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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1361

Elastic and Inelastic Electron Tunneling in Molecular Devices

Kula, Mathias January 2006 (has links)
<p>A theoretical framework for calculating electron transport through molecular junctions is presented. It is based on scattering theory using a Green's function formalism. The model can take both elastic and inelastic scattering into account and treats chemical and physical bonds on equal footing. It is shown that it is quite reliable with respect to the choice of functional and basis set. Applications concerning both elastic and inelastic transport are presented, though the emphasis is on the inelastic transport properties. The elastic scattering application part is divided in two part. The first part demonstrates how the current magnitude is strongly related to the junction width, which provides an explanation why experimentalists get two orders of magnitude differences when performing measurements on the same type of system. The second part is devoted to a study of how hydrogenbonding affects the current-voltage (I-V) characteristics. It is shown that for a conjugated molecule with functional groups, the effects can be quite dramatic. This shows the importance of taking possible intermolecular interactions into account when evaluating and comparing experimental data. The inelastic scattering part is devoted to get accurate predictions of inelastic electron tunneling spectroscopy (IETS) experiments. The emphasis has been on elucidating the importance of various bonding conditions for the IETS. It is shown that the IETS is very sensitive to the shape of the electrodes and it can also be used to discriminate between different intramolecular conformations. Temperature dependence is nicely reproduced. The junction width is shown to be of importance and comparisons between experiment as well as other theoretical predictions are made.</p>
1362

Formation and properties of polyelectrolyte multilayers on wood fibres: influence on paper strength and fibre wettability

Lingström, Rikard January 2006 (has links)
<p>The work in this licentiate thesis examines the adsorption of polyelectrolyte multilayers (PEM) onto wood fibres as a new way to influence the properties of the fibre surfaces and hence the fibres. Fundamental aspects of PEM formation on wood fibres have been studied, and discussed in terms of paper strength and wood fibre wettability.</p><p>PEMs have been formed from three different polymer systems: 1) two strong polyelectrolytes (i.e., fully charged over a wide pH range), polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulphonate (PSS); 2) polyethylene oxide (PEO) and polyacrylic acid (PAA), formed at low pH and held together by hydrogen bonding; and 3) two weak polyelectrolytes, polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA). The PEMs formed from PDADMAC/PSS and PEO/PAA were studied using Stagnation Point Adsorption Reflectometry (SPAR), with SiO2 as the substrate. This was done to establish the formation of PEMs and, using PDADMAC/PSS, also to predict the influence of salt concentration during PEM formation. The amount of PDADMAC/PSS adsorbed was found to increase with salt concentration up to approximately 0.1 M NaCl. The formation of PEMs from PAH/PAA has already been studied in terms of structure; amount adsorbed, and influence on paper strength.</p><p>Sheets were formed from fibres treated with either PDADMAC/PSS or PEO/PAA PEMs and tested to determine paper tensile strength. Both PEM systems increased the tensile index and strain at break in the range of 100% when approximately 10 layers had been adsorbed. After several PEM layers had been adsorbed, the sheets made of fibres treated with PDADMAC/PSS differed in tensile strength depending on the polymer adsorbed in the outermost layer. A higher tensile strength was detected when PDADMAC rather than PSS was adsorbed in the outermost layer. Sheets made of fibres treated with PEO/PAA displayed a linear increase in strength, independent of which polymer that was adsorbed in the outermost layer.</p><p>The amount of adsorbed PDADMAC/PSS, as analysed using nitrogen and sulphur analysis, respectively, increased linearly, but with a higher amount adsorbed in the first layer. A comparison of the adsorption onto the SiO<sub>2</sub>-surfaces (SPAR-measurements) and fibres shows some differences. This is apparent both regarding the adsorption in the first layer and in the change in adsorbed amount with salt concentration. Despite this, one can conclude that SiO<sub>2</sub> and wood fibres show very similar trends, and that SiO<sub>2 </sub>can be used as a convenient model surface in predicting PEM formation on wood fibres.</p><p>Individual fibres were also partially treated using a Dynamic Contact Angle Analyser, and the treated and untreated parts were analysed in terms of wettability and surface structure. The differences in wettability are significant, depending on the polymer system used and, with PAH/PAA PEMs, the pH strategy show a large influence in wettability. PDADMAC/PSS and PAH/PAA PEMs both had a large influence on wettability, depending on the polymer adsorbed in the outermost layer, wettability being lower when the cationic polymer was adsorbed in the outermost layer. With the PEO/PAA system, however, the polymer adsorbed in the outermost layer caused no detectable difference. These results, when compared against the paper strength results, indicate that the strongest sheets are formed of the fibres with the lowest wettability. This may be explained in terms of wet adhesion: since the fibre networks are formed in water, lower wettability would give a stronger force between the fibres during consolidation, resulting in a greater contact area and thus probably a stronger dry adhesion between the fibres in the formed sheet. This is furthermore also supported by wet adhesion measurements using Atomic Force Microscopy where PEMs formed from PAH/PAA, show that the pull-off force is increased when PAH is adsorbed in the outermost layer, compared to when PAA is adsorbed in the outermost layer.</p> / <p>Denna licentiatavhandling behandlar adsorption av polyelektrolytmultiskikt (multiskikt) på cellulosafibrer som ett nytt sätt att påverka en fibers ytegenskaper. Grundläggande förutsättningar för bildandet av multiskikt på fibrer diskuteras i termer av pappersstyrka och fibervätning.</p><p>Multiskikt har bildats med hjälp av tre olika polymerkombinationer; 1.) två starka polyelektrolyter, polydiallyldimetylammoniumklorid (PDADMAC) och polystyrensulfanat (PSS), 2.) polyetylenoxid (PEO) och polyakrylsyra (PAA), adsorberade vid lågt pH och sammanhållna av icke elektrostatiska vätebindningar, och 3.) två svaga polyelektrolyter, polyallylaminhydroklorid (PAH) och PAA. Uppbyggnaden av multiskikt bestående av PDADMAC/PSS och PEO/PAA på kiseloxid studerades med Stagnationspunktsreflektometri (SPAR) för att undersöka att uppbyggnad av PEM skett, samt att studera hur uppbyggnaden påverkas av koncentrationen NaCl i polymerlösningen. Försöken visade att den adsorberade mängden PDADMAC/PSS ökade med saltkoncentrationen upp till 0,05-0,1 M NaCl. Uppbyggnaden av multiskikt bestående av PAH/PAA är sedan tidigare studerad undersöks därför inte specifikt i detta arbete.</p><p>Laboratorieark tillverkades av fibrer som behandlats med multiskikt bestående av PDADMAC/PSS, respektive PAH/PAA. Fysikalisk pappersprovning av arken visade för båda systemen en ökning med cirka 100 % i dragindex för ark som tillverkats av fibrer som behandlats med cirka tio lager, jämfört med ark som tillverkats av icke-behandlade fibrer. Ark tillverkade från PDADMAC/PSS-behandlade fibrer visade att när 5-7 lager adsorberats, ett högre dragindex då PDADMAC adsorberats i det yttersta lagret, jämfört med då PSS adsorberats i det yttersta lagret. Ark tillverkade från fibrer behandlade med PEO/PAA visade ingen skillnad i dragindex beroende av vilken polymer som adsorberats i det yttersta lagret.</p><p>Den adsorberade mängden PDADMAC/PSS på fibrerna bestämdes med hjälp av kväve- respektive svavelanalys. Den adsorberade mängden polymer ökad linjärt som en funktion av antalet adsorberade lager, men med en högre adsorberad mängd i det första lagret. Dessa resultat har jämförts med den adsorberade mängden för multiskikt uppbyggda med SPAR på kiseloxid. Jämförelsen visade att det finns skillnader i uppbyggnaden mellan skikt byggda på kiseloxid och fibrer, men att kiseloxid med god tillförlitlighet kan användas som modellyta för att förutsäga generella trender för adsorptionen av samma polymersystem på cellulosafibrer.</p><p>Multiskikt har också bildats på enskilda fibrer med hjälp av en dynamisk kontaktvinkelmätare (DCA). Genom att behandla en del av en fiber, och jämföra den behandlade delen med den obehandlade delen på samma, kan ett multiskikts inverkan på fiberns ytstruktur och vätningsegenskaper studeras. De olika polymersystemen visade en avsevärd skillnad i förmågan att påverka en fibers vätningsegenskaper. För fibrer behandlade med PAH/PAA är också pH av stor betydelse för graden inverkan på fiberns vätningsegenskaper. Fibrer behandlade med PDADMAC/PSS och PAH/PAA, visade en sämre vätningsförmåga då den katjoniska polymeren adsorberats i det yttersta lagret, och vice versa. För enskilda fibrer behandlade med PEO/PAA, kunde inte konstateras någon skillnad beroende av vilken polymer som adsorberats i det yttersta lagret.</p><p>Vid en jämförelse mellan vätningsförmåga och pappersstyrka kan konstateras att de ark som visade den högsta styrkan tillverkats av fibrer där den lägsta vätningsförmågan har kunnat konstateras. Denna skillnad kan diskuteras med utgångspunkten i att en lägre vätningsförmåga resulterar i en högre våt adhesion och därmed en starkare interaktion mellan de polymerbehandlade ytorna i vått tillstånd. Det föreslås i avhandlingen att den ökade kraft som detta resulterar i vid bildandet av en fiber-fiberfog ger upphov till en högre kontaktarea och därmed, förmodligen, också en högre torr adhesion. Kraftmätningar i vått tillstånd för behandlade kiselmodellytor med hjälp av atomkraftsmikroskopi (AFM) har för PAH/PAA visat att den våta adhesionen är högre då PAH är adsorberats i det yttersta lagret, jämfört med då PAA adsorberats i det yttersta lagret. Detta stödjer hypotesen att en lägre vätning gynnar uppkomsten av en stark fiber-fiberfog.</p>
1363

Effects of HCO3- and ionic strength on the oxidation and dissolution of UO2

Hossain, Mohammad Moshin January 2006 (has links)
<p>The kinetics for radiation induced dissolution of spent nuclear fuel is a key issue in the safety assessment of a future deep repository. Spent nuclear fuel mainly consists of UO<sub>2</sub> and therefore the release of radionuclides (fission products and actinides) is assumed to be governed by the oxidation and subsequent dissolution of the UO<sub>2</sub> matrix. The process is influenced by the dose rate in the surrounding groundwater (a function of fuel age and burn up) and on the groundwater composition. In this licentiate thesis the effects of HCO<sub>3</sub>- (a strong complexing agent for UO2<sup>2+</sup>) and ionic strength on the kinetics of UO<sub>2</sub> oxidation and dissolution of oxidized UO<sub>2</sub> have been studied experimentally.</p><p>The experiments were performed using aqueous UO<sub>2 </sub>particle suspensions where the oxidant concentration was monitored as a function of reaction time. These reaction systems frequently display first order kinetics. Second order rate constants were obtained by varying the solid UO<sub>2 </sub>surface area to solution volume ratio and plotting the resulting pseudo first order rate constants against the surface area to solution volume ratio. The oxidants used were H<sub>2</sub>O<sub>2 </sub>(the most important oxidant under deep repository conditions), MnO<sub>4</sub>- and IrCl<sub>6</sub><sup>2-</sup>. The kinetics was studied as a function of HCO<sub>3</sub>- concentration and ionic strength (using NaCl and Na<sub>2</sub>SO<sub>4 </sub>as electrolytes).</p><p>The rate constant for the reaction between H<sub>2</sub>O<sub>2</sub> and UO<sub>2</sub> was found to increase linearly with the HCO3- concentration in the range 0-1 mM. Above 1 mM the rate constant is independent of the HCO3- concentration. The HCO<sub>3</sub>- concentration independent rate constant is interpreted as being the true rate constant for oxidation of UO<sub>2</sub> by H<sub>2</sub>O<sub>2</sub> [(4.4 ± 0.3) x 10-6 m min-1] while the HCO3- concentration dependent rate constant is used to estimate the rate constant for HCO<sub>3</sub>- facilitated dissolution of UO<sub>2</sub>2+ (oxidized UO<sub>2</sub>) [(8.8 ± 0.5) x 10-3 m min-1]. From experiments performed in suspensions free from HCO<sub>3</sub>- the rate constant for dissolution of UO<sub>2</sub>2+ was also determined [(7 ± 1) x 10<sup>-8 </sup>mol m<sup>-2</sup> s<sup>-1</sup>]. These rate constants are of significant importance for simulation of spent nuclear fuel dissolution.</p><p>The rate constant for the oxidation of UO<sub>2</sub> by H<sub>2</sub>O<sub>2</sub> (the HCO<sub>3</sub>- concentration independent rate constant) was found to be independent of ionic strength. However, the rate constant for dissolution of oxidized UO<sub>2</sub> displayed ionic strength dependence, namely it increases with increasing ionic strength.</p><p>The HCO<sub>3</sub>- concentration and ionic strength dependence for the anionic oxidants is more complex since also the electron transfer process is expected to be ionic strength dependent. Furthermore, the kinetics for the anionic oxidants is more pH sensitive. For both MnO<sub>4</sub>- and IrCl<sub>6</sub>2- the rate constant for the reaction with UO<sub>2 </sub>was found to be diffusion controlled at higher HCO3- concentrations (~0.2 M). Both oxidants also displayed ionic strength dependence even though the HCO<sub>3</sub>- independent reaction could not be studied exclusively.</p><p>Based on changes in reaction order from first to zeroth order kinetics (which occurs when the UO<sub>2</sub> surface is completely oxidized) in HCO<sub>3</sub>- deficient systems the oxidation site density of the UO<sub>2</sub> powder was determined. H<sub>2</sub>O<sub>2 </sub>and IrCl<sub>6</sub>2- were used in these experiments giving similar results [(2.1 ± 0.1) x 10-4 and (2.7 ± 0.5) x 10<sup>-4</sup> mol m<sup>-2</sup>, respectively].</p>
1364

Efficient carbohydrate synthesis by controlled inversion strategies

Dong, Hai January 2006 (has links)
<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>
1365

HNO3-Induced Atmospheric Corrosion of Copper, Zinc and Carbon Steel

Samie, Farid January 2006 (has links)
<p>The role of nitric acid (HNO<sub>3</sub>) on the atmospheric corrosion of metals has so far received little or no attention. However, the last decades of decreasing sulphur dioxide (SO<sub>2</sub>) levels and unchanged HNO<sub>3</sub> levels in many industrialized countries have resulted in an increased interest in possible HNO<sub>3</sub>-induced atmospheric corrosion effects. In this study a new method was developed for studying the corrosion effects of HNO<sub>3</sub> on metals at well-defined laboratory exposure conditions. The method has enabled studies to be performed on the influence of individual exposure parameters, namely HNO<sub>3</sub>-concentration, air velocity, temperature and relative humidity, as well as comparisons with newly generated field exposure data.</p><p>The corrosion rate and deposition rate of HNO<sub>3</sub> on copper was shown to follow a linear increase with HNO3 concentration. The deposition velocity (Vd) of HNO<sub>3</sub> increased up to an air velocity of 11.8 cm s<sup>-1</sup>. Only at a higher air velocity (35.4 cm s<sup>-1</sup>) the Vd on copper was lower than the Vd on an ideal absorbent, implying the Vd of HNO3 at lower air velocities to be mass-transport limited.</p><p>Within the investigated temperature range of 15 to 35 ºC only a minor decrease in the HNO<sub>3</sub>-induced copper corrosion rate could be observed. The effect of relative humidity (RH) was more evident. Already at 20 % RH a significant corrosion rate could be measured and at 65 % RH the Vd of HNO<sub>3</sub> on copper, zinc and carbon steel reached maximum and nearly ideal absorption conditions.</p><p>During identical exposure conditions in HNO<sub>3-</sub>containing atmosphere, the corrosion rate of carbon steel was nearly three times higher than that of copper and zinc. The HNO<sub>3</sub>-induced corrosion effect of copper, zinc and steel turned out to be significantly higher than that induced by SO2 alone or in combination with either NO<sub>2</sub> or O<sub>3</sub>. This is mainly attributed to the much higher water solubility and reactivity of HNO3 compared to SO<sub>2</sub>, NO<sub>2</sub> and O<sub>3.</sub> Relative to SO<sub>2</sub>, zinc exhibits the highest sensitivity to HNO<sub>3</sub>, followed by copper, and carbon steel with the lowest sensitivity.</p><p>Extrapolation of laboratory data to an assumed average outdoor wind velocity of 3.6 m s-1 enabled a good comparison with field data. Despite the fact that ambient SO<sub>2</sub> levels are still much higher than HNO<sub>3</sub> levels, the results show that HNO<sub>3</sub> plays a significant role for the atmospheric corrosion of copper and zinc, but not for carbon steel. The results generated within this doctoral study emphasize the importance of further research on the influence of HNO<sub>3</sub> on degradation of other materials, e.g. stone and glass, as well as of other metals. </p>
1366

An in situ spectro-electrochemical study of aluminium/polymer interfaces : development of ATR-FTIR and its integration with EIS for corrosion studies

Öhman, Maria January 2006 (has links)
<p>In order to extend the applications of aluminium, organic coatings may be applied on sheet materials, for instance for corrosion protection or aesthetic surface finish purposes in the automotive and construction industries, or on foil materials in the flexible packaging industry.</p><p>The most common mechanisms for deterioration and structural failure of organically coated aluminium structures are triggered by exposures to the surrounding environment. Despite the great importance to elucidate the influence of exposure parameters on a buried aluminium/polymer interface, there is still a lack of knowledge regarding the mechanisms that destabilise the structure. It is generally believed that a detailed <i>in situ</i> analysis of the transport of corroding species to the buried interface, or of surface processes occurring therein, is most difficult to perform at relevant climatic and real-time conditions.</p><p>In this work, Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) in the Kretschmann-ATR configuration was successfully applied to <i>in situ</i> studies of the transport of water and ionic species through polymer films to the aluminium/polymer interface upon exposure to ultra pure deionised water and to a 1 M sodium thiocyanate (NaSCN) model electrolyte. Other main processes distinguished were the formation of corrosion products on the aluminium surface and swelling of the surface-near polymer network. Hence, <i>in situ</i> ATR-FTIR was capable to separate deterioration-related processes from each other.</p><p>To perform more unambiguous interpretations, a spectro-electrochemical method was also developed for<i> in situ</i> studies of the buried aluminium/polymer interface by integrating the ATR-FTIR technique with a complementary acting technique, Electrical Impedance Spectroscopy (EIS). While transport of water and electrolyte through the polymer film to the aluminium/polymer interface and subsequent oxidation/corrosion of aluminium could be followed by ATR-FTIR, the protective properties of the polymer as well as of processes at the aluminium surface were simultaneously studied by EIS. The integrated set-up provided complementary information of the aluminium/polymer sample investigated, with ATR-FTIR being sensitive to the surface-near region and EIS being sensitive to the whole system. While oxidation/corrosion and delamination are difficult to distinguish by EIS, oxide formation could be confirmed by ATR-FTIR. Additionally, while delamination and polymer swelling may be difficult to separate with ATR-FTIR, EIS distinguished swelling of the polymer network and also identified ultimate failure as a result of delamination.</p><p>The capability of the integrated ATR-FTIR / EIS <i>in situ</i> technique was explored by studying aluminium/polymer systems of varying characteristics. Differences in water and electrolyte ingress could be monitored, as well as metal corrosion, polymer swelling and delamination.</p>
1367

Enzymes as catalysts in synthesis of enantiomerically pure building blocks : secondary alcohols bearing two vicinal stereocenters

Liu, Rong January 2005 (has links)
<p>Enzymes as tools in organic synthesis have provided enormous advantages. This thesis deals with the applications of enzymes in the kinetic resolutions of racemic compounds. The stereochemistry of chiral compounds and the kinetics of α/β hydrolase lipases are presented. From a practical point of view, the handling of a large number of parameters that influences the kinetic resolutions, especially enantioselectivity (E-value) are systematically described. A variety of approaches employed for raising the yields to over 50% are additionally discussed.</p><p>Methods for the preparation of synthetically useful chiral building blocks were developed in this thesis. Thus, resolution of secondary alcohols bearing two vicinal stereocentres are studied. These building blocks can serve as starting materials for the synthesis of various enantiomerically pure compounds for agrochemistry, pharmaceuticals, chemical industry, and particularly for the total synthesis of pheromones.</p><p>Racemic 3-substitued 2-hydroxybutane derivatives were produced in fairly high diastereomeric purities by a variety of chemical approaches, such as epimerization, metal-catalysed asymmetric addition etc. Kinetic resolution of these racemates was achieved by enzyme-catalysed reactions. Two lipases, Candida antarctica lipase B and Pseudomonas cepacia lipase were found to be useful in acylations as well as hydrolyses. In the biotransformations studied, the presence and nature of the second vicinal stereocentre in the chiral secondary alcohols investigated seemed to be important, e.g. in terms of the efficiencies of sequential kinetic resolutions, and altering the selectivities as well.</p>
1368

Quantitative in situ analysis of initial atmospheric corrosion of copper induced by carboxylic acids

Gil, Harveth January 2007 (has links)
<p>The interaction of carboxylic acids with copper is a phenomenon found both outdoors and, more commonly, indoors. The influence on copper of some carboxylic acids (formic, acetic, propionic, and butyric) have so far been studied at concentrations levels at least three or four orders of magnitude higher than actual indoor conditions (< 20 ppb, volume parts per billion), and with only limited emphasis on any mechanistic approach. In this licentiate study a unique analytical setup has been successfully applied for <i>in situ </i>characterization and quantification of corrosion products formed during initial atmospheric corrosion of copper in the presence of acetic, formic or propionic acid. The setup is based on monitoring mass changes by the quartz crystal microbalance (QCM) and simultaneously identifying the chemical species by infrared reflection-absorption spectroscopy (IRAS). Post-analysis of corrosion products was performed by coulometric reduction (mass of copper (I) oxide formed), grazing incidence x-ray diffraction (phase identification) and atomic force microscopy (surface topography).</p><p>The absolute amounts of mass of individual constituents in the corrosion products, mainly copper (I) oxide or cuprite, copper (II) carboxylate and water or hydroxyl groups, have been deduced<i> in situ</i> during exposure in 120 ppb of carboxylic acid concentration, 95% relative humidity and 20ºC. An overall result is the consistency of analytical information obtained. For copper (I) oxide the quantified data estimated from IRAS, QCM or coulomeric reduction agrees with a relative accuracy of 12 % or better.</p><p>The interaction of copper with the carboxylic acids seems to follow two spatially separated main pathways. A proton-induced dissolution of cuprous ions followed by the formation of copper (I) oxide, and a carboxylate-induced dissolution followed by the formation of copper (II) carboxylate. The first pathway is initially very fast but levels off with a more uniform growth over the surface. This pathway dominates in acetic acid. The second pathway exhibits a more constant growth rate and localized growth, and dominates in formic acid. Propionic acid exhibits low rates for both pathways. The difference between the carboxylic acids with respect to both total corrosion rate and carboxylate-induced dissolution can be attributed to differences in acid dissociation constant and deposition velocity.</p>
1369

Synthesis of Polyhydroxylated Surfactants : Comparison of Surfactant Stereoisomers and Investigation of Haemolytic Activity

Neimert-Andersson, Kristina January 2005 (has links)
<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>
1370

Study of Electrochemical Behaviour and Corrosion Resistance of Materials for Pacemaker Lead Applications

Örnberg, Andreas January 2007 (has links)
<p>For patients suffering bradycardia, i.e., too slow heart rhythm, the common treatment is having a pacemaker implanted. The pacemaker system consists of the pacemaker and a pacing lead. The pacing lead is connected to the pacemaker and at the other end there is a stimulation electrode. The most common conductor material is a cobalt-based super alloy (MP35N<sup>®</sup> or 35N LT<sup>®</sup>), with the main constituents Ni, Co, Cr and Mo. The pacemaker electrode is often made of a substrate material with a rough surface coating. The substrate materials are predominantly platinum/iridium alloy and titanium. The material choice is of great importance for the performance and stability during long-term service. Excellent corrosion resistance is required to minimize elution of metal ions in the human body.</p><p>In this thesis, the electrochemical behaviour and corrosion resistance of the Co-based alloys and Ta (as electrode substrate), in a phosphate buffer saline (PBS) solution with and without addition of H<sub>2</sub>O<sub>2</sub>, was investigated by means of potentiodynamic polarization, cyclic voltammetry, electrochemical impedance spectroscopy and simulated pacemaker pulsing. The metal release from the Co-based alloy during the passivation treatment and exposure in the synthetic biological media was measured by using inductive coupled plasma - atomic emission spectroscopy (ICP-AES). Moreover, surface composition was analyzed by using x-ray photoelectron spectroscopy.</p><p>The results show that the chemical passivation of Co-based alloy 35N LT<sup>®</sup> increased the corrosion resistance and reduced Co release significantly, even in more hostile environment, i.e. PBS with addition of H<sub>2</sub>O<sub>2</sub>. The increased corrosion resistance is due to the Cr enrichment in the surface layer. The reduced Co release is due to a preferential dissolution of Co from the surface oxide layer during the chemical passivation. The electrochemical investigation of uncoated and rough TiN coated Ta show that uncoated Ta is not suitable electrode material due to formation of a highly resistive surface oxide film. Whereas the rough TiN coated Ta exhibits desirable electrochemical performance for pacemaker electrodes. The addition of H<sub>2</sub>O<sub>2 </sub>in the PBS has a large influence on the electrochemical behaviour of Ta, but the influence is small on the rough TiN coated Ta. </p>

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