppkom i det ohärdade materialet innehållande RME, men den försvann under härdning. Toppen ökade med ökad mängd RME och syntes inte alls för de prover som inte innehöll RME.</p><p>Samtliga gjorda analyser indikerade att RME avgick vid härdning. Vid analys med GC-MS kunde de föreningar som avgick från RME identifieras som: metyl-14-metyl pentadekanoat och/eller metyl hexadekanoat, olika former av metyl oktadekanoat samt olika former av metyl eikosanoat. Andra föreningar från klarlacken som avgick var lösningsmedel x och y samt i två av proverna hexametoximetylmelamin, HMMM.</p> / <p>Problems with exhaust gases from paint that contaminates the ovens have been discovered at SSAB in Borlänge.  The exhaust gases contain solvents and other volatiles that vaporize from the paint and later on carbonize and fall down on the next coming sheets. SSAB and Akzo Nobel Industrial Finishes AB have developed a paint that is not supposed to vaporize any solvents and therefore reduce the contaminations of the ovens. The paint is called NOVA GreenCoat and contains rapeseed methyl ester, RME. RME is a reactive solvent that is supposed to react with the binder in the paint and therefore be prevented from leaving during thermal cure.</p><p>The purpose was to investigate whether a specific method worked well, for collecting the exhaust gases during thermal cure, or not. The collected exhaust gases were analyzed by using GC-MS and the cure was studied with FTIR. The work was executed both in Borlänge and Gamleby.</p><p>The method for collecting the exhaust gases worked, unfortunately it wasn’t particularly effective. It therefore needs to be optimized.</p><p>The cure could partially be studied by using FTIR. Changes in the IR-spectrum could be followed by looking at the hydroxyl peak at approximately 3500 cm^-1. A certain difference was observed for a peak at 2858 cm^-1 that appeared in the uncured material containing RME. The peak disappeared during cure. It increased with increased amount of RME and could not be observed at all for the samples that did not contain RME.</p><p>All the analyzed samples indicated that RME vaporize during cure. When analyzed with GC-MS the volatiles that vaporize from RME were identified as: hexadecanoic acid methyl ester and/or penta decanoic acid methyl-14-methyl ester, different forms of octadecanoic acid methyl ester and different forms of eicosanoic acid methyl ester. Other volatiles that vaporize from NOVA GreenCoat were solvent x and solvent y and for two of the samples hexa metoxy methyl melamine, HMMM, was also found.</p>

<p>This thesis concerns the development and utilisation of techniques for characterisation and transdermal delivery of various systems for pharmaceutical applications.</p><p>The degree of dissociation of drug molecules and the mobilities of the different species formed are essential factors affecting the rate of drug delivery by iontophoresis. Hence, determination of drug mobility parameters and equilibrium constants are important for the development of iontophoretic systems. With capillary zone electrophoresis using a partial filling technique and methyl-β-cyclodextrin as chiral selector, the enantiomers of orciprenaline were separated. The association constants between the enantiomers of the drug and the selector were also evaluated. Precision conductometry studies were performed for the hydrochloride salts of lidocaine and 5-aminolevulinic acid in aqueous propylene glycol and water as media, respectively.</p><p>Iontophoresis is a technique for drug delivery where charged molecules are transported into and through skin by application of a weak direct electrical current. The drugs 5-aminolevulinic acid and its methyl ester were used as model compounds and incorporated in two different drug delivery vehicles, a sponge phase and carbopol gel. The bicontinuous structure of the sponge phase, constituted of monoolein and a mixture of propylene glycol and water, makes it interesting for use in iontophoretic delivery, since ions can move more or less freely in the aqueous as well as in the lipid domains. Furthermore, all three components are known for their penetration enhancing abilities. Hydrogels like carbopol gels are interesting media with respect to iontophoretic studies, since devices for iontophoresis often utilize hydrogels as contact interfaces between the skin and the electrodes. The results indicate that the transport achieved iontophoretically using the gel (1 % active substance) was comparable with the passive delivery of clinically used formulations (16 % - 20 % active substance).</p>

Alkylierte polyzyklische aromatische Kohlenwasserstoffe werden in vielen Matrizes wie Fahrzeugabgasen und Tabakrauch und auch als Kontaminanten in Nahrungsmitteln neben rein aromatischen Kongeneren gefunden. Alkylierte PAK können über die Alkylseitenkette über benzylische Hydroxylierung und nachfolgende Sulfonierung katalysiert über Sulfotransferasen (SULT) zu reaktiven Schwefelsäureestern umgesetzt werden. Die SULT-vermittelte Bioaktivierung zu einem genotoxischen Schwefelsäureester wurde für den benzylischen Alkohol 1-Hydroxymethylpyren des Hepatokanzerogens 1-Methylpyren in früheren Arbeiten gezeigt. In der vorliegenden Arbeit wurde überprüft, ob die benzylischen Alkohole weiterer alkylierter PAK über Sulfonierung zu genotoxischen Schwefelsäureestern umgesetzt werden. Hierzu wurde eine Gruppe von 17 Modellsubstanzen ausgewählt, um die Ableitung von Struktur-Aktivitäts-Beziehungen zu ermöglichen. Das genotoxische Potenzial authentischer benzylischer Schwefelsäureester der Modellsubstanzen wurde zunächst in vitro über DNA-Adduktbildung im zellfreien System und Mutagenität im Salmonella-Rückmutationstest untersucht. Die Sulfate zeigten große Reaktivitätsunterschiede in Abhängigkeit von der Struktur des aromatischen Systems und der Position der Alkylseitenkette, wobei die Endpunkte DNA-Adduktbildung und Mutagenität gut korrelierten. Des Weiteren wurde der Salmonella-Mutagenitätstest mit den benzylischen Alkoholen der untersuchten alkylierten PAK und gentechnisch veränderten S. typhimurium-Stämmen, die SULT-Formen des Menschen heterolog exprimieren, durchgeführt. Bis auf die Alkohole 2- und 4-HMP zeigten alle untersuchten benzylischen Alkohole deutliche mutagene Effekte in einem oder mehreren humane SULT exprimierenden Stämmen. Die durchgeführten in vitro-Versuche zeigten das Potenzial der benzylischen Metabolite alkylierter PAK für genotoxische Wirkungen. Nachfolgend musste geklärt werden, welche Relevanz die beobachteten Effekte für die komplexere in vivo-Situation haben. Nach Verabreichung verschiedener benzylischer Schwefelsäureester und Alkohole an männliche Ratten konnten DNA-Addukte in den untersuchten Organen detektiert werden, was im Fall der Schwefelsäureester deren systemische Bioverfügbarkeit und im Fall der benzylischen Alkohole deren Umsatz durch SULT der männlichen Ratte zeigte. Da im Gegensatz zum Menschen die SULT-Expression in der Ratte auf die Leber fokussiert ist, musste ein Großteil des Umsatzes zu genotoxischen Sulfaten in der Leber stattgefunden haben. DNA-Addukte wurden jedoch auch in extrahepatischen Organen gefunden, was über einen hepatischen Export der gebildeten reaktiven Sulfate und deren Transport über den Blutkreislauf zu diesen Geweben erklärt werden kann. Für die weiterführenden in vivo-Studien wurden die benzylischen Alkohole 1-HMP und 1-HM-8-MP ausgewählt, die trotz großer struktureller Ähnlichkeit toxikodynamische Unterschiede zeigten. Zur Untersuchung der Bedeutung des SULT-vermittelten Toxifizierungsweges als auch konkurrierender detoxifizierender oxidativer Stoffwechselprozesse, wurden für 1-HMP und 1-HM-8-MP in vivo-Inhibitionsstudien mit SULT-Inhibitoren und für 1-HM-8-MP auch mit ADH/ALDH-Inhibitoren durchgeführt. Eine Vorbehandlung mit dem SULT-Hemmstoff Pentachlorphenol führte zu einer Reduktion der DNA-Adduktniveaus in Organen 1-HMP- und 1-HM-8-MP-behandelter Tiere. Die Verabreichung von Quercetin hatte keine Auswirkung auf die DNA-Adduktniveaus. Die Hemmung der DNA-Adduktbildung bei Verabreichung von Pentachlorphenol verdeutlichte jedoch, dass benzylische Alkohole alkylierter PAK in vivo über Sulfonierung bioaktiviert werden. Eine Vorbehandlung mit dem ADH-Inhibitor 4-Methylpyrazol und dem ADH-Substrat Ethanol führte zu erhöhten DNA-Adduktniveaus in Organen 1-HM-8-MP-behandelter Tiere. Den gleichen Effekt, jedoch in geringerem Ausmaß, hatte auch die Vorbehandlung mit dem ALDH-Inhibitor Disulfiram. Dies deutet darauf hin, dass oxidative Modifikationen an der Seitenkette des 1-HM-8-MP einen Detoxifizierungsmechanismus darstellen. Nach Verabreichung benzylischer Metabolite alkylierter PAK wurden oftmals hohe Adduktniveaus in der Niere detektiert. Als mögliche Ursache hierfür wurde eine Transporter-vermittelte renale Sekretion reaktiver Sulfate postuliert, die über Vorbehandlung mit Probenecid vor Verabreichung von 1-HMP und 1-HM-8-MP überprüft wurde. Der Haupteffekt der Probenecid-Behandlung wurde jedoch nicht in der Niere, sondern in der Leber beobachtet, die stark erhöhte Adduktniveaus zeigte. Eine mögliche Erklärung hierfür ist die Hemmung des Exportes in der Leber gebildeter reaktiver Sulfate über Inhibition hepatischer organischer Anionentransporter. / Alkylated polycyclic aromatic hydrocarbons are found besides purely aromatic congeners in numerous matrices like car engine exhausts and tobacco smoke and as contaminants in foods. Alkylated PAH can be converted at the alkyl side chain to reactive sulfuric acid esters via benzylic hydroxylation and subsequent sulfonation catalysed by sulfotransferases (SULT). The SULT-mediated bioactivation to a genotoxic sulfuric acid ester was shown for the benzylic alcohol 1-hydroxymethylpyrene of the hepatocarcinogen 1-methylpyrene in previous studies. In the thesis at hand it was studied if the benzylic alcohols of further alkylated PAH are converted to genotoxic sulfuric acid esters via sulfonation. For this purpose a group of 17 model substances was chosen to allow for deduction of structure activity relationships. The genotoxic potential of authentic benzylic sulfuric acid esters of the model substances was initially investigated in vitro via DNA adduct formation in a cell free system and mutagenicity in the Salmonella reverse mutation test. The sulfates showed large differences in reactivity depending on the structure of the aromatic system and the position of the alkyl side chain whereupon the endpoints DNA adduct formation and mutagenicity correlated well. Furthermore, the Salmonella mutagenicity test was carried out with the benzylic alcohols of the alkylated PAH studied and S. typhimurium strains genetically engineered for the heterologous expression of human SULT forms. Except for the alcohols 2- and 4-HMP all benzylic alcohols studied showed clear mutagenic effects in one or more SULT-expressing strains. The studies performed in vitro demonstrated the potential of benzylic metabolites of alkylated PAH for genotoxic effects. Consecutively, the relevance of the observed effects for the more complex in vivo situation had to be clarified. After administration of different benzylic sulfuric acid esters and alcohols to male rats DNA adducts were detected in the organs studied, in case of the sulfuric acid esters showing their systemic bioavailability and in case of the benzylic alcohols demonstrating their conversion to the corresponding reactive benzylic sulfuric acid esters by SULT of the male rat. Since in contrast to man SULT expression in the rat is focused on the liver, a large part of the conversion to genotoxic sulfates must have been taken place in the liver. However, DNA adducts were also found in extrahepatic tissues which can be attributed to a hepatic export of the reactive sulfates formed and their transport to these tissues via circulation. For the continuative in vivo studies the benzylic alcohols 1-HMP and 1-HM-8-MP were chosen that demonstrated toxicodynamic differences in spite of their great structural resemblance. To investigate the importance of the SULT-mediated toxification pathway as well as competing detoxifying oxidative metabolic pathways, in vivo inhibition studies with SULT inhibitors were performed for 1-HMP and 1-HM-8-MP and with ADH/ALDH inhibitors also for 1-HM-8-MP. A pretreatment with the SULT inhibitor pentachlorophenol led to a reduction of DNA adduct levels in organs of animals treated with 1-HMP and 1-HM-8-MP. Administration of quercetin had no impact on the DNA adduct levels. However, inhibition of DNA adduct formation at administration of pentachlorophenol demonstrated that benzylic alcohols of alkylated PAH are bioactivated via sulfonation in vivo. A pretreatment with the ADH inhibitor 4-methylpyrazole and the ADH substrate ethanol led to increased DNA adduct levels in organs of animals treated with 1-HM-8-MP. The same effect but to a lesser extent was caused by a pretreatment with the ALDH inhibitor disulfiram. This indicates that oxidative modifications at the side chain of 1-HM-8-MP represent a detoxification mechanism. After administration of benzylic metabolites of alkylated PAH often high DNA adduct levels were detected in kidney. A transporter-mediated renal secretion was postulated as possible cause which was investigated using a pretreatment with probenecid before administration of 1-HMP and 1-HM-8-MP. However, the main effect of the treatment with probenecid was not observed in kidney but in liver that showed strongly increased adduct levels. A possible explanation for this effect is the inhibition of the export of reactive sulfates formed in liver via inhibition of hepatic organic anion transporters.

This thesis describes methods to obtain value–addedcompounds from TMP-turpentine obtained from the spruce, Piceaabies. The methodology focuses on biotransformations using twoapproaches: an oxygenation approach (i.e. oxygenation ofterpene hydrocarbons by cell cultures) and an esterificationapproach (i.e. lipase-catalysed transesterification of vinylacetate with terpene alcohols, and a further fractionation ofthe TMP-turpentine). The main constituents of the turpentine, a-pinene, b-pineneand limonene, were subjected to a P. abies suspension culture.Allylic oxidation formed the major products for α-pineneand β-pinene, which were further oxidised to theirrespective aldehyde or ketone. One of the minor products froma-pinene, cis-verbenol, was not only transformed into verbenonebut also isomerised to trans-verbenol. Limonene gavelimonene-(1,2)-epoxide as the major product. Fractionation of monoterpenes is accomplished throughphysical separation methods, chromatography and distillation,and lipase-catalysed transesterification of vinyl acetate withterpene alcohols. The esters of myrtenol and trans-pinocarveolwere separated from the more slowly reacting alcohols such asborneol and carveol by use of a combination of the Mucor mieheilipase and Candida antarctica lipase A as catalysts.Furthermore, the non-reacting tertiary terpene alcohols wereseparated from the reacting alcohols in a single step byCandida antarctica lipase A. Lipase-catalysed (Candida antarctica lipase B andPseudomonas cepacia lipase) transesterification of vinylacetate with sterically hindered secondary alcoholsunexpectedly yielded hemiacetals or hemiacetal esters. Thereaction conditions required to obtain these side products havebeen studied. <b>Keywords:</b>Picea abies, Pinaceae, Essential oilscomposition; Terpene alcohol; Hemiacetal; Hemiacetal ester,TMP-turpentine; Monoterpene; α-Pinene; β-Pinene;Limonene; Verbenol; Pinocarveol; Borneol; Myrtenol; Suspensioncell culture; Biotransformation; Lipase-catalysed; Oxidation;Allylic oxidation; Transesterification; Autoxidation;Separation.

This thesis concerns the development and utilisation of techniques for characterisation and transdermal delivery of various systems for pharmaceutical applications. The degree of dissociation of drug molecules and the mobilities of the different species formed are essential factors affecting the rate of drug delivery by iontophoresis. Hence, determination of drug mobility parameters and equilibrium constants are important for the development of iontophoretic systems. With capillary zone electrophoresis using a partial filling technique and methyl-β-cyclodextrin as chiral selector, the enantiomers of orciprenaline were separated. The association constants between the enantiomers of the drug and the selector were also evaluated. Precision conductometry studies were performed for the hydrochloride salts of lidocaine and 5-aminolevulinic acid in aqueous propylene glycol and water as media, respectively. Iontophoresis is a technique for drug delivery where charged molecules are transported into and through skin by application of a weak direct electrical current. The drugs 5-aminolevulinic acid and its methyl ester were used as model compounds and incorporated in two different drug delivery vehicles, a sponge phase and carbopol gel. The bicontinuous structure of the sponge phase, constituted of monoolein and a mixture of propylene glycol and water, makes it interesting for use in iontophoretic delivery, since ions can move more or less freely in the aqueous as well as in the lipid domains. Furthermore, all three components are known for their penetration enhancing abilities. Hydrogels like carbopol gels are interesting media with respect to iontophoretic studies, since devices for iontophoresis often utilize hydrogels as contact interfaces between the skin and the electrodes. The results indicate that the transport achieved iontophoretically using the gel (1 % active substance) was comparable with the passive delivery of clinically used formulations (16 % - 20 % active substance).

På SSAB i Borlänge har man upptäckt att avgaser från färgen förorenar ugnarna vid härdning. Avgaserna består av lösningsmedel och andra flyktiga föreningar som sedan förkolnas och faller ner på lackerade plåtband. För att komma runt det här problemet har SSAB tillsammans med Akzo Nobel Industrial Finishes AB, i Gamleby, tillverkat en färg som inte ska ge ifrån sig något lösningsmedel och på så sätt minska bildandet av föroreningar i ugnarna. Färgen heter NOVA GreenCoat och innehåller rapsmetylester, RME, som är ett reaktivt lösningsmedel och ska binda till bindemedlet i färgen och på så sätt hindras från att avgå vid härdning. Syftet har varit att undersöka om en viss metod fungerar bra för att samla upp avgaser vid härdning. Avgaserna analyserades med GC-MS och härdningen studerades med FTIR. Arbetet har utförts både i Borlänge och i Gamleby. Metoden för uppsamling av avgaserna visade sig fungera, dock inte särskilt effektivt. Den skulle därför behöva optimeras. Härdningen kunde till viss del följas med hjälp av FTIR. Förändring i IR-spektrumet syntes för hydroxyltoppen vid cirka 3500 cm-1. En skillnad kunde ses för en topp vid 2858 cm-1 som uppkom i det ohärdade materialet innehållande RME, men den försvann under härdning. Toppen ökade med ökad mängd RME och syntes inte alls för de prover som inte innehöll RME. Samtliga gjorda analyser indikerade att RME avgick vid härdning. Vid analys med GC-MS kunde de föreningar som avgick från RME identifieras som: metyl-14-metyl pentadekanoat och/eller metyl hexadekanoat, olika former av metyl oktadekanoat samt olika former av metyl eikosanoat. Andra föreningar från klarlacken som avgick var lösningsmedel x och y samt i två av proverna hexametoximetylmelamin, HMMM. / Problems with exhaust gases from paint that contaminates the ovens have been discovered at SSAB in Borlänge.  The exhaust gases contain solvents and other volatiles that vaporize from the paint and later on carbonize and fall down on the next coming sheets. SSAB and Akzo Nobel Industrial Finishes AB have developed a paint that is not supposed to vaporize any solvents and therefore reduce the contaminations of the ovens. The paint is called NOVA GreenCoat and contains rapeseed methyl ester, RME. RME is a reactive solvent that is supposed to react with the binder in the paint and therefore be prevented from leaving during thermal cure. The purpose was to investigate whether a specific method worked well, for collecting the exhaust gases during thermal cure, or not. The collected exhaust gases were analyzed by using GC-MS and the cure was studied with FTIR. The work was executed both in Borlänge and Gamleby. The method for collecting the exhaust gases worked, unfortunately it wasn’t particularly effective. It therefore needs to be optimized. The cure could partially be studied by using FTIR. Changes in the IR-spectrum could be followed by looking at the hydroxyl peak at approximately 3500 cm-1. A certain difference was observed for a peak at 2858 cm-1 that appeared in the uncured material containing RME. The peak disappeared during cure. It increased with increased amount of RME and could not be observed at all for the samples that did not contain RME. All the analyzed samples indicated that RME vaporize during cure. When analyzed with GC-MS the volatiles that vaporize from RME were identified as: hexadecanoic acid methyl ester and/or penta decanoic acid methyl-14-methyl ester, different forms of octadecanoic acid methyl ester and different forms of eicosanoic acid methyl ester. Other volatiles that vaporize from NOVA GreenCoat were solvent x and solvent y and for two of the samples hexa metoxy methyl melamine, HMMM, was also found.

ABSTRACT SYNTHESIS AND ELECTROCHROMIC PROPERTIES OF CONDUCTING POLYMERS OF SUCCINIC ACID BIS-(2-THIOPHEN-3-YL-ETHYL) ESTER AND THEIR USE IN ELECTROCHROMIC DEVICES Sa&ccedil / an, Lale M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare June 2006, 59 pages A new monomer / succinic acid bis-(2-thiophen-3-yl-ethyl)ester (SATE) was synthesized through the esterification reaction of 2-thiophen-3-yl-ethanol and succinyl chloride. The chemical structure of monomer was characterized via Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Electrochemical behaviors of SATE alone and SATE in the presence of thiophene were studied by cyclic voltammetry (CV). The synthesis of homopolymer and copolymer were achieved via constant potential electrolysis. Both homopolymer (PSATE) and copolymer [P(SATE-co-Th)] were characterized by various techniques including cyclic voltammetry, FTIR, Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermal Gravimetry Analysis (TGA) and UV-VIS Spectrophotometer. Conductivities of samples were measured by four probe technique. The electrochromic properties of the polymers were investigated via spectroelectrochemistry, colorimetry and switching studies. In addition, dual type electrochromic devices (ECDs) composed of PSATE, P(SATE-co-Th) and poly(3,4-ethylenedioxythiophene) (PEDOT) were constructed and evaluated. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry. They have shown to possess good switching times, reasonable contrasts, high stabilities and optical memories.

Abdominal aortic aneurysms are a leading cause of death in the U.S. where 14,000 people die from aneurysm rupture and 178,000 are diagnosed each year. A novel alternative treatment for abdominal aortic aneurysms has been proposed, where a biodegradable polymer scaffold is photopolymerized in situ around the exterior of the aneurysm. This scaffold will mechanically constrain the aneurysm from further expansion, and will deliver a drug, doxycycline, to treat the underlying biological cause of the disease. In order for device development, a suitable polymer must be designed with appropriate mechanical properties, degradation rate, polymerization, and elution rate. Poly(β-amino ester) networks have been proposed as the material of choice; however, many of their structure-property relationships have yet to be determined. Therefore, the overall goal of this work is to determine the structure-property relationships of the poly(β-amino ester) networks in order to advance the design of the treatment, and has been divided into three objectives: (1) understand the structure-property relationships of poly(β-amino ester) networks, specifically the polymerization, degradation rate, and thermo-mechanical properties, (2) determine the impact of doxycycline incorporation on degradation rate and mechanical properties, (3) evaluate the effect of simulated physiological conditions on degradation rate and mechanical properties. In the initial chapters, the fundamental structure-property relationships are established between reactant chemical structure, step-growth polymerization, photopolymerization, thermo-mechanical properties, and degradation rate using a systematic approach of two homologous series of reactants. Further tailoring of degradation rate, water content, and modulus in vitro was performed by using a copolymer network. Doxycycline inhibited photopolymerization due to overlapping absorbance spectra with the photoinitiator, but full network formation occurred by increasing the photoinitiator concentration. Networks displayed varying controlled release rates, and the underlying release mechanism was determined for each network using established methods. In order to increase mechanical properties, a co-monomer, methyl methacrylate, was added to the network to increase the glass transition temperature, toughness, and deformation capacity. These co-networks displayed temporal-control of mechanical properties in simulated physiological conditions, since degradation caused a shift in the glass transition temperature, which changed the mechanical behavior of the network. The temporal-control of mechanical properties was further investigated under degradation conditions in vitro and in vivo. Due to the mechanically active loading environment in vivo, networks displayed a decrease in toughness, yet maintained mechanical properties similar to native biological tissues. These networks establish a multifunctional biomaterials platform with materials that can be easily synthesized, photopolymerized into various geometries, and sustain mechanical properties while undergoing degradation and therapeutic agent release.

<p>This thesis describes methods to obtain value–addedcompounds from TMP-turpentine obtained from the spruce, Piceaabies. The methodology focuses on biotransformations using twoapproaches: an oxygenation approach (i.e. oxygenation ofterpene hydrocarbons by cell cultures) and an esterificationapproach (i.e. lipase-catalysed transesterification of vinylacetate with terpene alcohols, and a further fractionation ofthe TMP-turpentine).</p><p>The main constituents of the turpentine, a-pinene, b-pineneand limonene, were subjected to a P. abies suspension culture.Allylic oxidation formed the major products for α-pineneand β-pinene, which were further oxidised to theirrespective aldehyde or ketone. One of the minor products froma-pinene, cis-verbenol, was not only transformed into verbenonebut also isomerised to trans-verbenol. Limonene gavelimonene-(1,2)-epoxide as the major product.</p><p>Fractionation of monoterpenes is accomplished throughphysical separation methods, chromatography and distillation,and lipase-catalysed transesterification of vinyl acetate withterpene alcohols. The esters of myrtenol and trans-pinocarveolwere separated from the more slowly reacting alcohols such asborneol and carveol by use of a combination of the Mucor mieheilipase and Candida antarctica lipase A as catalysts.Furthermore, the non-reacting tertiary terpene alcohols wereseparated from the reacting alcohols in a single step byCandida antarctica lipase A.</p><p>Lipase-catalysed (Candida antarctica lipase B andPseudomonas cepacia lipase) transesterification of vinylacetate with sterically hindered secondary alcoholsunexpectedly yielded hemiacetals or hemiacetal esters. Thereaction conditions required to obtain these side products havebeen studied.</p><p><b>Keywords:</b>Picea abies, Pinaceae, Essential oilscomposition; Terpene alcohol; Hemiacetal; Hemiacetal ester,TMP-turpentine; Monoterpene; α-Pinene; β-Pinene;Limonene; Verbenol; Pinocarveol; Borneol; Myrtenol; Suspensioncell culture; Biotransformation; Lipase-catalysed; Oxidation;Allylic oxidation; Transesterification; Autoxidation;Separation.</p>

L'huile minérale constitue le liquide isolant le plus communément employé dans les transformateurs de puissance d'une part pour ses propriétés physico-chimiques et d'autre part pour son faible coût et sa disponibilité. Cependant les performances de cette huile commencent à être limitées par rapport aux nouveaux critères. Pour palier à ce problème, deux solutions sont envisageables : trouver des liquides de substitution ou améliorer les propriétés de l'huile minérale. C'est à cette deuxième solution qu'est dédié ce travail. Il s'agit de trouver un mélange optimal d'huiles à base d'huile minérale, les additifs considérés étant des liquides isolants utilisés également dans les transformateurs tels que les huiles esters synthétiques et les huiles silicones. Des essais permettant d'analyser des caractéristiques fondamentales comme la miscibilité, la viscosité cinématique, la tenue diélectrique, la stabilité au vieillissement des huiles et des mélanges, et des mesures de tendance à la charge statique, ont été effectuées. Différents mélanges à différentes concentrations ont été étudiés. Pour des raisons techniques et économiques, l'accent est mis sur les mélanges composés de 80% d'huile minérale et 20% des autres types d'huile. Il ressort des différents essais réalisés que chaque type d'huile a un avantage. L'huile minérale est la plus efficace pour évacuer la chaleur de par sa faible viscosité, l'huile ester synthétique présente la meilleure tenue diélectrique de par sa haute solubilité de l'eau, et l'huile silicone est la plus stable au vieillissement. D'autre part, le mélange optimal obtenu se compose de 80% d'huile minérale et 20% d'ester synthétique. Ce mélange permet d'améliorer certaines caractéristiques de l'huile minérale sans toutefois dégrader ses bonnes propriétés, tout en restant dans un coût raisonnable. Il présente, par rapport à l'huile minérale seule, une aptitude à évacuer la chaleur pratiquement équivalente, une tenue diélectrique plus élevée, une meilleure stabilité au vieillissement et une tendance à la charge statique modérée.